JP2000119657A - Manufacture of liquid crystalline polymer layer and manufacture of display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an element which shows bright contrast and good and low driving voltage by forming a liquid crystalline polymer layer comprising a liquid crystal and a polymer obtained by polymerizing a precursor of a polymer having a polymerizable portion and an aromatic ring. SOLUTION: This liquid crystalline polymer layer comprises a liquid crystal and a polymer obtained by polymerizing a precursor of a polymer having a polymerizable portion of a (meth)acrylic acid derivative or the like and an aromatic ring. An electrode 2 and an electrode 5 are formed on substrates 1 and 6, each having a flat surface, and the two substrates are supported keeping a predetermined clearance between them. A mixture of the precursor 3 of the polymer and the liquid crystal 4 is heated to melt and put into the clearance and oriented followed by phase separation into a liquid phase and polymer by means of irradiation of ultraviolet ray to give a transparent element. The precursor of the polymer includes a compound represented by formula I which is a (meth)acrylic acid derivative having not less than 2 aromatic rings in side chains and ester groups between the aromatic rings, a compound represented by formula II having an amide group between the aromatic rings, a compound represented by formula III having acetylene group between the aromatic rings and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer-dispersed liquid crystal display device having a liquid crystal and a polymer dispersed in each other, and more particularly to a display device applied to a man-machine interface such as a computer display or a television and a method of manufacturing the same.

[0002]

2. Description of the Related Art In recent years, with the introduction of a computer into a place of social life, the development of a man-machine interface has been accelerated. Particularly in the field of displays, development is most urgently required, but at present the situation currently relies on a twisted nematic type liquid crystal display element having a dark display using two polarizing plates. Therefore, a polymer dispersed liquid crystal display device has recently been developed. Since this method does not use a polarizing plate, incident light can be used efficiently. In particular, in a mode in which dichroic dyes are mixed, the appearance when used as a reflection type is remarkable. For example, Fergason encapsulates a dichroic dye-containing liquid crystal and disperses it in a polymer (hereinafter referred to as microcapsule-type normal PDLC such as Japanese Patent Publication No. 3-52843). Also, Doane et al. Have proposed a method of mixing a dichroic dye-containing liquid crystal and a polymer precursor and then polymerizing the mixture to separate the liquid crystal and the polymer into a sponge-like phase to produce a display element. Showa 61-502
128, etc.).

Hikmet et al. Of Philips use a polymer precursor in a liquid crystal state, and form a polymer in an oriented state by irradiating ultraviolet rays in a state of being mixed with the liquid crystal, and the liquid crystal is contained in a gel network. (Mol. Crystal. Li)
q. Cryst. , 1992, Vol. 213 pp.
117-131, hereinafter referred to as network-type oriented PDLC).

[0004]

In this method, unlike the mode described above, white scattering occurs when an electric field is applied. on the other hand,
We have independently developed a technology to form polymer particles in an oriented state (European Patent EPO,
488, 116A2, etc.). However, sufficient brightness and contrast have not been obtained in any of the modes. Also, the driving voltage is not sufficiently low.

Accordingly, an object of the present invention is to provide a display device in which liquid crystal and a polymer are aligned and dispersed with respect to each other, which has a good contrast, a low driving voltage, and a method of manufacturing the same.

[0006]

According to the present invention, there is provided a display device in which a liquid crystal and a polymer are aligned and dispersed in one another, wherein the polymer to be used comprises a polymer precursor having a polymerized portion. Further, the polymer precursor contains at least one polymer precursor having a polymer portion and a side chain portion, and contains at least one polymer precursor having two or more polymer portions. May be.
Here, the polymer precursor is an ester derivative with methacrylic acid or acrylic acid, or an amide derivative with methacrylic acid or acrylic acid. Further, the polymer precursor contains a compound having an epoxy group as at least one component. The polymer precursor contains at least two aromatic rings (at least one of these aromatic rings may be hydrogenated) and a compound having an ester group between these aromatic rings as at least one component. You may. Further, the polymer precursor comprises at least two aromatic rings (at least one of these aromatic rings may be hydrogenated) and a compound having a urethane group or an amide group between these aromatic rings as at least one component. It may be contained. Further, the polymer precursor comprises at least one compound having at least two aromatic rings (at least one of these aromatic rings may be hydrogenated) and at least one acetylene group between the aromatic rings. It may be contained. Further, a cyano group, a halogen group or an aromatic ring may be directly or indirectly bonded to the aromatic ring contained in the polymer precursor. Further, an alkyl group or an alkoxy group may be bonded to the polymer precursor. Further, the polymer precursor may contain a polymerizable optically active compound. Further, the polymer may contain a polymerizable compound containing a fluorine element as at least one component. Further, a dichroic dye may be contained in the liquid crystal. Further, a chiral component may be contained in the liquid crystal. Further, the liquid crystal is a nematic liquid crystal. Further, the polymer is formed in a mixture of the polymer precursor and the liquid crystal by stimulating at least one of heat, light, and an electron beam. Further, the polymer is formed by preliminarily polymerizing the polymer precursor, making the polymer compatible with the liquid crystal while heating, and gradually cooling. Further, the polymer is obtained by preliminarily polymerizing the polymer precursor, making the polymer compatible with the liquid crystal using a solvent, developing the polymer on a base plate, and then depositing the polymer while aligning the polymer along the liquid crystal. The solvent is formed by slowly evaporating the solvent. Further, the liquid crystal and the polymer layer are characterized in that the orientation direction is inclined with respect to the substrate surface. Further, the alignment direction of the liquid crystal and the polymer layer is controlled by an alignment treatment on the substrate surface sandwiching the liquid crystal and the polymer. Further, among the substrates for aligning the liquid crystal and the polymer layer, at least the direction of the alignment treatment of the substrate on the incident light side is a direction orthogonal to the main incident light direction and a plane including the substrate radiation. Further, among the substrates for aligning the liquid crystal and the polymer layer, at least the direction of the alignment treatment of the substrate on the incident light side is within a plane including the main incident light direction and the substrate emission line. Further, a light reflecting layer or a light scattering layer is arranged on the back surface of the liquid crystal and polymer layers. A wavelength compensator (for example, 1) is provided between the liquid crystal and polymer layers and the reflective layer or light scattering layer.
/ 4 wavelength plate). Further, a color filter is formed on at least one of the substrates holding the liquid crystal and the polymer layer. An active element, for example, a two-terminal element or a three-terminal element is formed on at least one of the substrates sandwiching the liquid crystal and the polymer layer. Further, the two sets of display elements are overlapped so that the alignment directions of the liquid crystal and the polymer are orthogonal to each other. The mixture of the polymer precursor and liquid crystal in the liquid crystal phase, heat,
The method is characterized by a method of manufacturing a display element in which the liquid crystal and the polymer layer are formed by irradiating at least one of light and an electron beam. Further, the present invention is characterized in that the polymer precursor is polymerized in advance, the polymer precursor is made compatible with the liquid crystal while being heated, and then gradually cooled to form the polymer layer with the liquid crystal. The polymer precursor is polymerized in advance,
Compatible with the liquid crystal and the solvent, and after being spread on the substrate, the solvent is slowly distilled off to such an extent that the polymer is deposited while being oriented along the liquid crystal to form the liquid crystal and the polymer layer. It is characterized by a method for manufacturing a display element.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to explain the present invention in more detail, the present invention will be described by way of example with reference to the accompanying drawings.

