JP3215677B2 - Method for manufacturing liquid crystal electro-optical device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structure of a birefringent or optical rotation type liquid crystal electro-optical device and a method of manufacturing the same.

[0002] The present invention relates to a structure for maintaining a constant substrate spacing (distance between substrates) of a liquid crystal electro-optical device, particularly a large-area liquid crystal electro-optical device, and a method of manufacturing the same.

[0003] The present invention relates to a liquid crystal electro-optical device having a columnar resin obtained by curing an uncured resin precipitated from a liquid crystal material, and a method of manufacturing the same.

[0004]

2. Description of the Related Art As a conventional liquid crystal electro-optical device, a TN type or STN type using a nematic liquid crystal or the like is widely known.
Has been put to practical use. Recently, a device using a ferroelectric liquid crystal has been known. In these liquid crystal electro-optical devices, basically, a first substrate having an electrode on a substrate and a second substrate having an electrode on the substrate are provided so as to face each other with the surface having the electrode inside. A liquid crystal layer is formed by sandwiching a liquid crystal material on the substrate, a voltage is applied to the liquid crystal layer by an electrode on the substrate, and the anisotropy of the dielectric constant of the liquid crystal material itself, or in the case of a ferroelectric liquid crystal, By spontaneous polarization,
It changes the state of liquid crystal molecules, and as a result utilizes the electro-optic effect accompanying the change in the state of liquid crystal molecules.

In the TN and STN-type liquid crystal electro-optical devices, liquid crystal molecules are arranged in the rubbing direction on the contact surfaces of the liquid crystal layer with both substrates in accordance with the regulating force of rubbing performed for alignment treatment. In the upper and lower substrates, the rubbing direction is shifted so as to be located at 90 ° or 200 ° to 290 °. In the vicinity of the middle of the liquid crystal layer, the liquid crystal molecules are spirally arranged so that the energy between the upper and lower molecules located at 90 ° to 290 ° becomes the smallest. At this time,
In the case of the STN type, a chiral substance is mixed in the liquid crystal material as needed.

In the above TN and STN type liquid crystal electro-optical devices, the liquid crystal molecules arranged in a spiral form are arranged in parallel or perpendicular to the direction of the electric field due to the dielectric anisotropy of the liquid crystal molecules when a voltage is applied between both substrates. This solves the spiral structure. The device shows a bright state when the liquid crystal molecules are perpendicular to the substrate surface, and shows a dark state when the liquid crystal molecules are parallel to the substrate surface. Further, since the state of these liquid crystal molecules changes continuously by changing the voltage applied between the substrates, gradation display is possible by appropriately controlling the applied voltage.

In a liquid crystal electro-optical device using a ferroelectric liquid crystal or an antiferroelectric liquid crystal, liquid crystal molecules are arranged on at least one substrate surface in accordance with the rubbing control force. These liquid crystal molecules have a layer structure that is regularly stacked from one substrate surface to the other substrate surface.

In the above-mentioned liquid crystal electro-optical device using the ferroelectric liquid crystal or the antiferroelectric liquid crystal, the liquid crystal molecules having a layer structure parallel to the substrates are themselves applied by applying a voltage between the substrates. The direction of the spontaneous polarization of is changed by 180 ° (hereinafter referred to as inversion). The device changes the direction of the liquid crystal molecules arranged in the rubbing direction by a certain angle from the rubbing direction by the inversion of the liquid crystal molecules, and performs switching from the bright state to the dark state or from the dark state to the bright state.

In these liquid crystal electro-optical devices,
In a so-called active matrix type liquid crystal electro-optical device in which an electrode of one of the substrates holding a liquid crystal material is a plurality of pixel electrodes and a switching element such as a diode or a thin film transistor (TFT) is connected to each pixel, a higher speed and higher speed are realized. More sophisticated displays such as vivid and multi-tone displays are being performed.

The general cell structure of the liquid crystal electro-optical device described above will be described with reference to FIG. What is shown is a simple matrix type device. An electrode pattern 110 is formed on a transparent substrate 1100 or 1101 such as glass or resin.
2 and 1103 are formed. Alignment means 1104 and 1105 for arranging liquid crystals in a fixed direction are formed on the electrodes. The minimum distance between the electrodes is maintained by the spacers 1107 scattered on the substrates, and the two substrates are fixed with a sealing material. A liquid crystal material 1106 is injected between the substrates to form a liquid crystal layer.

