JP4196896B2 - Electronics - Google Patents

Description

  The present invention relates to a structure and a configuration of a reflective bright display element and an electronic device used for a meter panel of a wristwatch, an automobile, an electronic notebook, an information device terminal such as a computer or a television, or a display part of an information bulletin board.

In addition to digital watches equipped with hands-type analog watches and liquid crystal display elements in wrist watches, recently, a variety of information is displayed, so hybrid watches equipped with small liquid crystal windows, and the surface of hands-type analog watches. A two-layer timepiece in which a liquid crystal display element is stacked on top of each other has been developed.
JP 54-94940 JP 54-136718 A JP 55-26986 A JP 55-46845 A JP 55-188786 JP 5623024 JP 56-65618

In addition, in the field of watches and electronic notebooks, multifunctional models equipped with various functions are being developed. Development of a novel display element that can be used as a new watch face even in such applications is awaited.

  Further, in a display unit of a special-purpose electronic device, for example, an automobile meter panel, it is necessary to display a wide variety of information in a limited space. The car's instrument panel had to choose between analog and digital models.

  Further, in the field of information equipment including watches, miniaturization and portability have progressed, and power consumption is also required for display devices mounted thereon. In such a portable information display device or information processing device, a battery is generally used. Therefore, the life of the battery is an extremely important factor in using the device. For this reason, recently, devices combining solar cells are being developed. For example, in Japanese Patent Publication No. 3-61930, a liquid crystal display element and a solar cell are overlapped to save the space of the apparatus. Japanese Patent Application Laid-Open No. 63-106725 discloses a configuration in which a solar cell is disposed around a liquid crystal display element, and an example in which a display element in which liquid crystals are dispersed in a polymer form in a polymer is used as the liquid crystal display element at this time. Presenting.

  On the other hand, a bright reflective display element that solves such a problem or does not use a polarizing plate suitable for these uses is being developed. For example, a mode that is transparent when an electric field is applied and scatters when no electric field is applied (PDLC, abbreviated as JP-B-58-501631), a light that is scattered when an electric field is applied, and light absorption or transparency when no electric field is applied (abbreviated as reverse PDLC, gel JP-A-4-227684 has been developed as a network type, JP-A-5-119302 etc. as a particle orientation dispersion type, and US Pat. No. 4,994,204 etc. as a liquid crystal droplet dispersion type. In order to increase the refractive index anisotropy of the liquid crystal or polymer to be used and improve the scattering degree, a liquid crystal or polymer having a terphenyl skeleton or a terphenyl skeleton containing a hetero atom is used.

  However, in the conventional hybrid timepiece, it is necessary to provide an analog display unit and a digital display unit separately, so that the display area of each is reduced, and there is a problem that visibility is lowered. Further, since the digital display portion is a twisted nematic type using a polarizing plate, the display is dark and the visibility is further lowered. Furthermore, it has been extremely difficult to combine a solar cell with such a hybrid watch due to its area constraints. In order to solve such a problem, a configuration in which a solar cell and a liquid crystal display element are used in a hybrid timepiece or an electronic computer is established as a patent, but the transmittance of the liquid crystal display element combined with the solar cell is high. Because it is bad (transmittance is 30% or less for twisted nematic type using polarizing plate, 60% or less for transmission using guest-host type liquid crystal), the power generation efficiency is reduced, and the display mode is solar as the background. When a dark reflective plate such as a battery is used, there are problems such as extremely low visibility. In addition, when a liquid crystal display element using a dynamic scattering effect and a solar cell are stacked, the display principle involves ionic flow, so that power consumption is large and it is difficult to combine the solar cell with a solar cell.

  In addition, in the display section of special-purpose electronic devices such as in-vehicle meter panels, both analog display and digital display may be incorporated in a limited space. In such a case, it is necessary to increase the display space. It was.

  Recently, car navigation systems, in-vehicle TVs, and videos have become widespread, but the display is usually near the center console box, and it is necessary to turn the line of sight toward the passenger seat each time the display is viewed.

  In addition, conventional vehicle-mounted meter panels are self-luminous or pack-light type, and thus have a drawback that they are extremely difficult to see in the daytime when the surroundings are bright. Some users want to choose analog or digital instrument panels according to their mood.

  In addition, in conventional PDLC and reverse PDLC, a compound having fluorescence in the visible region such as a terphenyl skeleton was used in order to increase the refractive index anisotropy, and because of a mismatch between the refractive index of the liquid crystal and the polymer, it was transparent. Fluorescence and haze are conspicuous in the state, so that a good transparent state cannot be obtained and the display contrast is lowered. For example, in PDLC, the transparency when a voltage is applied is lowered, and when a light absorbing layer is arranged in the background, the background color appears cloudy due to the fluorescence and haze of the liquid crystal layer.

  Further, in the case of reverse PDLC, due to the fluorescence and haze of the liquid crystal layer, there is a problem that the transparency when no voltage is applied is lowered, and the background color appears cloudy when the light absorption layer is disposed on the background.

 Even in a reverse PDLC in which a dichroic dye is mixed in a liquid crystal and a light reflecting layer is arranged in the background, the colored state due to the dichroic dye when no electric field is applied appears to be turbid due to the fluorescence or haze emitted from the liquid crystal, resulting in a contrast. It has the problem of decreasing.

  In addition, in the conventional technology, a low molecular chiral component is included in the liquid crystal in order to improve the degree of scattering, and in the manufacturing process, the polymer precursor in the liquid crystal is polymerized to contain the low molecular chiral component in the liquid crystal. As the ratio increases, the chiral pitch in the liquid crystal becomes shorter, causing a mismatch between the twist structure of the polymer in the initial stage of polymerization and the twist structure in the liquid crystal after polymerization, causing haze in a transparent state when no electric field is applied. Had. Furthermore, such a chiral pitch due to a low molecular chiral component has temperature characteristics and causes haze.

  Such haze is a serious problem in the mode of switching between transparent and scattering that does not contain a dichroic dye. For example, when used as a watch cover glass or a dial, the haze in the transparent state of the display element has a commercial value. Reduce significantly. In addition, in the case of a structure containing a dichroic dye and having a reflective layer disposed on the back surface, the display element is in a mode for switching between light absorption and light scattering. In this case as well, the fluorescence and haze in the light absorption state are , Reduce the contrast.

  Therefore, the present invention solves such problems, and the object of the present invention is to make the brightness of the scattering state higher than the conventional level in PDLC and reverse PDLC, to suppress the fluorescence and haze in the transparent state, and to improve the contrast. It is to provide a display element that can improve the reliability by using a highly reliable liquid crystal and polymer, and can respond to various uses using an active element or a color filter. In addition to providing an electronic device with low power consumption and completely new value in combination with an optional display device or an electronic device equipped with a solar cell, it is also possible to provide a technology for improving visibility at that time Objective.

The present invention relates to a display in which a liquid crystal-polymer layer in which liquid crystal and polymer are phase-separated is enclosed between a display portion and a pair of substrates that are arranged to overlap the display portion and have electrodes facing each other. An element and a high refractive index layer having a refractive index of 1.8 or more disposed in a lower layer of the display element.

  With such a configuration, display can be performed by being superimposed on the display unit by the display device. Furthermore, the display brightness can be improved by arranging the high refractive index layers in an overlapping manner.

In the present invention, the high refractive index layer is disposed between the display element and the display portion.

The display unit may be disposed on the side opposite to the side on which the high refractive index layer is disposed with respect to the display element.

  Further, the liquid crystal-polymer layer is characterized in that a light transmission state and a light scattering state are controlled according to an applied voltage.

Further, when no voltage is applied to the liquid crystal-polymer layer, the display element is controlled to transmit light, and when a voltage is applied to the liquid crystal-polymer layer, the display element is controlled to light scattering. It is characterized by being.

  The high refractive index layer is an ITO layer.

The surface of the substrate opposite to the side where the high refractive index layer of the display element is disposed is subjected to non-glare treatment and / or anti-reflection treatment.

In addition, a color filter is formed on a surface of at least one of the pair of substrates facing the liquid crystal.

Further, an active element is formed on a surface of at least one of the pair of substrates facing the liquid crystal.

Further, an active element is formed on a surface of at least one of the pair of substrates facing the liquid crystal.

（ｎは整数、 Ｒはアルキル基またはアルコキシ基またはシクロアルキル基またはシクロアルコキシ基、Ｒ１、Ｒ２は独立でアルキル基またはシクロアルキル基またはアルコキシ基またはシクロアルコキシ基またはＨまたはＦ、ＸはＨまたはＦまたはＣ１またはＣＮ）なる化合物を含むことを特徴とする。

また、前記表示素子に用いる前記高分子が

（Ｒ、Ｒ’はそれそれ独立でＨ、またはＣＨ３である。Ｂ、Ｂ’、Ｂ”はそれぞれ独立で、ＯＣＯ、ＣＯＯ、ＯＣＯＮＨ、ＮＨＣＯＯ、ＣＯＮＨ、ＮＨＣＯ、−Ｃ＝Ｃ−、各種アルキル、Ｏ、Ｎ、Ｓの中から選ばれる。Ａ１、Ａ２はそれそれ独立で芳香環を含む。例えばフェニル、ビフェニル、ターフェニル、クォーターフェニル、ナフタレン、アントラセンなどであり、１部ハロゲン、アルキル基、シアノ基などで置換されていてもよい。）なる高分子前駆体を少なくとも１成分として重合して成ることを特徴とする。
In the liquid crystal used for the display element,

(N is an integer, R is an alkyl group, an alkoxy group, a cycloalkyl group or a cycloalkoxy group, R1 and R2 are independently an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, H or F, and X is an H or F group. Or C1 or CN).

The polymer used for the display element is

(R and R ′ are each independently H or CH 3. B, B ′ and B ″ are each independently OCO, COO, OCONH, NHCOO, CONH, NHCO, —C═C—, various alkyls, Selected from O, N, and S. A1 and A2 each independently contain an aromatic ring, such as phenyl, biphenyl, terphenyl, quarterphenyl, naphthalene, anthracene, etc. 1 part halogen, alkyl group, cyano It may be substituted with a group or the like.) The polymer precursor is polymerized as at least one component.

  In order to describe the present invention in more detail, this will be described with reference to lacquered drawings. According to the configuration of the present invention, by adding an appropriate amount of dichroic dye in reverse PDLC, or by using a liquid crystal or polymer having a small fluorescence quantum yield, the turbidity of display when no electric field is applied is made inconspicuous. Is possible.

  The amount of dichroic dye added varies depending on the application to be used, and when it is necessary to be transparent when no electric field is applied and when it is desired to reduce haze, for example, when a solar cell or other display device is disposed on the back surface. When the pigment is mixed so that the light absorptivity of the display element of the present invention is 1% to 20%, preferably about 5% to 10%, the haze becomes inconspicuous and the transparency is not impaired. In the case where a reflective layer is disposed on the back surface of the display element and light absorption is mainly performed when no electric field is applied, a contrast can be obtained by mixing a dichroic dye so that the light absorption rate of the display element is 20% or more. Becomes better.

  By using a liquid crystal or a polymer having a small fluorescence quantum yield, the turbidity of display when no electric field is applied can be reduced. As a specific structure, it is preferable to use a liquid crystal having a skeleton having a fluorescence quantum yield of approximately 0.3 or less, or a polymer precursor such as tolan or hyphenyl. When a compound having a fluorescence quantum yield of 0.3 or more, such as a terphenyl skeleton, is used as a liquid crystal or a polymer precursor, fluorescence is observed in a display state without an electric field, and the contrast is lowered.