(Embodiment 1) In this embodiment, a polymer precursor is a methacrylate or acrylate derivative having two or more aromatic rings in a side chain, and at least one of the aromatic rings is hydrogenated. An example using a polymer precursor having an ester group between these aromatic rings will be described. FIG. 1 shows a cross-sectional view of the horizontal alignment type display element of the present invention. FIG. 2 is a sectional view of the vertical alignment type display device of the present invention. As described above, the present invention is a technique applicable to both the horizontal alignment type and the vertical alignment type. In this embodiment, a case of a horizontal alignment type will be mainly described for simplicity. In all of the following examples, a description will be given of a method of manufacturing a device in which a vertical alignment process is performed on an element substrate in the case of a vertical alignment type and liquid crystal having a negative dielectric anisotropy may be used. First, the electrodes 2 and 5 were formed on the surfaces of the substrates 1 and 6 having flat surfaces. Either of these electrodes may be a reflective electrode. These substrates were subjected to an alignment treatment. It was fixed so that the gap between the two substrates was 5 μm. This gap need not be 5 microns, but may be determined according to the application. For example, if the transmission type is used, the optical path length is halved, so that sufficient contrast cannot be obtained unless it is set to 10 microns which is twice 5 microns.

As a precursor of polymer 3, 4-benzoyloxyphenyl methacrylate

[0010]

(Equation 1)

1: 9 liquid crystal 4 (PNOO2: 1-10% S-1011 as a chiral component in Roddick, S-428: 1.5% mixed with Mitsui Toatsu Dye as a dichroic dye) When the mixture was sealed and the mixture was oriented and irradiated with ultraviolet light, the liquid crystal and the polymer were phase-separated, and an almost transparent device was produced.

Next, measurement of the element will be described. A reflector was arranged on the back of the display element, an AC electric field of 10 kHz was applied between the two electrodes, and the reflectance of light when the voltage was changed was measured. Then, the display state started to be inverted at 3.3 V (reflectance 5%) and saturated at 4.8 V (reflectance 190%). Although slightly smaller than the conventional example, the driving voltage is reduced and the degree of scattering is improved. The reflectance is 100% for white paper. At this time, if the element is arranged such that the orientation direction of the polymer on the element front side or the element back side is perpendicular to the plane including the direction of the incident light and the normal to the element surface, the reflectivity seems to be improved. On the other hand,
4. When a device was produced in the same manner as in the present invention using the photocurable biphenyl derivative 4-biphenylmetallate as a polymer precursor, the display state began to be inverted at 3.5 V (reflectance: 5%). Saturated with OV (reflectance 180%). Here, 100% is the reflectance when white paper is arranged in place of the display element. It can be seen that the scattering degree of this embodiment is clearly improved at a low voltage.

The characteristics of the device were measured with a transmission type optical system. At this time, the electrode of the display element substrate is used as a transparent electrode, and 2
A display element was prepared without adding a chromatic dye, and the brightness of light passing through the element was measured with incident light having a brightness of 100%. At this time, an aperture was arranged immediately before the light detector in order to remove scattered light from the device. The diameter of the hole of the aperture at this time was set so that the expected angle of the element was 3 degrees. The electric field applied to the display element was applied under the conditions described above. At this time, the display state began to be inverted at 3.5 V (transmittance: 85%) and saturated at 5.0 V (transmittance: 5%). Thus, it can be applied to both the transmission type and the reflection type.

Next, as an example containing three or more aromatic rings, an example using a compound containing an ester group between a biphenyl group and a phenyl group will be described. For example, 4- (4'-biphenylcarboxy) phenyl methacrylate

[0015]

(Equation 2)

Was used. An element was manufactured in the same manner as in the method described above, and was driven in the same manner. The display state starts to be inverted at 4 V (reflectance: 5%) and becomes saturated at 5.5 V (reflectance: 19
0%). The same effect was exhibited in the transmission type.

Next, an example in which a polymer precursor containing a naphthalene group and the direction of addition of the ester group is reversed will be described. Devices other than the polymer precursor were prepared under the conditions described above. Here, the UV-curable polymer precursor is 4-
(2'-naphthoxycarbonyl) phenyl methacrylate

[0018]

(Equation 3)

Was used. The display state started to be inverted at 3 V (reflectance 5%), and saturated at 4 V (reflectance 80%). The same effect was exhibited in the transmission type.

As described above, the polymer precursor has a skeleton other than those shown in the present embodiment.

[0021]

(Equation 4)

The same effect can be obtained by having the basic skeleton shown in FIG.

Here, the polymer portion may be any polymer group used for a polymer such as acryl, methacryl, crotonic acid, fumaric acid, maleic acid, vinyl group, epoxy group and the like. Of course, R in the chemical formula may be an alkyl group or another substituent. Further, a polymer precursor having a polymerized portion which is cured by heat or an electron beam can also be used. As for the aromatic ring, at least one aromatic ring may be hydrogenated. For example

[0024]

(Equation 5)

May be used. The aromatic ring is not limited to a phenyl group, and may be a polycyclic aromatic ring such as biphenyl, terphenyl, naphthalene, and anthracene. In addition, although the substitution mode of the aromatic ring is para-substitution, the element can be operated as a meta-substitution or ortho-substitution. However, the degree of scattering tends to decrease. Further, here, the aromatic ring has no substituent other than the bond to another aromatic ring, but as shown later, a cyano group, a halogen group,
By inserting a substituent such as an alkyl group or an alkoxy group, excellent properties can be exhibited. Further, at least one structure such as a urethane group, an amide group, and an acetylene group described later can be incorporated. Further, H in the compound can be substituted by fluorine.

Here, ultraviolet light is used as an external field used for the polymerization, and its wavelength and intensity are from 4 to 300 nm.
Although a light having a wavelength of 00 nm and an intensity of 2 mW / cm 2 was used, any wavelength and intensity may be used as long as the polymer precursor is polymerized. In particular, when a weak light is irradiated for a long time, when a dichroic dye is used, the dye is hardly contained in the polymer, and the characteristics are improved. Further, if a polymerization initiator or a sensitizer is mixed, the polymerization can be effectively advanced. In addition, the polymerization can be carried out by an electron beam. For example, if an electron beam accelerated at 250 KV is used and the thickness of the substrate on the electron beam incident side is made sufficiently small (for example, 100 μm) and the electron beam is made incident, polymerization can be sufficiently performed. It is also possible to mix with a polymerization initiator and carry out polymerization by heat.

The alignment treatment may be performed by a conventionally used means, for example, rubbing the substrate, forming an alignment film and rubbing it, oblique deposition, a method using an LB film,
Any method can be used as long as the liquid crystal phase is aligned, such as a method using a vertical alignment agent. Further, the alignment treatment is effective even with only one side of the substrate. The orientation direction of the substrate may be any direction, and the orientation direction may be different between the front substrate and the back substrate, but it is optimized according to the incident direction of the light used and the scattering profile required for the element. There is a need. Further, as will be described later, by tilting the orientation direction of the polymer with respect to the substrate surface, the driving voltage can be reduced and the clear viewing direction can be optimized.

The liquid crystal used here preferably has a refractive index anisotropy Δn as large as possible. The liquid crystal may have a positive dielectric anisotropy. The content of the liquid crystal is optimally 50 to 97% based on the polymer monomer. If the content of the liquid crystal is less than this, no response to the electric field occurs, and if it is more than this, contrast cannot be obtained. In addition, if liquid crystal having high specific resistance is used, it can be driven by an active element.

The dichroic dye used here can be used even if it is not shown here, and the content ratio may be optimized according to the application. Electric field O if dichroic dye is not mixed
It was possible to set the mode to be transparent in FF and to scatter white when the electric field was ON.

Here, the chiral component is mixed, but any chiral component may be used, and the content may be determined according to the application. When a large amount is inserted, the driving voltage increases, but memory properties are exhibited. Also, the device operates as an element without a chiral component.

Example 2 In this example, the polymer precursor is a methacrylate or acrylate derivative, has two or more aromatic rings in the side chain, and at least one of the aromatic rings is hydrogenated. An example using a polymer precursor having a urethane group or an amide group between these aromatic rings will be described. 4-methacryloyloxyphenyl-phenylcarbamate as a polymer precursor

[0032]

(Equation 6)

Was used. The manufacturing conditions of the device were the same as in Example 1.

The electro-optical characteristics of the device were measured by the method of Example 1. The display starts to be inverted at 3.5 V (reflectance 5
%) And saturated at 5 V (reflectance: 180%).