Normally, when a rubbed polyimide film is used as the alignment means, the liquid crystal molecules have a horizontal alignment parallel to the substrate surface or arranged in one direction at a certain angle. When a silane coupling agent is used, the liquid crystal molecules have a vertical alignment that stands in a direction perpendicular to the substrate surface. Whether the liquid crystal molecules are aligned horizontally or vertically depends on the intended operation mode.

In this state, electrodes 1102 and 110 are provided on the liquid crystal.
Voltage is applied from 3. The liquid crystal molecules form a bright state or a dark state in response to the electric field generated there. If uniform display is performed over the entire surface of the cell, it is necessary to keep the distance between the substrates constant, that is, to arrange two substrates at a constant interval. Usually, the inter-substrate distance depends on the operation mode, but is between 1.2 and 20 μm, and its accuracy is required to be 0.05 μm or less.

[0013]

2. Description of the Related Art In recent years, a large-area screen has been required for such a liquid crystal electro-optical device, and efforts have been made to realize a huge liquid crystal display having a diagonal length of 40 inches. Has also been paid.

In this case, although the screen size is large, the required distance between the substrates is 1.2 to 20 as described above.
μm, which is extremely small, and the accuracy is required to be 0.05 μm or less.

In the case of the aforementioned diagonal of 40 inches, a size of 12
It will exceed 8 kg just by opposing a glass substrate of 0 cm square and 1.1 mm thick. When the distance between the substrates is 6 μm, the weight of the liquid crystal entering between the substrates is 60 g. With such a size, even if a rigid glass substrate is used, the area is large, and even if the substrate is erected, the substrate will bend as if by paper under its own weight.

When a liquid crystal cell in which such two large substrates are bonded together is erected, the lower side becomes a swollen gourd-like shape. As a result, the distance between the lower substrates was several times to several tens times, sometimes several hundred times, the distance between the upper substrates, and a constant electric field was not generated in the liquid crystal, so that uniform display was not possible.

In the case of a ferroelectric liquid crystal, since the orientation of the liquid crystal forms a layer structure, the layer structure is broken by the deformation of the substrate, resulting in a fatal damage that display is impossible. This phenomenon easily occurs even when the display area is as small as about 5 cm square, and has been one of the major problems of the ferroelectric liquid crystal display.

The structure of a conventional liquid crystal electro-optical device is shown in FIG. 1, but the two substrates are fixed at regular intervals only at the location of the sealing material around the glass substrate. The inside is merely supported by spacers so that the distance between the substrates does not become too narrow. Therefore, it is natural that the longer the distance from the seal portion, the more the cell is bent.

Conventionally, as a countermeasure, there has been a method in which adhesive particles are dispersed inside the cell in addition to the seal adhesive on the outer periphery to bond two substrates. However, there has been a phenomenon that the orientation around the adhesive is easily disturbed.

As a further problem of the prior art,
The state of the liquid crystal molecules between the substrates is mainly determined by the magnitude of the voltage applied to the electrodes of the two substrates.However, conventional devices contain liquid crystal or impurities with charges from the alignment film. It is well known that, when a voltage is applied, an extra charge is generated which generates a voltage in a direction opposite to the voltage.

These charges move freely in the liquid crystal layer sandwiched between the two substrates with the application of a voltage. Most of these charges move to reach the surface of the alignment film. However, since the alignment film is originally insulating, the charge does not move any further and is accumulated between the alignment film and the liquid crystal layer (the liquid crystal interface between the alignment film and the liquid crystal). It becomes a form.

These charges cause a problem which is not preferable for a liquid crystal electro-optical device. For example, an action of canceling the voltage applied between the two substrates occurs, and when sufficiently inverting the liquid crystal molecules, the applied voltage needs to be higher than the voltage necessary for inverting the spontaneous polarization.
In addition, when a voltage is applied between the electrodes, the state of the liquid crystal molecules is not stable because the amount of charge in the liquid crystal layer changes with time. Furthermore, the liquid crystal molecules that are electrically adsorbed by the electric charge accumulated at the interface between the alignment film and the liquid crystal require a higher voltage to change the state than the liquid crystal molecules that are not adsorbed inside the liquid crystal layer. However, there is a problem in that the state changes do not occur at the same time, and the most important light transmission characteristic of the liquid crystal electro-optical device is not stable.