  Also, in the reverse PDLC manufacturing process, the polymer precursor in the liquid crystal is polymerized and polymerized to increase the content ratio of the low molecular chiral component in the liquid crystal, while the chiral polymer precursor in the liquid crystal is increased. Is incorporated into the polymer and the content ratio in the liquid crystal is reduced, so that the content ratio of the chiral component in the liquid crystal is kept constant even when the polymerization proceeds, and the chiral pitch is also kept constant. For this reason, the twist structure of the polymer in the initial stage of polymerization coincides with the twist structure in the liquid crystal after polymerization, and the haze in the transparent state when no electric field is applied becomes extremely small.

  In addition, when a chiral component with little change in the temperature of the chiral pitch is used, after the reverse PDLC is manufactured, the alignment state of the liquid crystal becomes difficult to change in temperature, so that the occurrence of haze due to the change in temperature can be prevented. In this case, in the temperature dependence of the chiral pitch, it is preferable that the change in the chiral pitch is 20% or less in the operating temperature range.

  Further, since reverse PDLC is almost transparent when no electric field is applied, when this display element is arranged on the surface of an arbitrary display device, the display of the display device that is truly arranged can be seen. When an electric field is applied to the reverse PDLC in the table, a display on the display device arranged below and a white display due to light scattering can be simultaneously seen (FIG. 10).

  If a reflective layer, especially a transparent layer with a high refractive index, is placed between the display device placed below and the reverse PDLC placed above, light incident on the display device from the surroundings efficiently enters the reverse PDLC. It looks bright and contrasts (Fig. 12). Since the light incident from the front is not reflected so much, the display on the back side can be read. This can be well understood by referring to FIG. 18 showing the incident angle dependence of the reflectance when light is incident on a flat substrate surface. FIG. 18 shows the calculation result by the Fresnel formula when the layer folding ratio of the substrate is 2 and the substrate is in contact with air (refractive index 1). It is calculated by decomposing natural light into two orthogonal polarizations. Since the reflective layer is transparent, the display device disposed below does not become difficult to see. Of course, the same display can be realized even if these display elements are multilayered.

  In addition, by disposing a liquid crystal layer containing a dichroic dye sandwiched between two electrodes between the display device disposed below and the reverse PDLC disposed above, it is desirable to make the display element on the front side easier to see. In some cases, the electric field can be controlled so that the liquid crystal layer containing the dichroic dye is in a light-absorbing state so that the display by light scattering can be lifted (see FIG. 9). Of course, the display can be more easily seen by inserting a high refractive layer (see FIG. 8). A normal PDLC may be used instead of the reverse PDLC used at this time. In order to make the display device on the back side easier to see, the electric field is controlled in the reverse direction to make the layer containing the dichroic dye transparent.

  Further, since the reverse PDLC according to the present invention is transparent under no electric field, even if this display element is arranged on the surface of the solar cell, the power generation efficiency of the solar cell is hardly impaired. Since a solar cell and a display element can be overlapped, an electronic device using this display element can be saved in space, the device can be reduced in size, and the degree of freedom in design is improved.

  In the above configuration, when an active element or a color filter is formed on at least one substrate used for reverse PDLC, the display capacity can be further increased and color can be achieved. When used as a display of a recently developed car navigation system, it is extremely safe to drive because it can read a map with its face facing forward. Of course, it is also possible to display on a television or the like. When used for an electronic notebook or the like, it is possible to realize a small high-performance electronic notebook that is unrelated to battery consumption.

  Further, in the above configuration, when the surface substrate is subjected to non-reflection treatment or non-glare treatment, the visibility is greatly improved.

In this embodiment, an example is shown in which a dichroic dye is slightly mixed in order to make the haze of reverse PDLC inconspicuous. In particular, the liquid crystal composition used in Examples 2 to 4 will be described. 99.25% by weight of a 7: 3 mixture of TL202 and BL007 manufactured by Merck as liquid crystal, 0.25% by weight of G470 (manufactured by Nippon Photosensitivity Laboratories) as a dichroic dye, SI512 (manufactured by Mitsui Toatsu Dye) Of 0.1% by weight and 0.1% by weight of MIM137 (Mitsui Toatsu Dye Co., Ltd.) were mixed to obtain a guest-host liquid crystal. Furthermore, 2% by weight of CN617 manufactured by Asahi Denka Co., Ltd. as a chiral component was mixed with 98% by weight of the liquid crystal to obtain a chiral guest host liquid crystal.

などの化合物を含む液晶を用いることができる。ここでＲはアルキル基、シクロアルキル基、アルコキシ基またはシクロアルコキシ基、 Ｒ１はアルキル基、アルコキシ基、水素またはフツ素、Ｘはシアノ基、ハロゲン基、水素またはニトロ基、ｎは整数である。またこのほか液晶としては誘電異方性が負のものも用いることができる。この時、基板表面に施す配向処理は垂直配向処理とすることが望ましい。 As the skeleton of the liquid crystal, it is necessary to use a highly reliable one when combining a display element with an active element. Use it. In addition, RDP80616, RDP80616, RDP10248, etc. manufactured by Rodic Co., SS5004 manufactured by Chisso Co., Ltd., and BL007 manufactured by Merck Co., Ltd. can be used as the high birefringent liquid crystal. In other applications, a liquid crystal having any skeleton that satisfies the drive voltage and birefringence may be used. Specific examples of liquid crystal compounds include

A liquid crystal containing a compound such as can be used. Here, R is an alkyl group, cycloalkyl group, alkoxy group or cycloalkoxy group, R1 is an alkyl group, alkoxy group, hydrogen or fluorine, X is a cyano group, halogen group, hydrogen or nitro group, and n is an integer. In addition, liquid crystal having negative dielectric anisotropy can be used. At this time, the alignment treatment applied to the substrate surface is preferably a vertical alignment treatment.

  Any dichroic dye may be used as long as it exhibits dichroism. From the viewpoint of light resistance, anthraquinone, naphthoquinone, and perylene are used as shown in the present example. Are preferred. Further, for the purpose of reducing haze, a dark color tone is preferable, and those having a small fluorescence quantum yield are preferable. About the amount to mix, when using a solar cell for a back surface, it is good to add the minimum dichroic dye which suppresses haze in order not to reduce electric power generation efficiency. Since the size of the haze depends on the liquid crystal, polymer precursor, chiral component, and polymerization condition building to be used, the concentration of the dichroic dye is adjusted according to the actual situation.

  As the chiral component to be used, an appropriate amount of a component capable of twisting the alignment of liquid crystal may be used. Desirably, the orientation of the liquid crystal layer is twisted by 90 ° or more, more preferably 270 ° or more in the thickness direction of the face crystal layer. As the chiral agent to be used, for example, S811, R811, S1011, R1011, CB15, C15, CE2, etc. manufactured by Merck Corporation, CM series manufactured by Chisso Corporation, CNL series manufactured by Asahi Denka Co., Ltd. and the like can be used.

などを用いることができる。ここでＲ、Ｒ’はそれそれ独立でＨ、またはＣＨ３である。Ｂ、Ｂ’、Ｂ”はそれそれ独立で、 ＯＣＯ、ＣＯＯ、ＯＣＯＮＨ、ＮＨＣＯＯ、ＣＯＮＨ、ＮＨＣＯ、−Ｃ≡Ｃ−、各種アルキル、Ｏ、Ｎ、Ｓの中から選ばれる。Ａ１、Ａ２はそれぞれ独立で芳香環を含む。例えばフェニル、ヒフェニル、ターフェニル、クォーターフェニル、ナフタレン、アントラセンなどであり、１部ハロゲン、アルキル基、シアノ基などで置換されていてもよい。 As the polymer precursor used by mixing with the liquid crystal shown here, any polymer precursor that can be polymerized by light, electron beam, heat or the like and has a mesogen having a large post-refractive property can be used. For example, acrylate, methacrylate, crotonate, cinnamate, epoxy, and the like can be used for the polymerization portion, and phenyl, piphenyl, terphenyl, quarterphenyl, and the like can be used for the mesogen portion. In order to improve post-refractive properties and compatibility, an appropriate substituent may be introduced. In particular, in the precursor in which the polymer part and the mesogen part are directly bonded, the formed polymer tends to be in the form of particles. The polymer part and the mesogen part are connected by a spacer such as an alkyl chain or polymerized in one molecule. In the case of a precursor having a plurality of parts, the polymer formed tends to be in a gel network form. As an example of the former

Etc. can be used. Here, R and R ′ are each independently H or CH 3. B, B ′ and B ″ are each independently selected from OCO, COO, OCONH, NHCOO, CONH, NHCO, —C≡C—, various alkyls, O, N and S. A1 and A2 are respectively selected. Independently contains an aromatic ring, such as phenyl, hyphenyl, terphenyl, quarterphenyl, naphthalene, anthracene, etc., which may be substituted with 1 part halogen, alkyl group, cyano group and the like.

Examples of the latter include bifunctional monomers among the monomers listed above, and those having a structure in which a spacer such as an alkyl group is inserted between the polymerization portion and the mesogen portion. Commercially available products include C6H manufactured by Philips, Aronix and Reseda Macromonomer manufactured by Toa Gosei Co., Ltd., KAYARAD and KAYAER manufactured by Nippon Kayaku Co., Ltd., Nobcommer manufactured by Sannobuco, SICOMET and Photomer, Epototo manufactured by Tohto Kasei Co., Ltd. , Toblen and Dappo Tote, Shrimp Coat from Yuka Shell, Adeka Resin from Asahi Denka, Adekaoptomer and Adeka Opton, 2200 Series from ThreeBond, Riboxy and Spirak from Showa Polymer Co., Ltd., Nippon Polyurethane products, etc. be able to. One part of these monomers may be mixed and used in the former (an example in which the polymer is in the form of particles). A thermoplastic polymer such as ethyl cellulose can also be used as the other polymer.
(Comparative Example 1)

  The liquid crystal composition shown in Example 1 was prepared without a dichroic dye. Other material conditions are the same as those in the first embodiment.

  In this example, a polymer particle dispersion type reverse PDLC is produced using the liquid crystal composition produced in Example 1 and the haze thereof is examined.

A liquid crystal mixture using 7% by weight of hyphenyl methacrylate as the polymer precursor shown in Example 1 with respect to the liquid crystal was sealed in the empty panel shown in FIG. First, a method for manufacturing an empty panel will be described. After forming the transparent electrode 2 on the substrate 1, the surface of the electrode 2 was subjected to orientation treatment. Next, a TFT element was formed as an active element on the substrate 8. Specifically, aluminum was evaporated as the gate electrode 15, the gate insulating layer 18, the semiconductor layer 16, the source electrode 14, the drain electrode 17, and the reflective electrode 7. Further, the electrode surface was subjected to orientation treatment. These two substrates were bonded to each other while keeping the gap of 5 μm with the electrode surface inside. Although the thickness of the liquid crystal layer is 5 μm, it may be optimized between 3 μm and 10 μm according to the application. The liquid crystal / polymer precursor mixed layer was irradiated with ultraviolet rays having a wavelength of 300 nm to 400 nm and an intensity of 3.5 mW / cm ² in a liquid crystal phase to precipitate polymer particles from the liquid crystal. A solar cell was disposed as a light-absorbing reflector on the back surface of the display element, and the surface was subjected to non-glare treatment and anti-reflection treatment. Of course, such a process does not need to be performed, and only one of them can sufficiently improve the visibility.

  When a drive voltage of 5 V is applied to the liquid crystal / polymer layer of the display element thus fabricated, light is incident from a direction inclined by 20 degrees from the normal of the display element surface, and the reflected light intensity in the normal direction is measured In addition, it was 30% brighter than white paper. Further, the reflectivity in the black display state was measured with a drive voltage of 0 V, and it was 4%.