Next, an example in which an amide group is used as a polymer precursor will be described. Phenylcarbamoylphenyl-4-methacrylate as polymer precursor

[0036]

(Equation 7)

A device was manufactured under the same conditions as in Example 1.

The electro-optical characteristics of the device were measured by the method of Example 1. The display starts to be inverted at 3.5 V (reflectance 5
%) And saturated at 5 V (reflectance: 180%).

As described above, the polymer precursor has a skeleton other than those shown in this example.

[0040]

(Equation 8)

The same effect can be obtained by having the basic skeleton shown in FIG. Here, the polymer portion may be any polymer group used for a polymer such as acrylic, methacrylic, crotonic acid, fumaric acid, maleic acid, vinyl group, epoxy group, and the like. Of course, R in the chemical formula may be an alkyl group or another substituent. Further, a polymer precursor having a polymerized portion which is cured by heat or an electron beam can also be used. As for the aromatic ring, at least one aromatic ring may be hydrogenated. For example

[0042]

(Equation 9)

May be used. The aromatic ring is not limited to a phenyl group, and may be a polycyclic aromatic ring such as biphenyl, terphenyl, naphthalene, and anthracene. In addition, although the substitution mode of the aromatic ring is para-substitution, the element can be operated as a meta-substitution or ortho-substitution. However, the degree of scattering tends to decrease. Further, here, the aromatic ring has no substituent other than the bond to another aromatic ring, but as shown later, a cyano group, a halogen group,
By inserting a substituent such as an alkyl group or an alkoxy group, excellent properties can be exhibited. Further, at least one structure such as an ester group shown in Example 1 and an acetylene group shown later can be incorporated. Further, H in the compound can be substituted by fluorine.

Other element components, manufacturing conditions and applications are the same as in Example 1. (Example 3) In this example, the polymer precursor is a methacrylic acid ester or acrylate derivative.
Having two or more aromatic rings in the side chain, at least one of the aromatic rings
One example may be hydrogenated and has an acetylene group between these aromatic rings. First, an example using a polymer precursor having two polymerized portions will be described. Di (paramethacryloyloxyphenyl) acetylene as a polymer precursor

[0045]

(Equation 10)

Using Example 1 and other manufacturing conditions,
According to the same conditions as above. The liquid crystal and polymer were phase separated.

The electro-optical characteristics of the display device thus obtained were measured in the same manner as in Example 1. Display inversion started at 4 V (reflectance 5%), and was saturated at 6 V (reflectance 210%).

Next, an example using an acetylene compound having one polymerized part will be described. Paramethacryloyloxytran as a polymer precursor having one polymerized part

[0049]

[Equation 11]

Was used. The manufacturing conditions other than the polymer precursor are the same as in Example 1.

The electro-optical characteristics were measured in the same manner as in Example 1.
Display reversal started at 3.5 V (reflectance: 5%) and saturated at 5.5 V (reflectance: 200%).

Next, an example using a polymer precursor having two triple bonds and not containing an alkyl side chain will be described. An element was manufactured under the conditions in Example 1. Here, 1- (4′-methacryloyloxyphenyl) -4-phenyl-1,3-butadiyne is used as the polymer precursor.

[0053]

(Equation 12)

Was used.

Next, the electro-optical characteristics of the device were measured in the same manner as in Example 1. Display inversion started at 3.5 V (reflectance: 5%) and became saturated at 5.5 V (reflectance: 200%).

The polymer precursor used here has two polymerized parts.

[0057]

(Equation 13)

Those having one polymerized part have the general formula

[0059]

[Equation 14]

Can be written as Here, various compounds can be used in combination of X, Y, 1, m, and n. For example, n = 2 and two acetylene skeletons can be connected.

X is repeated a plurality of times when n is plural, but of course the skeleton may be changed each time.
The same applies to m. In addition to the aromatic ring and the acetylene skeleton, it may have a skeleton that increases the refractive index anisotropy. Furthermore, these polymer precursors are converted into other polymer precursors,
For example, it may be used by mixing with a monofunctional polymer precursor such as biphenyl methacrylate. Here, the polymerization part is acrylic, methacrylic, crotonic acid, fumaric acid, maleic acid,
Any polymer group used for a polymer, such as a vinyl group and an epoxy group, can be used. Of course, R in the chemical formula may be an alkyl group or another substituent. Further, a polymer precursor having a polymerized portion which is cured by heat or an electron beam can also be used. As for the aromatic ring, at least one aromatic ring may be hydrogenated. The aromatic ring is not limited to a phenyl group, and may be a polycyclic aromatic ring such as biphenyl, ta-phenyl, naphthalene, and anthracene. In addition, although the substitution mode of the aromatic ring is para-substitution, the element can be operated as a meta-substitution or ortho-substitution. However, the degree of scattering tends to decrease. Further, here, the aromatic ring has no substituent other than the bond with another aromatic ring, but as shown later, excellent properties can be obtained by inserting a substituent such as a cyano group, a halogen group, an alkyl group, or an alkoxy group. Can also be expressed. Further, at least one structure such as an ester group, an amide group, or a urethane group described above can be incorporated. Also,
H in the compound may be replaced by fluorine.

In this embodiment, the bifunctional and monofunctional polymer precursors are shown. However, when the bifunctional polymer precursor is used in combination with the monofunctional polymer precursor, the driving voltage is low and the heat resistance is low. A display element with good durability can be manufactured.

(Embodiment 4) This embodiment shows an example in which the polymer precursor is an amide of acrylic acid or methacrylic acid. Biphenyl methcuramide as polymer precursor

[0064]

(Equation 15)

A device was manufactured under the same conditions as in Example 3.

The electro-optical characteristics of the device were measured by the method of Example 1. The display starts to be inverted at 3.5 V (reflectance 5
%) And saturated at 5 V (reflectance: 180%).

N-methylbiphenylmethacrylamide and the like can be used in the same manner.

The polymer precursor used here is

[0069]

(Equation 16)

As shown in the above, it is sufficient that the side chain opening has an aromatic ring, and even if there are a plurality of aromatic rings, it functions as a display element. In Examples other than the present Example, the polymer group can be similarly used as a polymer precursor by changing the ester group connecting the polymerized part and the side chain part to an amide group. A display element can be manufactured. The aromatic ring is not limited to a phenyl group, and may be a polycyclic aromatic ring such as biphenyl, ta-phenyl, naphthalene, and anthracene. In addition, although the substitution mode of the aromatic ring is para-substitution, the element can be operated as a meta-substitution or ortho-substitution. Here, the aromatic ring does not contain any substituents other than a bond with another aromatic ring, but as shown later, a cyano group,
By inserting a substituent such as a halogen group, an alkyl group, or an alkoxy group, excellent properties can be exhibited. Further, at least one structure such as an ester group, an amide group, a urethane group, and an acetylene group described above can be incorporated. Further, at least one structure such as the ester group, amide group, urethane, and acetylene group described above can be incorporated. Further, H in the compound can be substituted by fluorine. Here, the polymer portion may be any polymer group used for a polymer such as acrylic, methacrylic, crotonic acid, fumaric acid, maleic acid, vinyl group, epoxy group, and the like. Of course, R in the chemical formula may be an alkyl group or another substituent. In the present compound, N
, H, CH3, an alkyl group and other substituents can be introduced into N. Of course, it may be a polymerizable substituent.

Embodiment 5 This embodiment shows an example in which a cyano group, a halogen group, or an aromatic ring is directly or indirectly bonded to an aromatic ring contained in a polymer precursor. As a polymer precursor

[0072]

[Equation 17]

As shown in the above, biphenyl methacrylate obtained by substituting a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, an aromatic ring and the like was used. The liquid crystal material, substrate relation, manufacturing conditions, and measurement conditions were as in Example 1. With respect to the electro-optical characteristics, when the cyano group was substituted, the display state started to be inverted at 3 V (reflectance: 5%) and saturated at 4.5 V (reflectance: 200%). When the halogen group is substituted, the reflectance when an electric field is applied is improved as compared with the case where no halogen group is substituted, and the iodine group (reflectance 195%)
> Bromo group (reflectance 190%)> Chloro group (reflectance 18)
5%) l> fluoro group (reflectance: 180%). When substituted with a phenyl group, the reflectance is 2
Very bright display is possible at 20%.