In order to solve this problem, a material for an alignment film that alleviates the accumulation of electric charges is selected, and instead of an alignment film serving as an insulating film, SiO ₂ or the like is obliquely deposited on an electrode to form liquid crystal molecules. Although there is a method of orienting, it is not a general method such that a lot of preliminary experiments are required, it takes a long time and the cost becomes high, and the effect changes depending on a material combination. There is also a method of purifying liquid crystal to remove impurities. However, this method has very few liquid crystals that can be purified and used, which is extremely unsuitable in view of mass productivity.

Further, by using a charge transfer complex, a charge existing in the liquid crystal layer is adsorbed or combined to make a plus or minus charge into a plus or minus 0 state (hereinafter referred to as cancellation or neutralization). However, it is difficult to measure just the right amount of charge-transfer complex into the device to completely cancel the charge. If the charge-transfer complex in the liquid crystal layer is insufficient, an undesired charge is obtained. Cannot be canceled, and the excess charge transfer complex moves in the liquid crystal layer in the same manner as the above-mentioned charge, causing a problem.

As described above, a factor that causes a change in the voltage applied to the liquid crystal layer, that is, a factor that causes a change in the state of the liquid crystal molecules over time and destabilizes the optical characteristics of the device, exists in the liquid crystal layer. Although various methods have been proposed to cancel charge, there is still no easy and complete method to cancel.

[0026]

SUMMARY OF THE INVENTION The present invention solves the various problems as described above. That is, the present invention provides a liquid crystal electro-optical device capable of bonding between substrates without disturbing the alignment state of the liquid crystal material, and a method for manufacturing the same. Another object of the present invention is to provide a high-performance liquid crystal electro-optical device which eliminates the influence of undesired charges in the liquid crystal layer, stabilizes the optical characteristics of the device, and has no flicker or tone change.

[0027]

Means for Solving the Problems To solve the above-mentioned problems, the present invention provides a pair of light-transmitting substrates having electrodes on their surfaces, facing each other with the electrodes inside. A liquid crystal material is provided between a pair of substrates, and an alignment means for arranging the liquid crystal material in a predetermined direction on an inner surface of at least one of the pair of substrates is provided, and the uncured material mixed in the liquid crystal material is provided. A liquid crystal electro-optical device, wherein a resin cured in a column shape formed by precipitation and curing of the resin is adhered to the alignment means or the substrate.

Further, according to the present invention, a pair of substrates having electrodes on their surfaces are provided so as to face each other with the electrode surface inside, and a liquid crystal material is provided between the pair of substrates, and at least one of the pair of substrates is provided. In a liquid crystal electro-optical device provided with alignment means for aligning the liquid crystal material in a certain direction on the inner surface of the substrate, the liquid crystal material comprises a cured resin material and a reaction initiator in the liquid crystal material, Liquid crystal electro-optical device.

According to the present invention, a pair of substrates each having an electrode on the surface are provided with the electrode surfaces facing each other inside, and a liquid crystal material is sandwiched between the substrates. A liquid crystal electro-optical device, further comprising an alignment unit for aligning the liquid crystal material in a predetermined direction, wherein the liquid crystal material contains a reaction initiator.

According to the present invention, there is provided a liquid crystal electro-optical device having a pair of substrates each having an electrode on the surface with the electrode surfaces facing each other, and having a liquid crystal material between the pair of substrates. Is a liquid crystal electro-optical device characterized in that a reaction initiator is present.

The present invention also includes a step of filling a liquid crystal mixture comprising a liquid crystal material, a resin constituent material, and a reaction initiator between a pair of opposed substrates having an electrode on an inner surface and an alignment film on at least one inner surface. And a step of separating the liquid crystal material and the resin constituent material in the liquid crystal mixture and a step of cleaving the reaction initiator.