  As for the alignment treatment, a polyimide alignment film is formed and the surface thereof is rubbed here, but another alignment film may be formed and subjected to a lapin process. Further, rubbing may be performed without forming an alignment film. An LB film or an oblique deposition film may be used.

  The light-absorbing reflector disposed on the back surface may not be a solar cell. It is also desirable that the surface of the light absorbing plate is subjected to electroreflection treatment. Moreover, it may not be a light absorptive reflector. For example, a reflector such as aluminum or chrome may be used. When a reflective plate having a high reflectance is used, the visibility can be improved by increasing the amount of the dichroic dye added.

  If a color filter is formed on the substrate, color display can be performed. In this case, the color used for the color filter is not limited to a combination of colors that can reproduce a full color, and a color with good visibility may be selected according to the application. A color filter material having no absorption in the ultraviolet region is preferred.

  In this embodiment, the display element surface is subjected to non-glare treatment and anti-reflection treatment. However, it is not always necessary to perform these treatments, and display can be performed without performing these treatments.

  In small and medium capacity applications such as watches, sufficient information can be displayed without forming active elements.

As the active element, a TFT element having another configuration, a transistor, an MIM element, a ferroelectric element, or the like can be used in addition to the TFT element shown here. In addition to glass, a substrate on which these active elements are formed can be made of a semiconductor such as silicon, gallium arsenide, or germanium, or an inorganic material such as an inorganic material or plastic. When a semiconductor is used as the substrate, a driver and a controller for driving can all be formed in the substrate, so that a display device can be manufactured at a very low cost.
(Comparative Example 2)

  In Example 2, the material of Comparative Example 1 was used as the liquid crystal composition. At this time, when the electro-optical characteristics were measured by the same measurement method as in Example 2, a brightness of 35% was obtained as compared with white paper when an electric field was applied. The reflectance when no electric field was applied was 8%.

  In this example, an example in which a polymer gel network alignment type liquid crystal display element was produced using the liquid crystal composition of Example 1 and its haze was examined is shown.

  The liquid crystal composition of Example 1, 5% by weight of M6200 manufactured by Toagosei Co., Ltd. as the polymer precursor, and 2% by weight of Irgacure 184 as the photopolymerization initiator were used. Other than that, a display element was fabricated in the same manner as in Example 2.

  When a drive voltage of 10 V is applied to the liquid crystal / polymer layer of the display element thus created, light is incident from a direction inclined by 20 degrees from the normal of the display element surface, and the reflected light intensity in the normal direction is measured In addition, the brightness of white paper was 28%. Further, the reflectivity in the black display state when no voltage was applied was 3%.

  As the polymer precursor to be used, a cheap one can be used that forms the gel network shown in Example 1.

The other conditions are the same as in Example 2.
(Comparative Example 3)

  A display element having the structure of Example 3 was prepared using the liquid crystal composition of Comparative Example 1, and the reflectance in a similar white display state was measured. When measured in the black display state, the reflectance was 5%. Met.

  In this example, a display element in which liquid crystal droplets are aligned and dispersed in a polymer using the liquid crystal composition of Example 1 and its haze is examined is shown.

  In the liquid crystal polymer precursor mixture of Example 1, 30% by weight of M6200 manufactured by Toagosei Chemical Co., Ltd. was used as the polymer precursor, and 2% by weight of Irgacure 184 was used as the photopolymerization initiator. Other than that, a display element was fabricated in the same manner as in Example 2.

  When a drive voltage of 20 V is applied to the liquid crystal / polymer layer of the display device thus fabricated, light is incident from a direction inclined by 20 degrees from the normal of the display device surface, and the reflected light intensity in the normal direction is measured In addition, the brightness of white paper was 28%. Further, the reflectance in the black display state when no voltage was applied was 10%.

  As the polymer precursor to be used, a cheap one can be used that forms the gel network shown in Example 1.

The other conditions are the same as in Example 2.
(Comparative Example 4)

  Using the liquid crystal composition of Comparative Example 1, a display device having the structure of Example 4 was prepared, and the reflectance in the same white display state was measured to be 33%. The reflectance in the black display state was measured to be 15%. Met.

  In the present embodiment, an example using a tolan type liquid crystal and a tolan type polymer in reverse PDLC is shown. FIG. 2 shows a simple sectional view of a part of the display element of this embodiment.

  First, a panel for encapsulating a liquid crystal / polymer precursor will be described. A transparent electrode having a desired pattern was formed on the substrate, and a lapink treatment was further applied to the surface thereof. The periphery of the two substrates was fixed with a gap of 4 μm with the electrode surface inside.

（Ｒ、Ｒ'は炭素数１から１２までのアルキル基）
化合物群II

（Ｒ, Ｒ'は炭素数１から１２までのアルキル基）
化合物群III

（Ｒは炭素数１から１２までのアルキル基、Ａｒはフェニル、ビリジン、ピリミジンを示し、ＸはＦまたはＨを示す）
をそれぞれ４７重量％：３３重量％：２０重量％で混合した物を用いた。各化合物群のアルキル基の炭素数については化合物群Ｉでは
（Ｒ＝１、Ｒ' ＝１１）２％
（Ｒ＝３、Ｒ' ＝２）８％
（Ｒ＝４、Ｒ' ＝１）８％
（Ｒ＝４、Ｒ' ＝２）９％
（Ｒ＝４、Ｒ' ＝３）５％
（Ｒ＝５、Ｒ' ＝１）８％
（Ｒ＝５、Ｒ’＝３）５％
（Ｒ＝５、Ｒ' ＝１１）２％
化合物群IIでは
（Ｒ＝３、Ｒ' ＝２）２１％
（Ｒ＝４、Ｒ' ＝２）１２％
化合物群IIIでは
（Ｒ＝４）６％
（Ｒ＝５）７％
（Ｒ＝７）７％
なる化合物を混合して用いた。ここではアルキル基として直鎖の物を用いたが、これに限らず分岐のあるアルキル基でも用いることができる。この液晶９８.５重量％にカイラル成分としてメルク社製Ｒ１０１１を１. ５重量％混合した。更にこのカイラル液晶９５重量％に高分子前駆体として

をそれぞれ３. ３重量％：１．７重量％混合して液晶／高分子前駆体混合物とした。 Next, the liquid crystal and polymer precursor sealed in this panel will be described. First, the liquid crystal is a tolanic liquid crystal compound group I.

(R and R ′ are alkyl groups having 1 to 12 carbon atoms)
Compound group II

(R and R ′ are alkyl groups having 1 to 12 carbon atoms)
Compound group III

(R represents an alkyl group having 1 to 12 carbon atoms, Ar represents phenyl, pyridine, or pyrimidine, and X represents F or H)
Were mixed at 47% by weight: 33% by weight: 20% by weight, respectively. Regarding the number of carbon atoms of the alkyl group of each compound group, in the compound group I (R = 1, R ′ = 11) 2%
(R = 3, R ′ = 2) 8%
(R = 4, R ′ = 1) 8%
(R = 4, R ′ = 2) 9%
(R = 4, R ′ = 3) 5%
(R = 5, R ′ = 1) 8%
(R = 5, R ′ = 3) 5%
(R = 5, R ′ = 11) 2%
In compound group II (R = 3, R ′ = 2) 21%
(R = 4, R ′ = 2) 12%
In compound group III (R = 4) 6%
(R = 5) 7%
(R = 7) 7%
The compound to be used was mixed and used. Here, a straight chain is used as the alkyl group, but not limited to this, a branched alkyl group can also be used. This liquid crystal 98.5% by weight was mixed with 1.5% by weight R1011 manufactured by Merck as a chiral component. Furthermore, 95% by weight of this chiral liquid crystal is used as a polymer precursor.

3.3 wt% and 1.7 wt% of each were mixed to obtain a liquid crystal / polymer precursor mixture.

The mixture thus obtained was then sealed in a vacuum in the panel shown above. Furthermore, in order to polymerize the polymer precursor, ultraviolet rays having a wavelength of 300 nm to 400 nm and an intensity of 3.5 mW / cm ² were irradiated for 10 minutes.

  A black light absorbing plate is disposed on the back surface of the display element thus manufactured, light is incident from a direction inclined by 20 degrees from the normal line of the display element surface, and the light reflected in the normal direction is detected and shown in FIG. The electro-optical characteristics shown are produced. The electro-optical characteristics of this example are indicated by solid lines. Since the transmittance was extremely high below the threshold voltage, black was reproduced by the light absorbing plate disposed on the back surface, and thus the contrast was 27.

  As the liquid crystal and polymer precursor to be used, the materials shown in Example 1 can be used. Among them, those having a low fluorescence quantum yield in the visible region and a large refractive index anisotropy are preferable. Tran, hyphenyl and the like are preferable as the skeleton. On the other hand, those having a high fluorescence quantum yield in the visible region, such as anthracene, terphenyl, quarterphenyl, and other linked phenyl groups, may be mentioned as undesirable ones. The combination and mixing ratio of R and R ′ alkyl groups in the compound group described above are not limited to this, and may be determined depending on the temperature range of the liquid crystal phase, the driving voltage, and the like. Further, other compounds may be mixed.

  The kind and the mixing amount of the chiral component are not limited to those shown here and the mixing amount, and those shown in Example 1 can be used and may be determined according to the application.

  The thickness of the liquid crystal / polymer layer may not be 4 μm and may be determined in accordance with the use within the range of 2 μm to 20 μm. As the thickness decreases, the transparency when no voltage is applied increases, but the scattering decreases. When the thickness is increased, the degree of scattering increases, but the driving voltage and turbidity when no voltage is applied increase.

As for the alignment treatment applied to the electrode surface, an alignment film may be provided to carry out a lapink treatment. The black absorption plate disposed on the back surface of the display element may be a solar cell or a reflective material.
(Comparative Example 5)

  A comparative example for Example 5 will be described. Here, as a liquid crystal containing a terphenyl skeleton compound, a mixture of 80% by weight of TL202 manufactured by Merck Co., Ltd. and 20% by weight of 4-cyano 14 ″ -pentylaphenyl (T15) was used. This liquid crystal composition was 95% by weight. % Of the polymer precursor 4-even-phenylmethacrylate and terphenyl-4,4 "-dimethacrylate were mixed with 3.3 wt% and 1.7 wt%, respectively. Other conditions were the same as in Example 5.

  The electro-optical characteristics of the display element thus manufactured were measured by the same method as in Example 5, and indicated by a broken line in FIG. Although it is in a transparent state below the threshold voltage, since fluorescence is seen in the visible region, it can be seen that the black background color looks whitish and the contrast is reduced (approximately 3).

  In this example, an example is shown in which a tolan-based liquid crystal having no fluorescence in the visible light region and a terphenyl polymer precursor having fluorescence are used. The liquid crystal shown in Example 5 was used as the liquid crystal, and terphenyl methacrylate and terphenyl dimethacrylate were used as the polymer precursor. A display element was manufactured according to Example 5 with respect to other structural conditions.

  The electro-optical characteristics of the display element manufactured in this way are shown by a solid line in FIG. As compared with Example 5, it can be seen that the black display below the threshold voltage is slightly white and the contrast is lowered (contrast is about 12).

  In this embodiment, an example using a tolan polymer having no fluorescence in the visible light region and a terphenyl liquid crystal having fluorescence is shown. The liquid crystal shown in Comparative Example 5 was used as the liquid crystal, and the Tolan series shown in Example 5 was used as the polymer precursor. A display element was manufactured according to Example 5 with respect to other structural conditions.