In addition, although the substitution mode of the aromatic ring is para-substitution, the device can operate as a device even with meta-substitution or ortho-substitution. The basic skeleton of the polymer precursor used here is, in addition to a phenyl group on the aromatic ring, biphenyl, ta-phenyl, naphthalene,
Polycyclic aromatic rings such as anthracene and the basic skeleton in Examples other than this Example can also be used. For example

[0075]

(Equation 18)

[0076]

[Equation 19]

[0077]

(Equation 20)

[0078]

(Equation 21)

As shown here, the substituents shown here may be introduced directly or indirectly, and the number thereof is not limited to one. Further, two or more ester groups, amide groups, urethane groups, acetylene groups and the like shown here may be included, including different types. In short, all of the compounds shown in the present invention can be used as the basic polymer precursor. In addition, the substitution method is not limited to bulk substitution, and meta-substituted ortho-substitution can be used. Of course, the same effect is exhibited even when a plurality of types of substituents are introduced. When an aromatic ring is used as a substituent, the aromatic ring may be directly or indirectly substituted with at least one or more or at least one kind of substituent, alkyl group or alkoxy group as described herein. Further, the polymer precursors shown here may be used in combination with each other or with the polymer precursors shown in other embodiments. Here, the polymer portion may be any polymer group used for a polymer such as acrylic, methacrylic, crotonic acid, fumaric acid, maleic acid, vinyl group, epoxy group, and the like. Of course, R in the chemical formula may be an alkyl group or another substituent. Since chemical formula 21 contains N, H, CH3, an alkyl group and other substituents can be introduced into N. Of course, it may be a polymerizable substituent.

(Embodiment 6) In this embodiment, an example using a polymer precursor containing fluorine will be described. Pentafluorobenzoyloxyphenyl methacrylate as a polymer precursor

[0081]

(Equation 22)

The liquid crystal, the substrate periphery, and the manufacturing conditions are the same as in the first embodiment. When the electro-optical characteristics were measured,
3. The display state starts to be inverted at 3.3 V (reflectance: 5%);
Saturated at 6 V (reflectance 200%).

The polymer precursor used here is a compound containing fluorine in the polymerized portion in addition to the above-mentioned examples, for example,

[0084]

(Equation 23)

Here, at least one of Y1, Y2 and Y3 contains fluorine, and it is desirable to use an alkyl group such as H, F, CH3 and CF3, but other substituents may be used. R preferably uses an ester substituent containing at least one phenyl group. For example, -CO2-
C6F4-C6F5, -CO2-C6F4-C6F4-
OCO-C6F5 (F may be partially H or another substituent such as a phenyl group) or the like can be used. The ester groups may be bonded in reverse. More preferably, the phenyl group is substituted with fluorine. R may be an ether substituent, an alkyl substituent, or the like in addition to the ester substituent, but basically, a substance having a refractive index close to that of a liquid crystal is selected. Further, regarding the fluorine substitution amount and the substitution site, it is preferable to select a fluorine substitution amount and a substitution site such that the polymer precursor is compatible with the liquid crystal before polymerization, and is not compatible with the liquid crystal and the dye after polymerization. .
R may include the polymerization site described above, that is, one compound may have a plurality of polymerization sites. For example

[0086]

(Equation 24)

[0087]

(Equation 25)

Compounds such as Also, here, the case where all the substitution modes of the benzene ring are in the rose position is shown, but they may be in the meta position or the ortho position. Further, these polymer precursors may be used in combination with each other or with another polymer precursor such as biphenyl acrylate. Here, the polymerized portion may be any polymerized group used for polymers, such as acrylic, methacrylic, crotonic acid, fumaric acid, maleic acid, vinyl group, epoxy group and the like. As described above, any material that can be subjected to ultraviolet polymerization or electron beam polymerization can be used. In addition, a polymerization unit that performs thermal polymerization can also be used.

Example 7 This example shows an example in which an aromatic ring is directly or indirectly substituted with an alkyl group or an alkoxy group as a polymer precursor.

First, an example in which a compound having an alkoxy group on an aromatic ring in Example 1 is used will be described. An element was manufactured under the same conditions as in Example 3 except for the polymer precursor. Here, 4- (4'-butoxybenzoyl) is used as the polymer precursor.
Phenyl methacrylate

[0091]

(Equation 26)

Was used. When the electro-optical characteristics were measured in the same manner as in Example 1, the display started to be inverted at 3 V (inversion ratio: 5%) and saturated at 4.5 V (reflectance: 200%).
Similarly, the transmission type has an effect.

Next, an example in which a compound having an alkyl side chain on an aromatic ring in Example 1 will be described. An element was manufactured under the same conditions as in Example 3 except for the polymer precursor. Here, 4- (4'-bentylbenzoyl) is used as the polymer precursor.
Phenyl methacrylate

[0094]

[Equation 27]

Was used. When the electro-optical characteristics were measured in the same manner as in Example 1, the display started to be inverted at 3 V (reflectance 5%) and saturated at 4.4 V (reflectance 200%).

Next, an example using an example in which an alkyl chain is bonded to the basic skeleton shown in Example 2 will be described. Here, 4-methacryloyloxyphenyl-4'-butoxyphenylcarbamate is used as the polymer precursor.

[0097]

[Equation 28]

Was used. The manufacturing conditions of the device were the same as in Example 1. The electro-optical characteristics of the device were measured by the method of Example 1. The display starts to be inverted at 3.4 V (reflectance 5%),
It was saturated at 4.8 V (reflectance 180%).

Next, an example in which an alkoxy group is bonded to the basic skeleton shown in Example 3 will be described. An element was manufactured under the same conditions as in Example 1. Here, 4-methacryloyloxy-4′-hexyloxytran was used as the polymer precursor.

[0100]

(Equation 29)

Was used. The electro-optical characteristics of the device were measured in the same manner as in Example 1. Display inversion starts at 3.4 V (reflectance 5%) and saturates at 5.4 V (reflectance 200
%).

Next, examples in which an alkyl group or an alkoxy group is indirectly bonded to an aromatic ring will be described.

[0103]

[Equation 30]

Here, the group linking the aromatic ring and the alkyl group is an ester, ether, amide or alkyl chain. The characteristics do not change much depending on the structure of this place.

As in the polymer precursor used in this example,
By introducing an alkyl group or an alkoxy group, the threshold voltage can be lowered while the reflectance is improved. As the basic polymer precursor, the compounds shown in all the examples of the present invention can be used. Regarding the length of the alkyl group or the alkoxy group, an experiment was conducted up to 9 carbon atoms, and it was confirmed that the device operates as a device. If the alkyl group or the alkoxy group is too long, the reflectance at the time of transparency increases and the contrast deteriorates. Desirably, those having 3 to 6 carbon atoms may be directly bonded to the aromatic ring portion.
It may be bonded via a hetero atom such as an ester bond. Regarding the substitution position, all experiments were performed with para substitution,
Similar effects can be expected with meta or para substitution. In some cases, these alkyl groups or alkoxy groups may be substituted with those having a large dipole moment such as a halogen atom and a cyano molecule. Further, these substituents may be substituted on a plurality of aromatic rings. Here, the polymer portion may be any polymer group used for a polymer such as acrylic, methacrylic, crotonic acid, fumaric acid, maleic acid, vinyl group, epoxy group and the like. Of course, CH3 of the methacryl group in the chemical formula may be an alkyl group or another substituent.

(Embodiment 8) This embodiment shows an example in which the polymer precursor is optically active. The polymer precursor used is 4'-
(2 ″ (S) -methylpropoxy) biphenyl-4
-Methacrylate

[0107]

(Equation 31)

The liquid crystal material, element surroundings, and manufacturing conditions were the same as in Example 1. The electro-optical characteristics of the device were measured. Then, the display state starts to be inverted at 3 V (reflectance 5%),
It was saturated at 4.5 V (reflectance: 200%).