Further, the present invention comprises at least a step of filling a liquid crystal mixture comprising a liquid crystal material and a reaction initiator between a pair of opposed substrates having electrodes on the inner surface, and a step of cleaving the reaction initiator. A method for manufacturing a liquid crystal electro-optical device, comprising:

Further, according to the present invention, for a mixture of a liquid crystal material and an uncured resin between a pair of opposing translucent substrates, a step of precipitating the uncured resin from the mixture, and orienting the liquid crystal material A method for manufacturing a liquid crystal electro-optical device, comprising: a step of curing the uncured resin; and a step of re-orienting the liquid crystal material.

Further, according to the present invention, a mixture of a liquid crystal material and an uncured resin which is cured by any of ultraviolet rays and heat is filled between a pair of opposed substrates having electrodes on the inner surface. A method for producing a liquid crystal electro-optical device, comprising: depositing from a mixture; and curing the deposited resin by ultraviolet light and heating.

Further, the present invention has a sealing material for bonding the pair of substrates, and a mixture of a liquid crystal material and an uncured resin, between a pair of opposed substrates at least one of which has a light transmitting property. A method of manufacturing a liquid crystal device, comprising: after depositing the uncured resin in a column from the mixture, curing the sealing material and the uncured resin in the same step.

"Description of Structure" The present invention relates to a liquid crystal mixture obtained by adding an uncured resin material comprising a resin constituent material (monomer or oligomer) and a reaction initiator to a liquid crystal material.
By sandwiching between the substrates of a liquid crystal electro-optical device and curing the resin between the substrates, the distance between the substrates is fixed without disturbing the orientation of the liquid crystal, and unwanted charges in the liquid crystal layer are removed. . In addition, an unwanted charge is removed by the action of a reaction initiator.

An example of the basic structure of the liquid crystal electro-optical device according to the present invention will be described with reference to FIG. Electrodes and leads 100,
101, a light-transmitting substrate 1 having polarizing plates 112 and 113
Alignment films 104 and 105 are formed on at least one of the substrates 02 and 103 as a means for aligning the liquid crystal. Further, in order to keep the distance between the substrates constant, for example, silica beads 106 are used as spacers, and the sealing material 1 is used.
At 07, both substrates are fixed. A column-shaped resin 108 in which the upper and lower substrates are bonded between the substrates, or a resin block 109
The liquid crystal 110 is sandwiched in such a manner that the reaction initiator 111 is diffused in the resin and the liquid crystal, thereby forming an apparatus.

In the liquid crystal electro-optical device according to the present invention, the reaction initiator added at the time of manufacturing is uniformly diffused in the liquid crystal mixture,
At room temperature, even if the resin constituent material separates and precipitates out of the liquid crystal mixture in a form rejected by the liquid crystal material, the reaction initiator remains diffused in the liquid crystal mixture, and the reaction initiator is cleaved and the resin material is cleaved. Even when is cured, the reaction initiator is present in the remaining liquid crystal material. Also, the resin material hardens,
It becomes a column (column) and adheres the upper and lower substrates and the surface of the alignment film, or exists as a resin mass (resin solid) in the liquid crystal layer.

The column-shaped resin of the present invention is a polymerized column spacer (Polymerized) in the meaning of a column-shaped resin spacer.
Column Spacer, abbreviated as PCS).

In order to manufacture this liquid crystal electro-optical device, a liquid crystal material, a resin constituent material, and a reaction initiator are mixed, and heated and stirred until the liquid crystal shows an isotropic phase so that the liquid crystal and the resin are more properly mixed. The liquid crystal mixture thus prepared is sandwiched between the substrates of the above device. When the temperature of the device is gradually lowered from the temperature at which the liquid crystal mixture exhibits an isotropic phase, the resin constituent material mixed in the liquid crystal mixture is rejected, and the resin is scattered in the device. The reaction initiator also diffuses into the liquid crystal material, but the diffused reaction initiator is not rejected from the liquid crystal material even if the temperature of the device is lowered. For this reason, the reaction initiator in the liquid crystal device exists in both the resin constituent material portion and the liquid crystal material portion.

If only unwanted charges are removed without forming a columnar resin, no resin constituent material is used,
Only the reaction initiator may be mixed with the liquid crystal material.

The liquid crystal mixture is desirably heated and stirred to a temperature at which the liquid crystal material exhibits an isotropic phase. When the liquid crystal material is gradually cooled until the liquid crystal material exhibits a liquid crystal phase, the resin composition is excluded from the liquid crystal material. Material separates.