  The electro-optical characteristics of the display element thus manufactured are indicated by broken lines in FIG. Compared to Example 5, it can be seen that the black display below the threshold voltage is slightly white and the contrast is lowered (contrast is about 6).

を用いた。実施例５と同様にして素子を作製し、電気光学特性を測定した（図５中の実線参照）。 In this embodiment, an example in which a liquid crystal having a low fluorescence in the visible light region and a polymer precursor are used and the polymer has a gel network structure is shown. The liquid crystal used was the one shown in Example 5. The polymer precursor is Phillips C6H

Was used. An element was fabricated in the same manner as in Example 5, and the electro-optical characteristics were measured (see the solid line in FIG. 5).

  Any polymer precursor can be used as long as it forms a gel network structure upon polymerization. In particular, it is desirable for the chemical structure that is easy to take a gel network structure to have a structure in which two polymerized portions are bonded to each other via a long alkyl space. The bifunctional monomer in Example 1 is preferred.

The above embodiments can be similarly applied to other embodiments of the present invention.
(Comparative Example 6)

  In this comparative example, an example in which a liquid crystal having large fluorescence in the visible region is used in Example 8 is shown. The liquid crystal used is E7 made by Merck Co., Ltd. containing ventilator phenyl carbonitrile which emits fluorescence.

  A display element was produced in the same manner as in Example 8, and the electro-optical characteristics were measured and indicated by a broken line in FIG. It can be seen that the contrast of Example 8 is improved compared to this comparative example.

  In this embodiment, an example in which a dichroic dye is mixed in liquid crystal in Embodiment 5 and an electrode formed on a substrate is formed of a reflective material, that is, an example in which light is absorbed without application of an electric field will be described. An empty panel was prepared according to Example 2.

  After this panel gap was evacuated, M361: SI512: M137 (both manufactured by Mitsui Toatsu Dye Co., Ltd.) as a dichroic dye in the liquid crystal / polymer precursor mixture shown in Example 5 = 1.5: 1. 7: 0.43 (% by weight) was mixed and sealed. Further, the panel was irradiated with ultraviolet rays having a wavelength of 300 to 400 nm and an intensity of 3.5 mW / cm 2 at 40 ° C. for 10 minutes to polymerize the polymer precursor and precipitate a polymer from the liquid crystal.

  A display device using the display element of the present invention was completed by pasting a non-glare film subjected to antireflection treatment on the surface of the display element, and further arranging a light absorption layer on the back surface of the display element. By connecting a driver for driving, a controller, a power source for driving display elements, and a computer (none of which are shown) to this display device, a computer screen could be displayed. Of course, if you connect a TV tuner, you can watch TV.

  The dichroic dye used here is preferably an anthraquinone dye having good light resistance, and more preferably a dichroic dye having good dichroic ratio and solubility. Also, the mixing amount is considered so as to ensure a sufficient contrast.

  In this embodiment, the reflective layer placed on the back side of the liquid crystal / polymer layer is also used as the electrode. However, the reflective layer may be disposed on the back surface of the display element by making the electrode transparent.

  The substrate on which the active element is formed may be arranged on the front side or the back side of the liquid crystal / polymer layer.

  Non-glare processing and anti-reflection processing may be performed as necessary.

  In this example, the liquid crystal of Example 8 and a polymer precursor are used, and a dichroic dye is mixed and sealed in a panel having the configuration of Example 9. The liquid crystal and polymer used were those shown in Example 8. However, M361, SI512, and M34 manufactured by Mitsui Toatsu Dye Co., Ltd. were mixed as the dichroic dye with respect to 96.7% by weight of the liquid crystal 1.3: 1.6: 0.4 (% by weight). A liquid crystal / polymer precursor mixture was sealed in the panel produced in Example 9 and further irradiated with ultraviolet rays to produce a display element. A display device using the display element of the present invention was completed by pasting a non-glare film subjected to antireflection treatment on the surface of the display element, and further arranging a light absorption layer on the back surface of the display element. By connecting a driver for driving, a controller, a power source for driving display elements, and a computer (none of which are shown) to this display device, a computer screen could be displayed. Of course, you can watch TV by connecting to a TV tuner.

をそれそれ３.３重量％、１.７重量％、０.３重量％混合した。これを先の空パネルに封入して５０℃にて紫外線を照射した。この表示素子表面にノングレア処理または減反射処理を施してもよい。 In this embodiment, an example in which the haze reduction technology in the present invention is integrated will be shown. First, the liquid crystal will be described. As the liquid crystal, a liquid crystal having a small fluorescence in the visible light region, RDP806616-2 manufactured by Rodick and ML1009 manufactured by Merck was mixed at a ratio of 7: 3. As a dichroic dye, 470% by weight of G470 (manufactured by Nippon Photosensitive Laboratories), 0.4% by weight of SI512 (manufactured by Mitsui Toatsu Dye Co., Ltd.) and M137 (manufactured by Mitsui Toatsu Dye Co., Ltd.) A guest-host liquid crystal was prepared by mixing with 0.1 wt% liquid crystal. This was mixed with 2% by weight of CNL611 (manufactured by Asahi Denka Co., Ltd.) having a small temperature dependence of the chiral pitch to obtain a chiral guest host liquid crystal. In this liquid crystal, as a polymer precursor, ptylphenyltranmethacrylate and biphenyldimethacrylate as chiral polymer precursors

Were mixed with 3.3% by weight, 1.7% by weight and 0.3% by weight, respectively. This was enclosed in the previous empty panel and irradiated with ultraviolet rays at 50 ° C. The display element surface may be subjected to non-glare treatment or anti-reflection treatment.

  A solar cell was arranged on the back surface of the display element thus manufactured, and the reflectance when no electric field was applied was measured by the same method as in Example 2 as a reflective display element. The reflectivity was 1% at 20 ° C. Here, a segment display for a watch could be performed by applying an electric field. Moreover, a solar cell disposed on the back surface could be used as a liquid crystal driving power source.

  Although no active element is used here, the same effect can be obtained by using an active element. At that time, it is necessary to use a liquid crystal having a good retention rate as shown in Embodiment 1 as the liquid crystal. Bright color display is possible by combining color filters. When no active element is used, any material having a nematic liquid crystal phase can be used.

  The thickness of the liquid crystal / polymer layer is preferably 3 μm to 10 μm. If it is thinner than this, the scattering becomes thin, and if it is thicker than this, the driving voltage becomes high and the contrast is lowered, which is not practical.

  Instead of the solar cell arranged on the back surface of the display element, a light absorption layer and a light reflection layer may be arranged. Further, nothing can be arranged on the back surface of the display element, and display can be performed as white scattering on a transparent glass.

Other members, manufacturing conditions, and the like are the same as in Reference Example 1. The chiral component shown in Example 15 can also be used.
(Reference Example 1)

をそれぞれ６．８６重量％および０．１４重量％溶かして先に作製した空パネルに封入した。５０℃にてこのパネルに基板１側から紫外線（３００ｎｍ〜４００ｎｍ、３．５ｎＷ／ｃｍ²）を照射して液晶中の高分子前駆体を重合して表示装置とした。さらにこの表示素子の表面にノングレア処理及び減反射処理を施した。この処理はなくてもよい。 In this reference example, an example is shown in which a chiral polymer precursor is applied to a display device in which a display element in which a polymer is dispersed in the form of particles or particles in a dichroic dye-containing liquid crystal is combined with an active element. FIG. 6 shows a simple cross-sectional view of an empty panel in which MIM elements used in the display device of the present invention are formed. First, an empty panel enclosing liquid crystal / polymer is prepared. A transparent electrode 2 was formed on the substrate 1 and subjected to an alignment treatment. For the alignment treatment, a method usually used for a TN type liquid crystal display element can be used. Here, a polyimide alignment film is formed and the surface thereof is rubbed. Next, 480 × 640 MIM elements and reflective electrodes 7 were formed as active elements on the substrate 8 opposite to the substrate 8, and the surface was subjected to orientation treatment as shown above. A layer for protecting the active element may be provided on the surface. Next, these substrates were faced to each other while maintaining a gap of 5 μm, and the surroundings were left and adhered and fixed. Next, the liquid crystal / polymer precursor mixture sealed in the empty panel will be described. An 8: 2 mixture of Merck TL213 and MJ91261 was used as the liquid crystal, and 97% by weight of this liquid crystal was mixed with 3% by weight of S811 made by Merck as a chiral component to obtain a chiral liquid crystal. M361, SI512, and M34 manufactured by Mitsui Toatsu Dye Co., Ltd. were mixed as 1.5% by weight, 1.7% by weight, and 0.5% by weight, respectively, as dichroic dye in 96.3% by weight of the liquid crystal. As a polymer precursor, 93% by weight of this guest-host chiral liquid crystal is used as a polymer precursor and as a chiral polymer precursor.

Were dissolved in 6.86% by weight and 0.14% by weight, respectively, and sealed in the previously prepared empty panels. The panel was irradiated with ultraviolet rays (300 nm to 400 nm, 3.5 nW / cm ² ) from the substrate 1 side at 50 ° C. to polymerize the polymer precursor in the liquid crystal to obtain a display device. Further, the surface of the display element was subjected to non-glare treatment and anti-reflection treatment. This processing may not be necessary.

  When the reflectance of this display element under no electric field was measured, it was 3% at 20 ° C. In addition, the LCD driver and controller circuit were connected, and the computer screen could be displayed brightly and with good contrast. Of course, it can also be used as a terminal of a television or a game machine. Bright color display is possible by combining color filters.

  As the chiral component, liquid crystal, and polymer precursor used in this reference example, those shown in Example 1 and Example 15 can be used.

  Concerning the content of the dichroic dye, the use of the dichroic dye is mainly used for transmission under no electric field, for example, when a solar cell is used as a reflector or another display device is arranged. The amount is reduced to improve the power generation efficiency of the solar cell, or to improve the visibility of the display device arranged on the back side. For other applications, as shown here, light absorption is sufficiently performed in the absence of an electric field so that sufficient contrast is obtained.

など、およびこれらの化合物のフェニル、ビフェニル、をフェニル、ビフェニルターフェニルなどの骨格に変えたものや、アルキル基の構造を変えたものなとも用いることができる。何れにしてもその混合量については、液晶部分のカイラルピッチと高分子前駆体部分のカイラルピッチが同じになるようにカイラル高分子前駆体の混合量を決める。例えば低分子カイラル成分Ｓ８１１では液晶に対して１重量％混合したときのカイラルピッチは１０μｍ程度である。一方先の実施例中で用いたカイラル高分子前駆体は液晶に対して１重量％混合したときのカイラルピッチは２０μｍ程度である。 そこで液晶をツイストするための低分子カイラル成分Ｓ８１１を液晶に対して３重量％混合してカイラルピッチを３μｍ程度として、前記カイラル高分子前駆体を高分子前駆体に対して、６重量％混合して高分子前駆体のカイラルピッチを３μｍに揃えるのである。すなわち重合前においては高分子前駆体は液晶中に溶けており液晶の量は低分子液晶と高分子前駆体の和であり、これをツイストするためのカイラル成分の量は、低分子カイラル成分とカイラル高分子前駆体の和になる。次に重合手段にて高分子前駆体を重合すると、高分子前駆体及びカイラル高分子前駆体は重合して液晶層から相分離して液晶中から除外される。そのため液晶中に残るカイラル成分は塩分子カイラル成分だけとなる。このため液晶中のカイラルピッチは変化しない。 As the chiral polymer precursor, the one used here has a chiral ability of about S811, but as other chiral polymer precursors,

And those obtained by changing phenyl or biphenyl of these compounds into a skeleton such as phenyl or biphenyl terphenyl, or those obtained by changing the structure of the alkyl group. In any case, the mixing amount of the chiral polymer precursor is determined so that the chiral pitch of the liquid crystal portion and the chiral pitch of the polymer precursor portion are the same. For example, in the low molecular chiral component S811, the chiral pitch when mixed at 1% by weight with respect to the liquid crystal is about 10 μm. On the other hand, the chiral polymer precursor used in the previous examples has a chiral pitch of about 20 μm when mixed with 1% by weight of the liquid crystal. Therefore, 3% by weight of the low molecular chiral component S811 for twisting the liquid crystal is mixed with the liquid crystal so that the chiral pitch is about 3 μm, and the chiral polymer precursor is mixed with 6% by weight with respect to the polymer precursor. Thus, the chiral pitch of the polymer precursor is adjusted to 3 μm. That is, before polymerization, the polymer precursor is dissolved in the liquid crystal, and the amount of the liquid crystal is the sum of the low-molecular liquid crystal and the polymer precursor, and the amount of the chiral component for twisting this is the low-molecular chiral component. Sum of chiral polymer precursors. Next, when the polymer precursor is polymerized by a polymerization means, the polymer precursor and the chiral polymer precursor are polymerized and phase-separated from the liquid crystal layer and excluded from the liquid crystal. Therefore, the only chiral component remaining in the liquid crystal is the salt molecule chiral component. For this reason, the chiral pitch in the liquid crystal does not change.