Here, the same effects as those of the polymer precursor other than those used in this example can be obtained as long as they are optically active. For example, the general formula

[0110]

(Equation 32)

As an example, 4- (2 ′ (S) -methylpropoxy) phenyl methacrylate

[0112]

[Equation 33]

And the like can be used. That is, a substituent having a chiral center may be introduced into the compounds shown in all the examples of the present invention. The substitution mode for the aromatic ring is para-substitution here, but may be meta-substitution or ortho-substitution. Further, it may be substituted with another substituent at the same time. Further, an optically active polymer precursor can be used as one component of the polymer precursor. Here, the polymerization part is acrylic, methacrylic, crotonic acid, fumaric acid, maleic acid,
Any polymer group used for a polymer, such as a vinyl group and an epoxy group, can be used. Of course, R in the chemical formula may be an alkyl group or another substituent.

Next, an example in which an optically active polymer precursor is used as one of the polymer precursors will be described. 4 ′-(2 ″ (S) -methylpropoxy) biphenyl-4-methacrylate and 4-
A mixture of biphenyl methacrylate at 1: 1 was used as a polymer precursor. Other configurations, manufacturing methods, conditions, and the like are the same as those in the first embodiment.

The element manufactured in this way had characteristics intermediate between the characteristics shown in the previous example of this embodiment and the characteristics of the conventional example. The optically active polymer precursor has a different molecular turning ability depending on the skeleton. If the turning ability is too large, the drive voltage will increase,
As shown here, it is necessary to dilute with an optically inactive polymer precursor.

In this embodiment, the S-form is used as the optically active substance, but the R-form can be used in exactly the same manner. Also, the liquid crystal shown here did not contain a chiral component,
Even if a chiral component is mixed, the contrast and brightness can be further improved.

(Embodiment 9) This embodiment shows an example in which a bifunctional molecule precursor and a monofunctional polymer precursor are mixed. The polymer precursors used here were cyanobiphenyl methacrylate and phenyl dimethacrylate

[0118]

(Equation 34)

Is a mixed system (here, 2: 1). The mixing ratio is not limited to this. The liquid crystal, the device periphery, and the manufacturing conditions were the same as in Example 1. According to this, the electro-optical properties were able to improve heat resistance and reliability without impairing the properties of the monofunctional polymer precursor (the polymer was melted at 100 ° C. in the past; Insoluble). Similar effects were observed for the polymer precursors in all Examples of the present invention. 1
The bifunctional polymer precursor mixed with the functional polymer precursor is

[0120]

(Equation 35)

In addition, the compounds shown in Example 3 and H
used by ikmet et al.

[0122]

[Equation 36]

A polymer precursor having a liquid crystal phase as described above, having a bisphenol A skeleton

[0124]

(37)

The following compounds can also be used. In this case, it is not necessary to include an aromatic ring. For example

[0126]

(38)

An acrylic or methacrylic group may be attached to both ends of the alkyl chain as described above. Here, the polymer portion may be any polymer group used for a polymer such as acrylic, methacrylic, crotonic acid, fumaric acid, maleic acid, vinyl group, epoxy group, and the like. Of course, R in the chemical formula may be an alkyl group or another substituent. Also,
It may not be bifunctional, but may be a trifunctional or higher polyfunctional polymer precursor (for example, M7100
(Example 10) In this example, an example in which two types of polymer precursors are used will be described. The same substrate as in Example 1 was used. Here, 4-benzoyloxyphenyl methacrylate and methacryloyloxyphenyl-4′-methylphenylcarbamate are used as polymer precursors.

[0128]

[Equation 39]

Using these precursors at a ratio of 1: 1 (W:
W), and a device was prepared under the same conditions as in Example 1.

The electro-optical characteristics of the device were measured by the method of Example 1. The display starts to be inverted at 3.5 V (reflectance 5
%) And saturated at 5 V (reflectance: 180%).

When two or more kinds of polymer precursors can be used as a mixture, the precursors to be mixed can be the polymer precursors described in all the examples of the present invention. Further, the mixing amount and the composition ratio with the liquid crystal are not limited to those in the present embodiment, but need to be optimized each time.
Further, as shown in Example 9, a polyfunctional polymer precursor may be mixed with such a mixed system of monofunctional polymer precursors. Here, the polymer portion may be any polymer group used for a polymer such as acrylic, methacrylic, clonic acid, fumaric acid, maleic acid, vinyl group, epoxy group, and the like.

(Embodiment 11) This embodiment shows an example in which a substrate subjected to a vertical alignment treatment is used. FIG. 2 shows a cross-sectional view of the display element of this embodiment. A method for manufacturing the element will be described. This is the same as Example 1 except that the substrate surface is subjected to a vertical alignment treatment, and the liquid crystal has a negative dielectric anisotropy, ie, a liquid crystal RDP007775 (made by Roddick Co., Ltd., but without or with a very small amount of chiral component).

The polymer precursor used was 4'-fluorobiphenyl methacrylate

[0134]

(Equation 40)

Is as follows.

The electro-optical characteristics were measured by the method of Example 1. However, a non-directional reflector is used as the reflector. Display starts to be inverted at 7V (reflectance 100%) 15V
(Reflectance 10%). Since the characteristics are opposite to those of the horizontal alignment type, different applications can be expected. It can be applied to light valves by using the transmission type. The polymer precursor used here is only used as a representative of the present invention, and all polymer precursors of the present invention can be used. Regardless of the liquid crystal shown here, any liquid crystal can be used as long as the large dielectric anisotropy of Δn is negative.
Also, it functions as a display element with or without a dichroic dye.

(Embodiment 12) This embodiment shows an example in which the orientation direction of the polymer is inclined with respect to the substrate surface. FIG. 3 shows a cross-sectional view of the display element of this example. A method for manufacturing an element will be described. JAS23 and JIB are used as pretilt alignment agents on the surfaces of substrates 1 and 6 on which electrodes 2 and 5 are formed.
(All manufactured by Nippon Synthetic Rubber Co., Ltd.) were mixed and applied at a ratio of 1: 1 and dried, followed by horizontal orientation treatment. Using the substrate thus manufactured, a display element was manufactured according to Example 1.

Display starts to be inverted at 3 V (reflectance: 5%) 4
It was saturated with V (reflectance 170%).

It can be seen that the driving voltage is low.
The polymer precursor used here is only used as a representative of the polymer precursor of the present invention, and all polymer precursors of the present invention can be used. This embodiment can be applied to all embodiments of the present invention.

(Example 13) In this example, the above polymer precursor was used, and RDP00 having a high specific resistance was used as a liquid crystal.
536 (produced by Roddick), S-1 as a chiral component
011 (manufactured by Merck) as a dichroic dye S-344
An example in which an active element is used as an element substrate using (manufactured by Mitsui Toatsu Dye Co., Ltd.) will be described.

First, the liquid crystal composition sealed between the substrates will be described. The liquid crystal RDP00536 shown above has S-1
011 and 0.5% of S-344 were mixed, and 8% of 4-benzoyloxyphenyl methacrylate and 2% of tetrafluorophenyl dimethacrylate 2 used in Example 1 were mixed.
% Mixed.

Next, a substrate with an active element for enclosing the liquid crystal composition will be described. FIG. 4 shows a partial cross-sectional view of the display element of this embodiment. An example in which a MIM element is used as an active element will be described. Substrate 1 has transparent electrode 2 as IT
O was formed and the surface was subjected to an orientation treatment. After a tantalum layer 7 was formed on the substrate 6, the surface was oxidized to form an insulating layer 8 and further a reflective pixel electrode 9 (optionally a non-directional reflection process). A protective layer may be provided on the element surface for protecting the active element. Further, the surface was subjected to an orientation treatment. The substrate 1 and the substrate 6 were fixed so that the electrode surfaces faced each other with a gap of about 5 μm so that the orientation directions were substantially parallel between the upper and lower substrates. Here, the active element substrate side is subjected to reflection processing to make the opposing substrate transparent, but conversely, the opposite substrate side may be subjected to reflection processing to make the element substrate side transparent. Although the reflective layer and the electrode are integrated here, the electrode and the reflective layer may be separate.