When the initiator in the apparatus is cleaved, charges are generated, and some of the charges from these initiators contribute to the curing of the resin, and some directly cancel the extra charges in the apparatus. Will be.

When the ratio of the area of the cured resin occupying the display portion of the liquid crystal electro-optical device is 0.1 to 20%, sufficient display characteristics and strength of the device itself can be obtained as the liquid crystal electro-optical device.

In producing the liquid crystal mixture, a so-called resin material (uncured resin) generally commercially available is used.
Since a reaction initiator is added to a resin constituent material, the resin material may be mixed into a liquid crystal material to prepare a liquid crystal mixture, or the amount of the reaction initiator added to the resin material May be changed, the resin constituent material and the reaction initiator may be divided and mixed separately.

The reaction initiator may be mixed in the liquid crystal material in advance, may be mixed in the alignment film material as alignment means, or may be applied on the alignment film surface. That is, the reaction initiator 111 may be mixed in the above-described alignment films 104 and 105 or may be applied to the surface.

As the reaction initiator, an ultraviolet-excitation cleavage type reaction initiator is most suitable. In this case, the polarizing plates 112, 1
13 is provided on the substrates 102 and 103 after irradiating ultraviolet rays to cleave the reaction initiator.

The addition amount of the reaction initiator can be arbitrarily changed according to the degree of cleanliness of the substrate and the degree of purification of the liquid crystal material. .1 to 3% is effective in solving the above-mentioned problem.

[0049]

According to the present invention, a resin-constituting material is separated and precipitated from a mixture of a liquid crystal material between substrates and an uncured resin (a resin-constituting material (monomer or oligomer) and a reaction initiator). Then, the liquid crystal material is oriented, and then the reaction initiator is cleaved to cure the resin in a column shape and adhere to both substrates, thereby fixing the distance between the substrates.

When the temperature of the mixture of the liquid crystal material and the uncured resin filled between the substrates is increased and the liquid crystal material in the mixture is in an isotropic state, it is not possible to distinguish between the uncured resin and the liquid crystal. However, when the temperature decreases to about room temperature, the uncured resin is rejected from the liquid crystal material and precipitates and is scattered between the substrates. By applying a means for curing the resin at this stage, the scattered resin is cured in a column (column) shape and the two substrates can be bonded to each other.

In order to improve the orientation of the liquid crystal, it is preferable to heat the mixture of the liquid crystal material and the uncured resin until the liquid crystal material is in an isotropic phase, and then gradually cool the mixture to a temperature indicating the liquid crystal phase. In particular, when a liquid crystal material having a highly ordered smectic phase is used, slow cooling is effective, and the alignment can be improved. In addition, the uncured resin can be simultaneously separated and precipitated from the mixture by this step. The resin is cured in a subsequent curing step.

As described above, according to the present invention, since the liquid crystal material is arranged according to the alignment means and the resin is cured, it is possible to maintain a good alignment state of the liquid crystal before curing, and the effect of the cured resin on the alignment. Is extremely small. Since the resin is cured while the alignment state is good, it is quite natural that the alignment is not impaired after the resin is cured.

When the content of the resin in the mixture of the liquid crystal material and the uncured resin is 0.1 to 20%, the orientation of the liquid crystal material is different from the orientation shown in a normal cell sandwiching only the liquid crystal material. It is almost the same, and the influence of the mixture of the resins on the orientation is small.

When this is cured, the ratio of the area of the resin cured in a column (column) to the entire area of the display portion viewed from the substrate surface of the apparatus is determined by the ratio of uncured resin mixed into the mixture. It is about 0.1 to 20%, which is almost in agreement with the ratio. That is, most of the mixed uncured resin is cured. The ratio of the area occupied by the remaining liquid crystal material is 80 to
99.9%. The mixing amount of the resin may be adjusted according to the force required for bonding the two substrates. As a matter of course, if the hardened resin portion in the display portion is large, the strength of the liquid crystal cell itself, that is, the force for maintaining the distance between the substrates is increased, but the area through which light passes is impaired, and the electric power such as contrast ratio is reduced. Optical properties are degraded. The above range was preferable as a numerical value satisfying both the strength and the electro-optical characteristics.