  In contrast, since no chiral polymer precursor is used in the past, the polymer precursor is dissolved in the liquid crystal before polymerization, and the amount of liquid crystal is the sum of the low-molecular liquid crystal and the polymer precursor. The amount of the chiral component for twisting is only the low-molecular chiral component. Next, when the polymer precursor is polymerized by a polymerization means, the polymer precursor is polymerized and phase-separated from the liquid crystal layer and excluded from the liquid crystal. Therefore, although the amount of liquid crystal is reduced by the amount of the polymer precursor, the amount of the low molecular chiral component remaining therein remains unchanged. For this reason, the chiral pitch in the liquid crystal is shortened, and an alignment mismatch occurs between the polymer and the liquid crystal.

  The thickness of the liquid crystal / polymer layer is preferably 3 μm to 10 μm. If it is thinner than this, the scattering becomes thin, and if it is thicker than this, the driving voltage becomes high and the contrast is lowered, which is not practical.

  As the active element used here, in addition to the MIM element shown here, an element having a transistor structure such as a polysilicon TFT or an amorphous silicon TFT element, an element having an MIM structure, a ferroelectric element, or the like can be used. The number of active elements is not limited to the number shown here, and may be determined according to the application. Of course, an active element is not formed, and display can be performed as a clock or an electronic notebook as shown below.

A reflective layer may be disposed on the back surface of the display element using the reflective electrode 7 as a transparent electrode. The reflective layer may be given light scattering properties. Of course, a solar cell may be used as the reflective layer.
(Comparative Example 7)

Here, in Reference Example 1, an example in which only S811 is used as the chiral component is shown. Specifically, 7% by weight of hyphenyl methacrylate as a polymer precursor was mixed with the guest-host chiral liquid crystal shown in Example 1 to produce a display device in the same manner as in Reference Example 1. When the reflectance of the display element thus produced was measured under no electric field, it was 5% at 20 ° C.
(Reference Example 2)

  This reference example shows an example in which a chiral polymer precursor is applied to a display element that does not contain a dichroic dye and in which a polymer is dispersed in a liquid crystal in the form of particles or particles. An empty panel was prepared according to Example 5. Next, the liquid crystal and polymer precursor mixture sealed in the empty panel will be described. As a liquid crystal, RDP80661-2 manufactured by Roddick Co. was mixed with 98% by weight and 2% by weight CNL611 manufactured by Asahi Denka Co., Ltd. as a chiral component to obtain a chiral liquid crystal. In this chiral liquid crystal, ptylphenyltranmethacrylate and hyphenyldimethacrylate as polymer precursors and the compound of Example 11 as chiral polymer precursors were 3.3% by weight, 1.7% by weight, 0.3% by weight, respectively. Mixed. This was enclosed in the previous empty panel and irradiated with ultraviolet rays at 50 ° C. The display element surface may be subjected to non-glare treatment or anti-reflection treatment.

  A solar cell was arranged on the back surface of the display element thus manufactured, and the reflectance when no electric field was applied was measured by the same method as in Example 2 as a reflective display element. The reflectance was 1.8% at 20 ° C. Here, a segment display for a watch could be performed by applying an electric field. Moreover, a solar cell disposed on the back surface could be used as a liquid crystal driving power source.

  Although no active element is used here, the same effect can be obtained by using an active element. At that time, it is necessary to use a liquid crystal having a good retention rate as shown in Embodiment 1 as the liquid crystal. Bright color display is possible by combining color filters. When no active element is used, any material having a nematic liquid crystal phase can be used.

  The thickness of the liquid crystal / polymer layer is preferably 3 μm to 10 μm. If it is thinner than this, the scattering becomes thin, and if it is thicker than this, the driving voltage becomes high and the contrast is lowered, which is not practical.

  Instead of the solar cell arranged on the back surface of the display element, a light absorption layer and a light reflection layer may be arranged. Further, nothing can be arranged on the back surface of the display element, and display can be performed as white scattering on a transparent glass.

Other members, manufacturing conditions, and the like are the same as in Reference Example 1. The chiral component shown in Example 15 can also be used.
(Comparative Example 8)

Here, an example using only a low molecular chiral component in Reference Example 2 is shown. Specifically, the chiral liquid crystal shown in Reference Example 2 was mixed with 3.4% by weight and 1.6% by weight, respectively, of ptylphenyltranmethacrylate and biphenyldimethacrylate as polymer precursors. A display element was fabricated in the same manner as in Reference Example 2 except for the other member conditions. The reflectance of the display element thus produced under no electric field was measured and found to be 3% at 20 ° C.
(Reference Example 3)

を０.１重量％混合して先に作製した空パネルに封入した。５０ＢＣにてこのパネルに基板１側から紫外線（３００ｎｍ〜４００ｎｍ、３．５ｍＷ／ｃｍ²）を照射して液晶中の高分子前駆体を重合して表示装置とした。さらにこの表示装置の表面にノングレア処理及び減反射処理を施した。この処理はなくてもよい。 In this reference example, an example in which a chiral polymer precursor is applied to a display device in which a liquid crystal containing a dichroic dye is aligned and dispersed in a polymer gel network and an active element is shown. In accordance with Example 9, an empty panel in which a TFT element was formed was produced. Next, the liquid crystal / polymer precursor mixture sealed in the empty panel will be described. A 7: 3 mixture of Merck TL205 and BL007 was used as the liquid crystal, and 2% by weight of CNL611 manufactured by Asahi Denka Co., Ltd. as a chiral component was mixed with 98% by weight of this liquid crystal to obtain a chiral liquid crystal. M361, M370, and M483 manufactured by Mitsui Toatsu Dye Co., Ltd. were mixed with 1.2 wt%, 2 wt%, and 0.5 wt% of the dichroic dye, respectively, in 96.3% by weight of the liquid crystal. 97% by weight of the guest host chiral liquid crystal, 3% by weight of C6H manufactured by Philips as a polymer precursor, and as a chiral polymer precursor

Was mixed in 0.1% by weight and enclosed in an empty panel prepared earlier. The panel was irradiated with ultraviolet rays (300 nm to 400 nm, 3.5 mW / cm ² ) from the substrate 1 side at 50 BC to polymerize the polymer precursor in the liquid crystal to obtain a display device. Further, non-glare treatment and anti-reflection treatment were performed on the surface of the display device. This processing may not be necessary.

  When the reflectance of this display device under no electric field was measured according to Example 1, it was 3% at 20 ° C. In addition, by connecting the driver for driving the liquid crystal and the controller circuit, the computer screen could be displayed brightly and with good contrast. Of course, it can also be used as a terminal of a television or a game machine. Bright color display is possible by combining color filters.

  As the chiral component, the liquid crystal, the polymer precursor, the active element, the production conditions and the like used in this example, those shown in Reference Example 1 can be used. As the chiral component, those shown in Example 15 can also be used.

  Concerning the content of dichroic dyes, the use of dichroic dyes in applications where transmission is mainly performed under no electric field, for example, when using solar cells as reflectors or arranging other display devices The amount is reduced to improve the power generation efficiency of the solar cell, or to improve the visibility of the display device arranged on the back side. For other applications, as shown here, light absorption is sufficiently performed in the absence of an electric field so that sufficient contrast is obtained.

The thickness of the liquid crystal / polymer layer is preferably 3 μm to 10 μm. If it is thinner than this, the scattering becomes thin, and if it is thicker than this, the driving voltage becomes high and the contrast is lowered, which is not practical.
(Comparative Example 9)

  Here, an example using only a low molecular chiral component in Reference Example 3 is shown. Specifically, 3% by weight of C6H as a polymer precursor was mixed with the guest-host chiral liquid crystal shown in Reference Example 3. A display element was fabricated in the same manner as in Reference Example 3 except for the other member conditions.

When the reflectance of the display element thus produced was measured under no electric field, it was 4% at 20 ° C.
(Reference Example 4)

を０．１重量％混合した。これを先の空パネルに封入して５０℃にて紫外線を照射した。この表示素子表面にノングレア処理または減反射処理を施してもよい。 In this embodiment, an example is shown in which a chiral polymer precursor is applied to a display element in which liquid crystal containing no dichroic dye is oriented and dispersed in a polymer gel network. First, an empty panel enclosing the liquid crystal / polymer precursor was prepared according to Example 5. Next, the liquid crystal and polymer precursor mixture sealed in the empty panel will be described. As a liquid crystal, 10% by weight of CM22 manufactured by Chisso and 2.5% by weight of CB15 manufactured by Merck were mixed as BL 007 manufactured by Merck to obtain a chiral liquid crystal. In this chiral liquid crystal, 3% by weight of C6H used in Reference Example 3 as a polymer precursor was used as a chiral polymer precursor.

Was mixed by 0.1% by weight. This was enclosed in the previous empty panel and irradiated with ultraviolet rays at 50 ° C. The display element surface may be subjected to non-glare treatment or anti-reflection treatment.

  A solar cell was placed on the back surface of the display element thus fabricated, and the reflectance when no electric field was applied was measured by the same method as in Example 1 as a reflective display element. The reflectivity was 1.5% at 20 ° C.

旭電化社製ＦＬ５１９、ＣＮＬ６２１、ＣＮＬ６１７、ＣＮＬ６１６、ＣＮＬ６２３、ＣＮＬ６３７、ＣＮＬ６３８、ＣＮＬ６３９などがある。温度依存性が正のカイラル成分の例としては、チッソ社製ＣＭ１９、ＣＭ２０、メルク社製ＣＢ１５、Ｃ１５、Ｓ８１１、Ｒ８１１、Ｓ１０１１、Ｒ１０１１、Ｓ１０８２、Ｒ１０８２などがある。もちろんこの他のカイラル成分も利用できる。またここでは２種頬のカイラル成分を用いたが、３種類以上混合してもよい。もちろん実施例１に示したようなカイラルピッチの温度依存性の極めて小さいカイラル成分を用いてもよい。 The chiral component used in this example has the ability to turn the liquid crystal to the right for C = 22 and CB15. CB15 has a tendency to increase the chiral pitch when the temperature rises (temperature dependence is positive). As the temperature rises, the chiral pitch tends to be shorter (temperature dependence is negative). Thus, it is desirable to add two or more types of chiral components having a tendency that the temperature dependence of the chiral pitch is opposite to each other. Examples of other chiral components with negative temperature dependence include CM22 manufactured by Chisso Corporation,

Asahi Denka Co., Ltd. FL519, CNL621, CNL617, CNL616, CNL623, CNL637, CNL638, CNL639 and the like are available. Examples of chiral components having a positive temperature dependence include Chisso CM19 and CM20, Merck CB15, C15, S811, R811, S1011, R1011, S1082, and R1082. Of course, other chiral components can also be used. Here, two types of cheek chiral components are used, but three or more types may be mixed. Of course, a chiral component having extremely small temperature dependence of the chiral pitch as shown in the first embodiment may be used.