The liquid crystal composition described above was sealed in the empty panel thus produced, and the liquid crystal and the polymer were phase-separated by irradiating ultraviolet rays to photopolymerize the polymer precursor.

When a signal for driving the MIM element is applied to the display element thus manufactured (selection period: 60 microseconds, non-selection period: 16 milliseconds), the display is inverted by a signal having a peak value of 35 V and the reflectance is 150%. Was. The reason why the reflectivity is lower than that of the previous embodiment is that the aperture ratio of the active element substrate is as low as 70%.

Any liquid crystal having a high holding ratio, specifically a liquid crystal having a high specific resistance (10 10 Ωcm or more), a large dielectric constant, and a large birefringence can be used. it can.

The chiral component can be used without being limited to those shown here. As the chiral component, a polymer precursor having a chiral center as shown in Example 8 can also be used. Also, the mixing ratio is not limited to the amount shown here. However, if the mixing ratio is too large, the hysteresis increases and the driving voltage tends to increase.

The dichroic dye preferably has a large dichroic ratio with little absorption in the ultraviolet region. The color of the dye can be arbitrarily selected depending on the application. The content of the dye is not limited to the amount shown here, but if it is too large, the dye crystallizes or the display becomes dark.

The polymerization initiator was not used here, but may be used including a photosensitizer. However,
Use with care because the specific resistance tends to decrease.

As the polymer precursor to be used, the polymer precursor shown in all the examples of the present invention can be used. In particular, when a bifunctional or polyfunctional polymer precursor is mixed, phenomena such as burn-in of a display state are less likely to occur even if the polymer content is reduced. The content of the polymer precursor may not be the amount shown here, but if it is too small, the scattering degree becomes weak, and if it is too large, the driving voltage becomes high.

As the polymerization conditions, those described in Example 1 can be used. However, the polymerization is carried out with care because the specific resistance decreases and the price is low. The light intensity was 3 mW / cm 2, but is not limited to this. If the light intensity is low, the polymerization time is lengthened, and if the light intensity is high, the polymerization time is shortened. However, if the light intensity is too strong, the specific resistance tends to decrease. If it is slightly heated (about 20 to 50 ° C.) during the photopolymerization time, it is easy to polymerize.

Although aluminum is used for the reflective electrode used here, any electrode that reflects light, such as silver, nickel, or chromium, can be used. Alternatively, the electrode may be transparent, and a reflective background plate 9 may be used on the back side of the element.

Although the MIM element is used here as an active element, any element that can drive liquid crystal such as a TFT element can be used as described later.

For the alignment treatment, any method may be used as long as the liquid crystal is aligned. As described in the twelfth embodiment, it is of course possible to incline and orient the substrate surface. Vertical alignment treatment may be performed. However, in this case, a negative liquid crystal having a dielectric anisotropy must be used as the liquid crystal. Also, the orientation direction may be optimized according to the application because the clear viewing direction changes.

In this embodiment, the reflection processing is not performed, and if no dye is added, the display device can be used as a transmission type display element or a light valve.

(Embodiment 14) Next, an example in which a color filter is used in combination with an active element will be described. FIG. 5 shows a partial cross-sectional view of a color display element using a TFT element. Actually, the pixels corresponding to each color as shown here are arranged in a mosaic or grid pattern. Example 13 can be used as it is for the liquid crystal 4 and the three polymer layers. The TFT element will be described.
First, a gate electrode 11 is formed on a substrate 6, a gate insulating layer 14 is formed thereon, and a semiconductor layer 12 and a drain electrode 1 are formed thereon.
3. A source electrode 10 and a pixel electrode 9 also serving as a reflective layer (non-directional reflection processing is performed as necessary) were formed. Further, a protective layer may be provided on the pixel electrode for protecting the active element. Further, an alignment treatment was performed on the pixel electrode. Next, the counter substrate 1
However, after forming the color filter 15, the transparent electrode 2 was formed, and an alignment treatment was performed thereon.

In this way, two substrates were prepared and bonded so that the liquid crystal layer had a thickness of about 5 μm with the electrode side inside. The liquid crystal layer does not have to be 5 microns, but if it is too thick, the driving voltage will be high and it will not be possible to drive the TFT element. Here, the active element substrate was subjected to reflection processing,
Conversely, the opposite substrate side may be subjected to reflection processing. The position of the color filter may be on the surface side of the display element or on the reflection substrate side. Further, it may be between the electrode and the substrate or between the electrode and the liquid crystal layer.

A mixture of a liquid crystal and a polymer precursor corresponding to the display mode was sealed in the gap, and an external field was applied if necessary to produce a device.

Example 13 can be used for all the liquid crystal, polymer precursor, dichroic dye, chiral component and production conditions used here.

In this embodiment, the reflection processing is not performed, and if no dye is used, the display device can be used as a transmission type display element or a light valve.

As described above, the example using the active element has been described. According to the present embodiment, a large-capacity reflective color display element can be manufactured, and a full-color display can be realized.

In this embodiment, a TFT is used as an active element.
In addition to the element and the MIM element, T
An FT or MIM element can be used, and an active element using a ferroelectric can be used in exactly the same manner.

(Example 15) This example shows an example in which a polymerizable compound having an epoxy group is used as at least one component as a polymer precursor. here,

[0163]

[Equation 41]

A display element was manufactured in accordance with Example 1 by using other materials and a manufacturing method. However, SP-150 manufactured by Asahi Denka Kogyo KK was used as a photopolymerization initiator in an amount of 5% based on the polymer precursor. The display element manufactured in this manner shows the same element characteristics as those in the case of using the methacryl or acrylic polymer shown in the above embodiment, and 3.5.
The display state started to be inverted at V, and the display state was inverted at 5 V.

The proton precursor used in this example is a compound in which the polymerized part is an epoxy group in the previous example.

[0166]

(Equation 42)

[0167]

[Equation 43]

[0168]

[Equation 44]

[0169]

[Equation 45]

[0170]

[Equation 46]

[0171]

[Equation 47]

[0172]

[Equation 48]

[0173]

[Equation 49]

Is a compound represented by the formula: Z in the chemical formula is 0 or N. In the case of N, one more epoxy group or side chain can be introduced. Here, a compound derived from epichlorohydrin, which is the most common epoxy group, is shown, but any substituent may be included as long as the epoxy group is introduced. Alkyl, ether, ester, amide, urethane and the like can be used as a spacer between the epoxy group and the aromatic ring. The electro-optical characteristics of the display element when each of the compounds shown here are used show almost the same tendency as the result in the above-described embodiment, but the driving voltage tends to be higher as a whole.

Regarding the photopolymerization initiator, SP-150 and S
P-170, UV-1014, UVE-10 manufactured by GE
16, CyracureUVI-697 manufactured by UCC
4, UVI-6990, etc. can be used as long as they act as an initiator, sensitizer, or polymerization catalyst when curing an epoxy resin with light. In addition, the mixing ratio may be a catalytic amount with respect to the polymer precursor, and the absolute amount may vary depending on the prepolymer medium to be used. However, if the mixing ratio is too large, the specific resistance of the element decreases, and the reliability also decreases.

(Example 16) In this example, the polymer precursor obtained in the previous example was polymerized in advance, heated and made compatible with the liquid crystal, and cooled to remove the polymer from the liquid crystal. An example of deposition will be described.

The polymer precursor used was 4-menzoyloxyphenyl methacrylate used in Example 1, the liquid crystal was TL202, manufactured by Merck, and the chiral component was CB15, manufactured by BDH, as a chiral component. S-Dye Co., Ltd.
428 were mixed. First, the polymer prepolymer was polymerized by ultraviolet light to be polymerized. This was heated at 120 ° C. to make it compatible with the liquid crystal, and sealed between two substrates with electrodes subjected to alignment treatment. The panel was cooled at a rate of 1 ° C./min to precipitate the polymer in an oriented state. The slower the cooling rate, the better. If the cooling rate is too rapid, the polymer precipitates without orientation.