It is desirable that the resin used in such a method exhibits a mixed state with the liquid crystal material at a high temperature, and separates and precipitates from the liquid crystal material at a low temperature. In order to cure the resin while being sandwiched between two substrates, it is extremely desirable that the uncured resin contains no solvent. Further, since the separation of the liquid crystal material from the resin and the formation of the alignment state of the liquid crystal material largely depend on the temperature, it is preferable that the resin is cured by a factor different from the temperature. In consideration of such matters, for example, using an ultraviolet-curable resin as the uncured resin and using ultraviolet rays as the resin curing means is extremely suitable for implementing the present invention.

"Cancellation of Undesired Charges" The present inventors have also made use of the fact that undesired charges existing in the liquid crystal layer, which makes the liquid crystal molecular state unstable, cure the resin in the liquid crystal layer, It has been found that it can be canceled by cleavage of the initiator. By these methods, the transfer of electric charge and the accumulation of electric charge at the liquid crystal interface of the alignment film, which have conventionally been problems, are eliminated. Therefore, the voltage between the two substrates (between the electrodes) sandwiching the liquid crystal layer does not change with time, and an undesired state change of the liquid crystal molecules does not occur. Therefore, the state change of the liquid crystal molecules and the control of the optical characteristics can be easily performed. Become like Further, since no liquid crystal molecules are adsorbed on the substrate, the entire liquid crystal layer undergoes a state change at the same time as the application of a voltage, so that more stable optical characteristics can be obtained.

The mechanism for canceling undesired charges in the liquid crystal layer is considered as follows. That is, first, the unwanted charges are canceled by being taken into the resin when the resin material cures. Second, the unwanted charge is canceled by adsorbing or binding to the reaction initiator diffused in the liquid crystal material.

The first method utilizes a reaction when the ultraviolet curable resin is cured. In other words, the curing of the ultraviolet curable resin means that the monomers and oligomers of the resin constituent material are excited and cleaved by the reaction initiator giving energy as heat or short-wavelength light such as ultraviolet light, which is less than visible light. The polymerization reaction proceeds with the generated charges as a starting factor, and during the progress of the polymerization reaction, the side chains of the monomers and oligomers also become very reactive (hereinafter referred to as active). Incorporating the charge into the resin means reacting the active side chain moiety with an undesired charge existing in the device. Further, the cured resin does not usually decompose easily, so that the captured electric charge does not move through the liquid crystal layer again.

According to the second method, the reaction initiator diffused in the liquid crystal material even after the slow cooling is sufficiently irradiated with active ultraviolet irradiation at the time of curing the resin to cancel the unwanted charges. Generates electric charge. In addition, excess charges generated by the second method in excess of that required to cancel undesired charges are recombined with themselves and become stable.

Therefore, even if only the reaction initiator is mixed into the liquid crystal material without using the resin constituent material, the undesired electric charge itself existing in the liquid crystal electro-optical device can be canceled.

The rate of charge generation by the above first and second methods is usually one or more from one reaction initiator.
Generally, two or more charges are generated, one or more charges are generated from one molecule of monomer, and one or more, usually two or more are generated from one molecule of oligomer.

The reaction initiator may be cleaved spontaneously, but is easily excited and cleaved by applying heat or short-wavelength light such as ultraviolet light or the like as energy to generate charges. The generated charge is highly reactive,
Reacts readily with other charges. If no other charge is present, it reacts with the own charge of the other cleaved and becomes stable.

Whether or not the unwanted charge has been canceled cannot be directly confirmed by looking at it.
In general, it can be regarded as a temporal change of a current value when a certain voltage is applied to the device for a certain period of time, or as a current value change when the applied voltage is continuously changed.

FIG. 5 shows the result of measuring a current value with respect to a voltage change by applying a ± 30 V, 5 Hz triangular wave between the electrodes to the liquid crystal electro-optical device of FIG. 4 using the present invention.
As can be seen from FIG. 5, in the liquid crystal electro-optical device of the present invention, only a current peak (hereinafter referred to as a Ps peak) associated with reversal of spontaneous polarization is observed in the positive and negative directions of the current. On the other hand, in the conventional liquid crystal electro-optical device, since undesired electric charges exist in the liquid crystal layer, as shown in FIG.
Another peak (hereinafter, referred to as a second peak) occurs in addition to the s peak. The second peak indicates an extra current due to undesired charges, and the larger the second peak, the more unstable the state of the liquid crystal molecules. In the liquid crystal electro-optical device of the present invention, the second peak hardly occurs, and the state of liquid crystal molecules is extremely stable.