Reference Example 2 can be used for the liquid crystal, polymer precursor, empty panel, other member manufacturing conditions, and the like used here. Moreover, the structure of the chiral component shown here can also be applied when the polymer is a particle or a particle connected body.
(Comparative Example 10)

  Here, an example using only a low molecular chiral component in Example 15 is shown. Specifically, 3% by weight of C6H as a polymer precursor was mixed with the chiral liquid crystal shown in Example 15. A display element was fabricated in the same manner as in Example 15 except for the other member conditions.

When the reflectance of the display element thus produced was measured under no electric field, it was 3% at 20 ° C.
(Reference Example 5)

を０．４重量％および光重合開始剤としてチバガイギー社製イルガキュア１８４を２重量％混合して先に作製した空パネルに封入した。５０℃にてこのパネルに基板１側から紫外線（３００ｎｍ〜４００ｎｍ、３０ｍＷ／ｃｍ²）を照射して液晶中の高分子前駆体を重合して表示装置とした。きらにこの表示装置の表面にノングレア処理及び減反射処理を施した.この処理はなくてもよい。 In this embodiment, an example is shown in which a chiral polymer precursor and an active element are combined in a display element in which liquid crystal containing a dichroic dye is oriented and dispersed in a polymer matrix. An empty panel enclosing the liquid crystal / polymer was produced in the same manner as in Reference Example 1. Next, the liquid crystal / polymer precursor mixture sealed in the empty panel will be described. As the liquid crystal, an 8: 2 mixture of TL213, TL213, and MJ91261 manufactured by Merck Co. was used, and 2 weights of CN617 manufactured by Asahi Denka Co., Ltd. as a chiral component was mixed with 98% by weight of this liquid crystal to obtain a chiral liquid crystal. M361, SI512, and M34 manufactured by Mitsui Toatsu Dye Co., Ltd. were mixed as 1.5% by weight, 1.7% by weight, and 0.4% by weight, respectively, as a dichroic dye in 96.4% by weight of the liquid crystal. The guest host chiral liquid crystal is 77.6% by weight, the polymer precursor is 20% by weight of M6200 manufactured by Toa Gosei Chemical Co., Ltd., and the chiral polymer precursor.

Was mixed with 0.4% by weight and 2% by weight of Irgacure 184 manufactured by Ciba Geigy Co. as a photopolymerization initiator, and sealed in an empty panel prepared previously. The panel was irradiated with ultraviolet rays (300 nm to 400 nm, 30 mW / cm ² ) from the substrate 1 side at 50 ° C. to polymerize the polymer precursor in the liquid crystal to obtain a display device. The surface of this display device was subjected to non-glare treatment and anti-reflection treatment. This treatment is not necessary.

  When the reflectance of this display device under no electric field was measured according to Reference Example 2, it was 8% at 20 ° C. In addition, when a liquid crystal drive driver and a controller circuit were connected and a computer was connected, display was possible with good contrast. Of course, it can also be used as a terminal of a television or a game machine. Bright color display is possible by combining color filters.

  As the chiral component used in this reference example, the single-component system or multi-component system shown in Reference Examples 1 and 4 can be used.

  As the liquid crystal, polymer precursor, dichroic dye, active element, and other member conditions, those shown in Example 1 and Reference Example 1 can be used.

  Concerning the content of dichroic dyes, the use of dichroic dyes in applications where transmission is mainly performed under no electric field, for example, when using solar cells as reflectors or arranging other display devices The amount is reduced to improve the power generation efficiency of the solar cell, or to improve the visibility of the display device arranged on the back side. For other applications, as shown here, light absorption is sufficiently performed in the absence of an electric field so that sufficient contrast is obtained.

The thickness of the liquid crystal / polymer layer is preferably 3 μm to 10 μm. If it is thinner than this, the scattering becomes thin, and if it is thicker than this, the driving voltage becomes high and the contrast is lowered, which is not practical.
(Comparative Example 11)

Here, an example using only a low molecular chiral component in Reference Example 5 is shown. Specifically, only the polymer precursor and the photopolymerization initiator are mixed with the chiral liquid crystal shown in Reference Example 5 and the chiral polymer precursor is not used, and other member conditions are the same as in Reference Example 5. Thus, a display element was manufactured. When the reflectance of the display device thus produced was measured under no electric field, it was 10% at 20 ° C.
(Reference Example 6)

を１重量％、さらに光重合開始剤として日本化薬社製Ｄ ETXを２重量％混合した。これを先の空パネルに封入して５０℃にて紫外線を照射した。この表示素子表面にノングレア処理または減反射処理を施してもよい。 In this embodiment, an example in which a liquid crystal is aligned and dispersed in a polymer matrix without using a dichroic dye and a chiral polymer precursor is used for bare hands is shown. First, an empty panel enclosing the liquid crystal / polymer precursor was prepared according to Example 5. The liquid crystal and polymer precursor mixture sealed in the empty panel will be described. 3 wt% of Merck R811 as a chiral component was mixed with Mercury BL007 as a liquid crystal to obtain a chiral liquid crystal. To this chiral liquid crystal, 30% by weight of M7100 manufactured by Toa Gosei Chemical Co., Ltd.

1% by weight, and further 2% by weight of D ETX manufactured by Nippon Kayaku Co., Ltd. as a photopolymerization initiator was mixed. This was enclosed in the previous empty panel and irradiated with ultraviolet rays at 50 ° C. The display element surface may be subjected to non-glare treatment or anti-reflection treatment.

A solar cell was placed on the back surface of the display element thus fabricated, and the reflectance when no electric field was applied was measured by the same method as in Example 1 as a reflective display element. The reflectivity was 6% at 20 ° C.
As the chiral component used in this reference example, those shown in Reference Example 1 and Reference Example 4 can be used.

Reference Example 1 can be used for the liquid crystal, polymer precursor, empty panel, and other member manufacturing conditions used here.
(Comparative Example 12)

Here, an example using only a low molecular chiral component in Reference Example 6 is shown. Specifically, only the polymer precursor and the photopolymerization initiator are mixed with the chiral liquid crystal shown in Reference Example 6 and the chiral polymer precursor is not used, and other member conditions are the same as in Reference Example 6. Thus, a display element was manufactured. The reflectance of the display element thus produced under no electric field was measured and found to be 10% at 20 ° C.
(Reference Example 7)

を２重量％混合してカイラル液晶とした。この液晶９６．３重量％に２色性色素として三井東圧染料社製Ｍ３６１、Ｍ３７０、Ｍ４８３をそれぞれ１.２重量％、２重量％、 ０.５重量％混合した。このゲストホストカイラル液晶に高分子前駆体としてビフェニルメタクリレートを７重量％溶かして先に作製した空パネルに封入した。５０℃にてこのパネルに基板１側から紫外線（３００ｎｍ〜４００ｎｍ、３．５ｍＷ／ｃｍ²）を照射して準晶中の高分子前駆体を重合して表示装置とした。さらにこの表示素子の表面にノングレア処理及び減反射処理を施した。この処理はなくてもよい。 In this reference example, an example in which a chiral element having little temperature dependence of the chiral pitch is used in a display device in which a display element in which a polymer is dispersed in a liquid crystal containing a dichroic dye in the form of particles or a particle connected body is combined with seven Acty elements. showed that. The same empty panel as in Reference Example 1 was used. Next, the liquid crystal / polymer precursor mixture sealed in the empty panel will be described. As a liquid crystal, an 8: 2 mixture of TL205 and MJ91261 manufactured by Merck Co., Ltd. was used as a chiral component in 98% by weight of the liquid crystal.

Was mixed to obtain a chiral liquid crystal. M361, M370, and M483 manufactured by Mitsui Toatsu Dye Co., Ltd. were mixed as 1.2% by weight, 2% by weight, and 0.5% by weight, respectively, with 96.3% by weight of the liquid crystal. 7% by weight of biphenyl methacrylate as a polymer precursor was dissolved in this guest-host chiral liquid crystal and sealed in the previously produced empty panel. The panel was irradiated with ultraviolet rays (300 nm to 400 nm, 3.5 mW / cm ² ) from the substrate 1 side at 50 ° C. to polymerize the polymer precursor in the quasicrystal to obtain a display device. Further, the surface of the display element was subjected to non-glare treatment and anti-reflection treatment. This processing may not be necessary.

  When the reflectance of this display element under no electric field was measured, it was 2% at 50 ° C. and 3% at 20 ° C. In addition, by connecting the driver for driving the liquid crystal and the controller circuit, the computer screen could be displayed brightly and with good contrast. Of course, it can also be used as a terminal of a television or a game machine. Bright color display is possible by combining color filters.

などを用いることができる。また旭電化社製ＣＮＬ６１１、ＣＮＬ６２１、ＣＮＬ６ １７、ＣＮＬ６１６、ＣＮＬ６２３等も同様に用いることができる。また参考例４で示すような多成分系のカイラル成分も用いることができる。 The chiral component used in the present embodiment only needs to have a small temperature dependency of the chiral pitch, and more preferably has a chiral pitch change rate within 20% in the operating temperature range. If it is out of this range, the contrast is significantly lowered due to temperature changes during use. As a chiral component that can be used in this embodiment,

Etc. can be used. Asahi Denka Co., Ltd. CNL611, CNL621, CNL617, CNL616, CNL623, etc. can be used similarly. A multi-component chiral component as shown in Reference Example 4 can also be used.

  As the liquid crystal and polymer precursor, those shown in Example 1 can be used. The thickness of the liquid crystal / polymer layer is preferably 3 μm to 10 μm. If it is thinner than this, the scattering becomes thin, and if it is thicker than this, the driving voltage becomes high and the contrast is lowered, which is not practical.

  As the active element used here, in addition to the MIM element shown here, an element having a transistor structure such as a polysilicon TFT or an amorphous silicon TFT element, an element having an MIM structure, a ferroelectric element, or the like can be used. The number of active elements is not limited to the number shown here, and may be determined according to the application. Of course, display can be performed without forming active elements. Of course, an active element is not formed, and simple matrix or static driving can also be performed.

A reflective layer or a solar cell may be disposed on the back surface of the display element using the reflective electrode 7 as a transparent electrode. The reflective layer may be given light scattering properties.
(Comparative Example 13)

  Here, in Reference Example 7, a case where only the chiral component having a positive temperature dependence of the chiral pitch is used as the chiral component. Specifically, 2.5% by weight of CB15 manufactured by Merck was mixed as a chiral component with respect to the liquid crystal. A display device was fabricated in the same manner as in Reference Example 7 except for the other member conditions.