In this embodiment, the device functions as an element if the ratio of the polymer to the liquid crystal is between 3:97 and 50:50. Further, a chiral component and a dye need not be added. As the polymer precursor, the liquid crystal, the chiral component, and the dichroic dye, any of the materials described in the above embodiments other than those shown here can be used. Although two substrates are used here, the same process can be applied to one substrate, and the same process can be performed. Further, a counter electrode can be formed to form a display element. Further, the liquid crystal polymer layers formed on a single substrate can be attached to each other so as to face each other to form an element. Further, an active element can be used as the substrate described above, whereby a large-capacity display element can be manufactured. Further, as described in the previous embodiment, a display can be made in color by combining with a color filter.

(Example 17) In this example, the polymer precursor obtained in the previous example was polymerized in advance, heated and made compatible with the liquid crystal, and cooled to remove the polymer from the liquid crystal. An example of deposition will be described.

The polymer precursor used was 4- (p-bentylbenzoyloxy) phenyl methacrylate, the liquid crystal was MJ90657 manufactured by Merck, and the chiral component was CM20 manufactured by Chisso, and the two dyes were manufactured by Mitsui Toatsu Dye Co., Ltd. S-3
44 were mixed. First, the polymer precursor is polymerized with ultraviolet light,
Polymerized. This and the liquid crystal were made compatible with each other using methyl ethyl ketone as a solvent, and developed on an alignment-treated substrate with electrodes. The panel was heated and dried at 50 ° C., and the solvent was distilled off to precipitate the polymer in an oriented state. Thereafter, a counter electrode or a substrate provided with the counter electrode was attached to form a display element.

If the orientation of the polymer is poor, the solvent may be distilled off, and then subjected to the heating and cooling treatment as shown in Example 16.

In this embodiment, if the ratio of the polymer to the liquid crystal is between 3:97 and 50:50, the device functions as an element. In addition, chiral components and pigments need not be added. The polymer precursor, the liquid crystal, the chiral component, the dichroic dye, and the solvent other than those shown here can be used as long as they are the materials shown in the above embodiments. Although two substrates are used here, the same process can be applied to one substrate, and the same process can be performed. Further, a counter electrode can be formed to form a display element. Further, the liquid crystal polymer layers formed on a single substrate can be attached to each other so as to face each other to form an element. Further, an active element can be used as the substrate described above, whereby a large-capacity display element can be manufactured. Further, a color display can be formed by combining with a color filter as shown in the above embodiment.

(Embodiment 18) In this embodiment, among the substrates for aligning liquid crystal and polymer, at least the alignment direction 16 of the substrate on the incident light side is the main light incident direction 18 and the normal direction 19 of the substrate. Here is an example that is orthogonal to the plane containing. A simple layout is shown in FIG. In the present embodiment, the orientation processing direction 16 of the substrate on the back side is set to the same direction as the front side, and as a comparative example, an example in which the display device is arranged by rotating the orientation processing method by 90 degrees with respect to the present embodiment. All of the embodiments shown in the present invention can be used for the configuration and the manufacturing method of the used display element. FIG. 7 shows the electro-optical characteristics of a display element in which a reflecting plate 20 is arranged using a system in which a dichroic dye and a chiral component are mixed. A solid line indicates the present example, and a broken line indicates a comparative example. As described above, the reflectivity could be improved by about 30% in the electro-optical characteristics. Regarding the orientation processing direction on the back side substrate, the same effects as those of the present embodiment can be obtained in any direction other than the same direction as the front side.

(Embodiment 19) In this embodiment, a wavelength correction plate 2 is provided on the back side of a substrate sandwiching a layer in which liquid crystals and polymers are aligned and dispersed.
1 and an example in which a reflection plate or a light scattering plate 20 is arranged.

FIG. 8 shows an example in which the liquid crystal and the polymer are horizontally aligned with respect to the substrate surface, and FIG. 9 shows an example in which the liquid crystal and the polymer are vertically aligned with respect to the substrate surface. Here, the principle will be described using a system in which a dichroic dye is mixed into a liquid crystal and a chiral component is not used, and a quarter wavelength plate is used as a wavelength correction plate.

First, referring to FIG. 8, the incident light can be considered by being decomposed into polarized light in vertical and horizontal directions as shown in the figure. At this time, it is assumed that the liquid crystal / polymer layer 17 is oriented in the horizontal direction 16. The orientation direction of the 波長 wavelength plate 21 is arranged at an angle of about 45 ° with respect to the orientation direction 16 of the liquid crystal / polymer layer.

When no electric field is applied, the vertically polarized light passes through the liquid crystal / polymer layer 17 without being absorbed by the dye, passes through the quarter-wave plate 21, and is reflected or scattered.
When the light passes through the wave plate, the polarization plane is rotated by 90 degrees. Therefore, this time, absorption occurs by the dye in the liquid crystal / polymer layer,
No reflected light appears on the table. In contrast, horizontal polarized light is absorbed by the dichroic dye in the liquid crystal / polymer layer.

Next, when an electric field is applied, absorption by the dichroic dye is reduced. At this time, when vertically polarized light is incident, the light passes through the liquid crystal / polymer layer, and is further reflected or scattered by passing through the ４ wavelength plate. I have. Therefore, light is scattered by the liquid crystal / polymer layer. Next, when horizontal polarized light enters, light scattering occurs in the liquid crystal / polymer layer. According to this, all polarized light, that is, natural light, can be efficiently modulated by this display element.

Next, FIG. 9 will be described. Here, the liquid crystal / polymer layer 17 is slightly inclined in the horizontal direction 23 with respect to the substrate surface and is vertically oriented (16). The quarter-wave plate 21 is disposed at an angle of about 45 degrees with respect to the horizontal direction.

When no electric field is applied, neither vertically polarized light nor horizontally polarized light returns without being scattered and absorbed, but is scattered or reflected.

When an electric field is applied, the liquid crystal and the dichroic dye become
It is mainly oriented in the horizontal direction 23. When the vertically polarized light enters here, it passes through the liquid crystal / polymer layer, passes through the quarter-wave plate, is scattered or reflected, and passes through the quarter-wave plate again. At this time, since the deflected surface is rotated by 90 degrees, absorption by the dye in the liquid crystal / polymer layer and scattering at the liquid crystal / polymer interface are simultaneously received. Next, when the horizontally polarized light is incident, the light is absorbed by the dichroic dye in the liquid crystal / polymer and simultaneously scattered at the liquid crystal / polymer interface. In this way, it becomes possible to effectively modulate all polarized light, that is, natural light.

The above configuration can be applied to all embodiments of the present invention. For example, the present invention can be applied to a case where a chiral component is mixed, or can be applied to a system in which a dichroic dye is not mixed, so that the scattering intensity can be improved. Of course, large-capacity display can be performed in combination with an active element, and color display can be performed in combination with a color filter.

(Embodiment 20) In this embodiment, an example is shown in which two sets of the display elements shown in the previous embodiment are combined. FIG.
0 shows the configuration of this embodiment. Here, two sets of horizontally oriented display elements are combined with their orientation directions orthogonal to each other. Regarding the principle of movable property, it can be considered that another set of display elements is arranged so that the orientation directions are orthogonal to each other in place of the wavelength correction plate and the reflection plate in Example 19, and the same operation is performed. That is, the display element of the present invention which does not contain or slightly contains a chiral component has a polarization dependence in the scattering characteristic when an electric field is applied, and therefore, is transmitted without being scattered in the first display element. The polarized light is scattered by the second display element arranged so as to scatter the polarized light, so that any polarized light, that is, natural light can be efficiently modulated.

The above configuration can be applied to all embodiments of the present invention. For example, the present invention can be applied to a case where a chiral component is mixed, or can be applied to a system in which a dichroic dye is not mixed, so that the scattering intensity can be improved. Of course, large-capacity display can be performed in combination with an active element, and color display can be performed in combination with a color filter.