The reflectance of the display element thus produced under no electric field was measured and found to be 2% at 50 ° C. and 5% at 20 ° C.
(Reference Example 8)

  This reference example shows an example in which a chiral component having little temperature dependence of the chiral pitch is used for a display element that does not contain a dichroic dye and in which liquid crystal and polymer are aligned and dispersed with each other. An empty panel in which no active element was formed was learned from Example 5. Next, the liquid crystal and polymer precursor mixture sealed in the empty panel will be described. As a liquid crystal, RDP80661-2 manufactured by Roddick and ML1009 manufactured by Merck were mixed at a ratio of 7: 3, and 2% by weight of CNL617 (manufactured by Asahi Denka Co., Ltd.) was mixed as a chiral liquid crystal. This chiral liquid crystal was mixed with 4% by weight of methyl terphenyl dimethacrylate as a polymer precursor. This was enclosed in the previous empty panel and irradiated with ultraviolet rays at 50 ° C. The display element surface may be subjected to non-glare treatment or anti-reflection treatment.

  A solar cell was placed on the back surface of the display element thus manufactured, and the reflectance when no electric field was applied was measured by the same method as in Reference Example 7 as a reflective display element. The reflectance was 1% at 50 ° C. and the reflectance was 3% at 20 ° C. Here, a segment display for a watch could be performed by applying an electric field.

  Although no active element is used here, the same effect can be obtained by using an active element. At that time, it is necessary to use a liquid crystal having a high holding ratio as shown in the first embodiment as the liquid crystal. For example, TL202, TL204, TL205, TL213, TL215, and TL216 manufactured by Merck may be used as a base. Bright color display is possible by combining color filters. When no active element is used, any material having a nematic liquid crystal phase can be used.

  The thickness of the liquid crystal / polymer layer is preferably 3 μm to 10 μm. If it is thinner than this, the scattering becomes thin, and if it is thicker than this, the driving voltage becomes high and the contrast is lowered, which is not practical.

  Instead of the solar cell arranged on the back surface of the display element, a light absorption layer and a light reflection layer may be arranged. Further, nothing can be arranged on the back surface of the display element, and display can be performed as white scattering on a transparent glass.

Other members, manufacturing conditions, and the like are the same as in Reference Example 7. For the chiral component, the multi-component system shown in Reference Example 4 can also be used.
(Comparative Example 14)

Here, in Reference Example 8, a case where only a chiral component having a positive temperature dependence of the chiral pitch is used as the chiral component. Specifically, 5% by weight of CB15 manufactured by Merck was mixed as a chiral component with respect to the liquid crystal. A display element was fabricated by using the same member conditions as in Reference Example 8. The reflectance of the display element thus produced under no electric field was measured and found to be 1% at 50 ° C. and 3% at 20 ° C.
(Reference Example 9)

In this reference example, an example in which a chiral device having a small chiral pitch temperature dependency is used in a display device in which a liquid crystal containing a dichroic dye is aligned and dispersed in a polymer gel network and an active element is used. Indicated. An empty panel in which a TFT element was formed was prepared according to Example 2. Next, the liquid crystal / polymer precursor mixture sealed in the empty panel will be described. A 7: 3 mixture of Merck TL205 and BL007 was used as the liquid crystal, and 2% by weight of CNL611 manufactured by Asahi Denka Co., Ltd. as a chiral component was mixed with 98% by weight of this liquid crystal to obtain a chiral liquid crystal. M361, M370, and M483 manufactured by Mitsui Toatsu Dye Co., Ltd. were mixed as 1.2% by weight, 2% by weight, and 0.5% by weight, respectively. The guest host chiral liquid crystal (97% by weight) was mixed with 3% by weight of C6H manufactured by Philips as a polymer precursor and sealed in the previously produced empty panel. The panel was irradiated with ultraviolet rays (300 nm to 400 nm, 3.5 mW / cm ² ) from the substrate 1 side at 50 ° C. to polymerize the polymer precursor in the liquid crystal to obtain a display device. Further, non-glare treatment and anti-reflection treatment were performed on the surface of the display device. This processing may not be necessary.

  When the reflectance of this display device under no electric field was measured, it was 2% at 50 ° C. and 3% at 20 ° C. In addition, by connecting the driver for driving the liquid crystal and the controller circuit, the computer screen could be displayed brightly and with good contrast. Of course, it can also be used as a terminal of a television or a game machine. Bright color display is possible by combining color filters.

  As the chiral component, the liquid crystal, the polymer precursor, the active element, the production conditions and the like used in this reference example, those shown in Example 2 can be used. For the chiral component, the multi-component system shown in Reference Example 4 can also be used.

The thickness of the liquid crystal / polymer layer is preferably 3 μm to 10 μm. If it is thinner than this, the scattering becomes thin, and if it is thicker than this, the driving voltage becomes high and the contrast is lowered, which is not practical.
(Comparative Example 15)

Here, in Reference Example 9, a case where only a chiral component having a positive chiral pitch temperature dependency is used is shown. Specifically, 2% by weight of CB15 manufactured by Merck was mixed as a chiral component with respect to the liquid crystal. A display device was fabricated in the same manner as in Reference Example 9 except for the other member conditions. When the reflectance of the display device thus produced was stabbed with no electric field, it was 3% at 50 ° C. and 10% at 20 ° C.
(Reference Example 10)

  In this reference example, an example is shown in which a chiral component having a small temperature dependence of the chiral pitch is used for a display element in which a liquid crystal containing no dichroic dye is oriented and dispersed in a polymer gel network. First, an empty panel enclosing the liquid crystal / polymer precursor was prepared according to Example 5. Next, the liquid crystal and polymer precursor mixture sealed in the empty panel will be described. 10% by weight of CM22 manufactured by Chisso and 2.5% by weight of CB15 manufactured by Merck were mixed with CB1007 manufactured by Merck as a liquid crystal to obtain a chiral liquid crystal. This chiral liquid crystal was mixed with 3% by weight of C6H used in Example 3 as a polymer precursor. This was enclosed in the previous empty panel and irradiated with ultraviolet rays at 50 ° C. The display element surface may be subjected to non-glare treatment or anti-reflection treatment.

  A solar cell was placed on the back surface of the display element thus fabricated, and the reflectance when no electric field was applied was measured by the same method as in Example 1 as a reflective display element. The reflectance was 2% at 50 ° C. and the reflectance was 5% at 20 ° C.

As the chiral component used in this reference example, those shown in Reference example 4 can be used. Reference Example 8 can be used for the liquid crystal, polymer precursor, empty panel, and other member manufacturing conditions used here.
(Comparative Example 16)

  Here, in Reference Example 10, a case where only a chiral component having a positive temperature dependence of the chiral pitch is used as the chiral component. Specifically, 5% by weight of CB15 manufactured by Merck was mixed as a chiral component with respect to the liquid crystal. A display element was fabricated in the same manner as in Reference Example 10 except for the other member conditions. The reflectance of the display element thus produced under no electric field was measured and found to be 1% at 50 ° C. and 3% at 20 ° C.

  In this embodiment, an example in which the above-described embodiment and reference examples are applied to a color display device using a color filter is shown. FIG. 7 shows a simple sectional view of a part of an empty panel on which the color filter 10 used in this embodiment is formed. About the members other than the color filter and the manufacturing conditions, the members and conditions of the examples and reference examples were used. However, no dichroic dye is added here. In order to increase the contrast, a dichroic dye may be added. When a color display liquid crystal driver was connected to this color display device and used as a computer terminal, color display with good contrast could be performed. Of course, it is also possible to display a clock, TV or game console.

  For the chiral component, the liquid crystal / polymer layer, the configuration of the empty panel, the manufacturing conditions, and the like used here, those having the configurations shown in Examples 1 to 11 and Reference Examples 1 to 10 can be used. Further, the present invention can be similarly applied to the following electronic devices.

  As for the color filter, a bright display can be obtained when the color density is made thinner than that of a commonly used transmissive color filter. In addition to the three primary colors of red, blue, and green, the colors can be freely selected from combinations of colors that can be displayed in color such as yellow, cyan, and magenta.

  In addition, although the color filter is formed on the side of the display device on the display side substrate 1 in contact with the liquid crystal at the position where the color filter is inserted, the color filter may be formed on the substrate 8. The color filter is preferably formed between the substrate and the electrode from the viewpoint of driving voltage, but a transparent electrode may be formed on the color filter.

  When the color filter is formed on the substrate 1, it is necessary to form the color filter with a material that transmits ultraviolet rays for polymerizing the polymer precursor.

  As the active element, a TFT element having another configuration, a transistor, an MIM element, a ferroelectric element, or the like can be used in addition to the TFT element shown here. In addition to glass, a substrate on which these active elements are formed can be made of a semiconductor such as silicon, gallium arsenide, or germanium, or an inorganic material such as an inorganic material or plastic. When a semiconductor is used as the substrate, a driver and a controller for driving can all be formed in the substrate, so that a display device can be manufactured at a very low cost.

  An embodiment in which the display elements manufactured in the above-described embodiments and comparative examples are used in the display portion of an electronic notebook which is an information processing apparatus will be described. FIG. 8 shows a simple cross-sectional view of the information processing apparatus of this embodiment. A display element is manufactured according to the above-described example or comparative example, and a solar cell is disposed on the back surface thereof. When the power of the solar cell is connected to the power source of the electronic notebook, the visibility is greatly improved. It is possible to extend the usage time significantly.

  In addition, the solar battery was connected to a storage battery built in the electronic device, and the power generated by the solar battery was stored in the storage battery so that the device could work sufficiently even in a dark place.

  Thus, in the past, the solar cell took up space and the design and size were limited. However, since the display element is almost transparent, the display panel can be overlaid on the solar cell, making it extremely compact. Moreover, it is possible to realize an electronic notebook without worrying about running out of batteries. An information input device such as a tablet or a touch panel may be disposed on the front surface or the back surface of the display device.

  The example which applied the display element produced in the Example mentioned above or the comparative example to the timepiece as an information display device was shown. In particular, an example in which a display element is used for a dial is shown here. FIG. 9 shows a simple cross-sectional view of the information display device of this embodiment. A display device with a hole in the center is manufactured according to the above-described examples or comparative examples, a solar cell is arranged on the back surface, and a hand is attached through an analog watch shaft to manufacture a hybrid watch. It was possible to perform display with extremely high visibility.

  In addition, the solar battery was connected to a storage battery built in the electronic device, and the power generated by the solar battery was stored in the storage battery so that the device could work sufficiently even in a dark place.

  Further, since the display element cannot be driven sufficiently by the voltage of the solar cell, a very bright display could be obtained when the voltage of the solar cell was increased to 5 V by incorporating a booster circuit.

  Further, as a driving method, a voltage that is substantially twice the power supply voltage can be applied by turning the ground of the liquid crystal driver in accordance with the driving timing. According to this, the display element described in the previous embodiment Can be driven sufficiently, and an extremely bright display can be obtained.

  Although the display element mentioned in the previous embodiment has sufficiently low power consumption, it is possible to display on the display element only when the switch is pressed in order to further extend the battery life as a watch.

  Of course, the same display can be performed even if a light absorbing plate is arranged instead of the solar cell. At this time, the drive power supply is only the built-in battery.

  The example which applied the display element produced in the Example mentioned above or the comparative example to the timepiece as an information display device was shown. In particular, here, an example in which a display element is used for a cover glass of a watch is shown (see FIG. 10). When the display element was manufactured according to the above-described examples or comparative examples, a solar cell was used as a dial, and a hybrid wristwatch was manufactured by attaching a hand through the axis of an analog timepiece. It was possible to do. Other configurations described in the fourteenth embodiment can be used as they are.

An example in which the display element manufactured in the above-described example or comparative example is applied to a portable television as an information display device is shown (FIG. 11). When the display element is manufactured according to the above-described example or comparative example, and the solar cell is arranged on the back surface and incorporated in the case of a portable television, display with extremely high visibility can be performed. In addition, the usage time could be greatly extended.
Other configurations described in the fourteenth embodiment can be used as they are.

  In the past, solar cells took up space and were limited in design and size, but since the display element is almost transparent, it is possible to stack the display panel on the solar cell, making it extremely compact and running out of battery. It has become possible to realize a portable information display device that does not have to worry about.

  In this example, the display element manufactured in the above-described example or comparative example was overlapped with an arbitrary display device or solar cell, and an example in which a high refractive index layer was disposed between them was shown. FIG. 12 shows a simple diagram of the electronic apparatus of this embodiment. The display element placed on the watch was prepared and used in accordance with the above-described examples or comparative examples. This display element can be sufficiently driven by a conventional watch IC. This display element was superimposed on a dark dial clock. At this time, ITO (refractive index 1.8) was used as a high refractive index layer on the surface of a smooth dark dial. When the date, time, and timekeeping function were displayed on the two-layer display device thus manufactured, it was possible to perform digital display in large letters on the face of a conventional analog watch, and it was very functional and fashionable. The brightness was 1.5 times brighter than when no high refractive index layer was deposited. Other configurations described in the fourteenth embodiment can be used as they are.

  The display device used here is not limited to a wristwatch or a table clock, but may be a meter of a machine, a display unit of a household electrical appliance or an electronic device, or any of an analog type, a digital type, and a hybrid type. However, it is preferable that the dial has a dark color or a reflective one in order to make the display easy to see. If a solar cell is used as the dial and the generated electric power is used as a power source for driving the device, the battery life of the device can be greatly extended. It can also be applied to meter panels for automobiles and the like.

  As a material for the high refractive index layer, in addition to ITO, high refractive index glass (for example, FDS1 (refractive index 2) manufactured by HOYA), inorganic oxide, metal thin film, organic or polymer thin film (terphenyl, Any material having a high refractive index such as berylene or tetracene is preferable. Positions as shown in FIGS. 13 and 14 are also effective as positions for inserting the high refractive index layer.

  The present embodiment can be applied to a timepiece, a vehicle-mounted meter panel, a mechanical meter, a household electrical appliance, a display unit of an electronic device, and the like, and an analog display and a digital display can be realized by a single display unit. In particular, since the quality of the analog display is not impaired at all, it is most suitable for applications requiring a high-class feeling. Of course, the same effect can be obtained even if the present invention is applied to a digital display device (twisted nematic liquid crystal element, LED, VFD, plasma display, etc.).

  In this example, an example in which a liquid crystal layer containing a dichroic dye is arranged between the display device arranged on the lower side and the display element arranged on the upper side in Example 13 (see FIG. 15). The layer containing a dichroic dye will be described. The two transparent substrates with electrodes were subjected to an orientation treatment and then bonded together while maintaining a gap of 7 μm (adjusted according to the application). Liquid crystal (ZLI1840 (manufactured by Merck), S344 (manufactured by Mitsui Toatsu Dye) and CB15 (manufactured by Merck)) mixed at 95: 3: 2 in this gap, and the materials used and the mixing ratio were optimized according to the application Then it was good). The panel thus prepared was arranged as shown in FIG.

  When it is desired to make the display element on the front side easier to see, the liquid crystal layer containing the dichroic dye can be controlled to absorb light by controlling the electric field so that the display by light scattering can be lifted. A normal PDLC may be used instead of the reverse PDLC used at this time. In order to make the display device on the back side easier to see, the electric field is controlled in the reverse direction to make the layer containing the dichroic dye transparent.

  The liquid crystal layer containing the dichroic dye can use a liquid crystal having a positive dielectric anisotropy or a liquid crystal having a negative dielectric anisotropy. At this time, a vertical alignment treatment may be performed on the surface of the substrate sandwiching the liquid crystal. By doing so, contrary to the previous example, it can be transparent when no electric field is applied, and light can be absorbed when an electric field is applied.

  Although the high refractive layer is arranged in FIG. 15, the display is possible without arranging it as shown in FIG.

  The present embodiment can be applied to a display unit of a clock, a vehicle-mounted meter panel, other mechanical meters, household electric appliances, electronic devices, and the like, and an analog display and a digital display can be realized with one display window. In particular, since the quality of the analog display is not impaired at all, it is most suitable for applications requiring a high-class feeling. As an application example, as shown in FIG. 17, when a panel in which the reflective electrode is replaced with a transparent electrode in Example 2 or Comparative Example 2 is used on an analog meter, it is used as a display for car navigation, television or video. It can be used, and it is extremely safe because the display can be seen while driving with the head in the direction of travel. The same effect can be obtained even when the present invention is applied to a digital display device (twisted nematic liquid crystal element, LED, VFD, plasma display, etc.).

  As described above, according to the present invention, when PDLC or reverse PDLC is used in an application in which haze is conspicuous, an appropriate amount of a dichroic dye is added to the liquid crystal, and a material having a low fluorescence quantum yield or a twist of a liquid crystal layer is added before and after polymerization. By using a material to be corrected by (1) and a material having a small temperature dependence, the haze is made inconspicuous and the visibility can be improved. The haze reduction technology of the display element of the present invention is extremely effective for applications that emphasize fashionable design such as watches. For example, when a reverse PDLC is arranged as a dial or cover glass in a wristwatch, the haze in the PDLC panel is hardly noticeable, and the contrast is remarkably increased. Of course, the same effect can be obtained in other electronic devices such as electronic notebooks, televisions, and meter panels. In addition, it is possible to provide a bright and easy-to-see multifunction electronic device by superimposing the reverse PDLC on a conventional display device or solar cell as it is or via a high refractive index layer.

  By using the present invention, it is possible to manufacture electronic devices such as wrist watches, table clocks, household appliances, and electronic devices that have extremely large display capacity and are very easy to see.

  In addition, when a solar cell is incorporated, it is possible to manufacture a display device and an electronic device that are extremely easy to see, low power consumption, and compact. For example, reverse PDLC can be applied as a cover glass or a dial of an analog timepiece with a solar battery, and it is possible to have both the beauty of an analog timepiece and the multifunctionality of a digital timepiece.

  In addition, by using it for the display part of electronic notebooks and portable televisions, it has become possible to produce an extremely compact and easy-to-view set despite the built-in solar cells. The built-in solar battery allows the device to be used without worrying about running out of battery.

  It can also be used as an in-vehicle meter panel with good visibility. For example, the panel placed on the back side is a conventional analog display device, the reverse PD LC is placed on the front side, the back side display is illuminated by the backlight, and the display element on the front side is illuminated from the front side (necessary in daytime) Then, a display with extremely good visibility can be obtained in which the display on the front side floats on the display on the back side. Thus, since the present invention can be arranged on a conventional mechanical meter, its application range is wide. The electronic device according to the present invention is basically a reflection type, and the brighter the surroundings, the better the appearance. Further, the same effect can be obtained by arranging a display element using a conventional backlight type or reflective type twisted nematic liquid crystal on the back side. When the present invention is used as a recently developed automobile navigation system, television or video display, it is extremely safe to drive because the map can be read with the face facing forward.

It is a figure which shows the structure of the panel in which the TFTT element used for Example 2 was formed. It is a figure which shows the structure of the panel used for Example 5. FIG. FIG. 6 is a diagram showing electro-optical characteristics of display elements in Example 5 and Comparative Example 5. It is a figure which shows the electro-optical characteristic of the display element in Example 6 and Example 7. FIG. It is a figure which shows the electro-optical characteristic of the display element in Example 8 and Comparative Example 6. It is a figure which shows the structure of the panel in which the MIM element used for the reference example 1 was formed. It is a figure which shows the structure of the panel in which the color filter and MIM element which were used for Example 12 were formed. FIG. 14 is a cross-sectional view illustrating a simple configuration of an information processing apparatus according to a thirteenth embodiment. It is a figure which shows the simple structure of the information display apparatus of Example 14. FIG. It is a figure which shows the simple structure of the information display apparatus of Example 15. It is sectional drawing which shows the simple structure of the information display apparatus of Example 16. FIG. 18 is a diagram illustrating an electronic apparatus according to a seventeenth embodiment. FIG. 18 is a diagram illustrating an electronic apparatus according to a seventeenth embodiment. FIG. 18 is a diagram illustrating an electronic apparatus according to a seventeenth embodiment. FIG. 20 is a diagram illustrating a simple configuration of an electronic device according to an eighteenth embodiment. FIG. 20 is a diagram illustrating a simple configuration of an electronic device according to an eighteenth embodiment. FIG. 20 is a diagram illustrating a simple configuration of an electronic device according to an eighteenth embodiment. It is the figure which showed the incident angle dependence of the reflectance when light injects into the flat board | substrate surface.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Electrode 3 Liquid crystal / polymer layer 7 Reflective electrode 8 Substrate 9 Non-glare / Non-reflection layer 10 Color filter 12 Insulating layer 13 Signal electrode 14 Source electrode
15 Gate electrode 16 Semiconductor layer 17 Drain electrode 18 Gate extinction layer 21 Display element 22 Solar cell 23 Cut panel 24 Information processing device 25 Information display device 26 Clock hand 27 Protection panel 28 Conventional display device 29 High refractive index layer 30 Conventional Meter panel 31 Liquid crystal layer containing dichroic dye

Claims (11)

A display unit;
A display element in which a liquid crystal-polymer layer in which a liquid crystal and a polymer are phase-separated is sealed between a pair of substrates disposed on the display portion and provided on a surface on the opposite side of the electrode;
A high refractive index layer having a refractive index of 1.8 or more disposed in a lower layer of the display element;
An electronic device comprising:   The electronic apparatus according to claim 1, wherein the high refractive index layer is disposed between the display element and the display unit.   The electronic device according to claim 1, wherein the display unit is disposed on a side opposite to a side on which the high refractive index layer is disposed with respect to the display element.   4. The electronic device according to claim 1, wherein the liquid crystal-polymer layer is controlled in a light transmission state and a scattering state in accordance with an applied voltage. 5.   When no voltage is applied to the liquid crystal-polymer layer, the display element is controlled to transmit light, and when a voltage is applied to the liquid crystal-polymer layer, the display device is controlled to light scattering. The electronic device according to claim 4.   The electronic device according to claim 1, wherein the high refractive index layer is an ITO layer.   6. The surface of the substrate opposite to the side on which the high refractive index layer of the display element is disposed is subjected to non-glare treatment and / or anti-reflection treatment. An electronic device according to any one of the above.   6. The electronic apparatus according to claim 1, wherein a color filter is formed on a surface of at least one of the pair of substrates facing the liquid crystal.   6. The electronic apparatus according to claim 1, wherein an active element is formed on a surface of at least one of the pair of substrates facing the liquid crystal. In the liquid crystal used in the display device

(N is an integer, R is an alkyl group, an alkoxy group, a cycloalkyl group or a cycloalkoxy group, R1 and R2 are independently an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, H or F, and X is an H or F group. Or an electronic device according to claim 1, wherein the electronic device includes a compound of C 1 or CN). The polymer used for the display element is

(R and R ′ are each independently H or CH 3. B, B ′ and B ″ are each independently OCO, COO, OCONH, NHCOO, CONH, NHCO, —C═C—, various alkyls, Selected from O, N, and S. A1 and A2 each independently contain an aromatic ring, such as phenyl, biphenyl, terphenyl, quarterphenyl, naphthalene, anthracene, etc. 1 part halogen, alkyl group, cyano 6. The electronic device according to claim 1, wherein the electronic device is polymerized with at least one component as a polymer precursor.

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