The compounds shown in all the examples can be used in combination with the compounds in other examples.
The electro-optical characteristics at that time are often intermediate between the characteristics when using each compound.

In all the embodiments described above, when a non-reflection layer or a reflection diffusion layer is provided on the surface of the display element, the display can be easily viewed.

In all of the above embodiments, particularly, a display element in which a chiral component is not mixed or slightly mixed has a polarization characteristic, so that it can be used as an electric field control type polarizing element.

As described above, the display element according to the present invention can make the reflection type display element which is dark and difficult to see conventionally bright and easy to see in each stage, and can be combined with the active element which has been difficult so far. Thus, a large-capacity reflective display can be manufactured. Furthermore, colorization is also possible. Thereby, a reflection type full-color large-capacity display of a computer terminal and a reflection type wall-mounted television are also possible. Further, it can be used as an electric field control type polarizing element in a simple direction.

[Brief description of the drawings]

FIG. 1 is a diagram simply showing a cross section of a horizontal alignment type display element in Example 1 of the present invention.

FIG. 2 is a diagram simply showing a cross section of a vertical alignment type display element in Example 1 of the present invention.

FIG. 3 is a diagram simply showing a cross section of an obliquely oriented display element in Example 12 of the present invention.

FIG. 4 is a diagram simply showing a partial cross section of a display element with an active element in Example 13 of the present invention.

FIG. 5 is a diagram simply showing a partial cross section of a display element with a color filter in Example 14 of the present invention.

FIG. 6 is a diagram simply showing a cross section of a display element in Example 18 of the present invention.

FIG. 7 is a diagram showing electro-optical characteristics of a display element in Example 18 of the present invention.

FIG. 8 is a diagram simply showing a cross section of a horizontal alignment type display element in Example 19 of the present invention. (A) shows a diagram without application of an electric field, and (B) shows a diagram with application of an electric field.

FIG. 9 is a diagram simply showing a cross section of a vertical alignment type display element in an embodiment 19 of the present invention. (A) shows a diagram without applying an electric field, and (B) shows a diagram with an electric field.

FIG. 10 is a diagram showing a two-layer display element in Example 20 of the present invention. (A) is a diagram without an electric field applied,
(B) shows a diagram when an electric field is applied.

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[Procedure amendment]

[Submission date] November 19, 1999 (1999.11.
19)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

Patent application title: Method for manufacturing liquid crystal polymer layer and method for manufacturing display element

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. Hei 4-9540 (32) Priority date January 22, 1992 (199.2.1.22) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-106899 (32) Priority date April 24, 1992 (1992.4.24) (33) Priority claim country Japan (JP) (31) Priority claim number Patent application 4-140343 (32) Priority date June 1, 1992 (1992.6.1) (33) Priority claiming country Japan (JP)

Claims (31)

[Claims] 1. A display element in which a liquid crystal and a polymer are aligned and dispersed in one another, wherein the polymer used comprises a polymer precursor having a polymerized part and an aromatic ring. 2. The display element according to claim 1, wherein the polymer precursor contains, as at least one component, a polymer precursor having a side chain portion including a polymer portion and an aromatic ring portion. . 3. The display device according to claim 1, wherein the polymer precursor contains a polymer precursor having two or more polymerized parts as at least one component. 4. The display element according to claim 1, wherein the polymer precursor contains at least one component of an ester derivative with methacrylic acid or acrylic acid. 5. The display device according to claim 1, wherein the polymer precursor contains at least one amide derivative with methacrylic acid or acrylic acid. 6. The display element according to claim 1, wherein the polymer precursor contains at least one compound having an epoxy group. 7. The polymer precursor comprises at least one aromatic ring (at least one of these aromatic rings may be hydrogenated) and a compound having an ester group between the aromatic rings. The display element according to claim 1, wherein the display element is contained as a component. 8. The polymer precursor comprising a compound having at least two aromatic rings (at least one of these aromatic rings may be hydrogenated) and a urethane group or an amide group between these aromatic rings. The display element according to claim 1, wherein the display element is contained as at least one component. 9. The polymer precursor comprising a compound having at least two aromatic rings (at least one of these aromatic rings may be hydrogenated) and at least one acetylene group between these aromatic rings. The display element according to claim 1, wherein the display element is contained as at least one component. 10. The polymer precursor according to claim 1, wherein the polymer precursor contains, as at least one component, a compound in which an alkyl group or an alkoxy group is directly or indirectly bonded to the aromatic ring. Display element. 11. The polymer precursor according to claim 1, wherein a compound in which at least one of a cyano group halogen group and an aromatic ring is directly or indirectly bonded to the aromatic ring is contained as at least one component. Claim 1 to do
The display element as described in the above. 12. The display device according to claim 1, wherein the polymer precursor contains at least one polymerizable compound containing a fluorine element. 13. The display device according to claim 1, wherein the polymer precursor contains at least one optically active polymerizable compound. 14. The display device according to claim 1, wherein the liquid crystal contains a dichroic dye. 15. The display element according to claim 1, wherein the liquid crystal contains a chiral component. 16. The display device according to claim 1, wherein the liquid crystal is a nematic liquid crystal. 17. The method according to claim 1, wherein the polymer is formed in a mixture of the polymer precursor and liquid crystal in a liquid crystal phase by at least one stimulus of heat, light, and an electron beam. 2. The display element according to 1. 18. The method according to claim 1, wherein the polymer is formed by polymerizing the polymer precursor in advance, making the polymer compatible with the liquid crystal while heating, and gradually cooling the liquid crystal.
The display element as described in the above. 19. The polymer is prepared by polymerizing the polymer precursor in advance, making the polymer compatible with the liquid crystal using a solvent, and developing the polymer on a substrate. 2. The display element according to claim 1, wherein the solvent is slowly distilled off to such an extent as to precipitate. 20. The display device according to claim 1, wherein the orientation directions of the liquid crystal and the polymer layer are inclined with respect to the substrate surface. 21. An alignment direction of the liquid crystal and the polymer layer,
2. The display device according to claim 1, wherein the control is performed by an alignment treatment of the substrate surface sandwiching the liquid crystal and the polymer. 22. Among the substrates for aligning the liquid crystal and the polymer layer, at least the direction of the alignment treatment of the substrate on the incident light side is a direction orthogonal to the main incident light direction and a plane including the substrate emission line. The display device according to claim 1, wherein the display device is a display device. 23. Among the substrates for aligning the liquid crystal and the polymer layer, at least the incident light side substrate has an alignment direction:
2. The display device according to claim 1, wherein the display device is in a plane including a main incident light direction and a substrate radiation. 24. The display device according to claim 1, wherein a light reflection layer or a light scattering layer is disposed on the back surface of the liquid crystal and polymer layers. 25. The display device according to claim 1, wherein a wavelength correction plate (for example, a quarter-wave plate) is arranged between said liquid crystal and polymer layers and said reflection layer or light scattering layer. . 26. The display element according to claim 1, wherein a color filter is formed on at least one of the substrates sandwiching the liquid crystal and polymer layers. 27. The display element according to claim 1, wherein an active element, for example, a two-terminal element or a three-terminal element is formed on at least one of the substrates sandwiching the liquid crystal and the polymer layer. 28. The display device according to claim 1, wherein the two sets of display devices are overlapped so that the alignment directions of the liquid crystal and the polymer are orthogonal to each other. 29. The liquid crystal and the polymer layer are formed by applying at least one of heat, light and electron beam to a mixture of the polymer precursor and the liquid crystal in a liquid crystal phase. A method for manufacturing a display element. 30. A method for manufacturing a display element, comprising polymerizing the polymer precursor in advance, making the polymer precursor compatible with the liquid crystal while heating, and slowly cooling to form the polymer layer with the liquid crystal. . 31. A method in which the polymer precursor is preliminarily polymerized, is compatible with the liquid crystal using a solvent, and is spread on a substrate. A method for manufacturing a display element, wherein the solvent is slowly distilled off to form the liquid crystal and the polymer layer.