In the liquid crystal electro-optical device, glass or polyethylene terephthalate (PET) is used as a substrate material, and polyvinyl alcohol (PVA) or polycarbonate is used as a main material in order to utilize the uniaxiality of the liquid crystal molecules and the accompanying polarization. A polarizing plate or a retardation plate is used.
Occasionally, an ultraviolet absorber may be mixed with the polarizing plate or the retardation plate, or an ultraviolet absorbing filter may be added to the apparatus. These glasses, polarizers, retarders, UV absorbers or UV-absorbing filters actively absorb light in the wavelength range below the visible light. Light hardly reaches, and unnecessary cleavage of the initiator after completion of the apparatus does not occur.

Therefore, when the reaction initiator added to the liquid crystal is cleaved spontaneously and cancels the electric charge that causes an undesired state change of the liquid crystal molecules existing in the device, the reaction is stable without being cleaved thereafter. Get the state.

In the case where the electric charge that causes an undesired change in the state of the liquid crystal molecules existing in the device as described above cannot be completely canceled only by the electric charge caused by the natural cleavage of the reaction initiator, for example, ultraviolet light irradiation or the like is used. , The charge from the reaction initiator required to cancel the charge can be provided.
Then, the excess charge from the reaction initiator generated more than the amount necessary for cancellation is recombined with itself and becomes a stable state.

Also, when the reaction initiator is added to the liquid crystal material, there is a concern that the liquid crystal material is deteriorated. However, in the present invention, no deterioration of the liquid crystal material is observed.

In the present invention, various operation modes of the liquid crystal can be used. For example, by using a nematic liquid crystal having a positive dielectric anisotropy, the orientation of liquid crystal molecules between substrates is twisted by 90 ° in a TN type, a STN type in which a liquid crystal molecule is twisted by 180 to 270 °, and a STN type in which a substrate surface and liquid crystal molecules are twisted. The angle (pre-tilt angle) is 3 to 10 °, the liquid crystal material is a liquid crystal material which has been subjected to a vertical alignment process and has a negative dielectric anisotropy, and further has a smectic liquid crystal. And so on.

[Reorientation after Curing of Resin] On the other hand, the resin undergoes volume shrinkage upon curing, and the liquid crystal molecules which have been orientated around the uncured resin after the separation of the resin and liquid crystal are easily replaced by the volume upon curing of the resin. The shrinkage may cause a disorder in the alignment, which may cause a decrease in contrast due to a decrease in optical characteristics, particularly in a dark state.

A voltage holding ratio is one of indexes indicating whether or not these optical characteristics are stable with time.
The voltage holding ratio is a value indicating how much a voltage applied to one pixel for a short time is held after voltage removal. In other words, it is how the alignment of the liquid crystal molecules is maintained. Therefore, in order to increase the voltage holding ratio, it is desirable that the liquid crystal molecules are more stable and the alignment is uniform.

For this purpose, it is possible to prevent the disorder of the alignment of the liquid crystal material including the periphery of the resin due to the volume shrinkage of the cured column-shaped resin, thereby improving the alignment property, promoting the voltage holding ratio, and further improving the optical characteristics. It is desired.

To solve this problem, a step of precipitating the uncured resin from the mixture between the liquid crystal material and the uncured resin between the pair of opposing translucent substrates, The liquid crystal material may be formed by a step of aligning, a step of curing the uncured resin, and a step of realigning the liquid crystal material.

That is, first, the mixture of the liquid crystal material and the uncured resin in the cell is gradually cooled to precipitate the uncured resin material and to orient the liquid crystal material, and then the uncured resin is cured. At this time, if the volume shrinkage of the resin is large, the alignment of the liquid crystal around the resin may be disturbed. After that, a step of re-aligning the liquid crystal material by, for example, a heating / slow cooling step (hereinafter referred to as an aging step) is added. Thus, the disorder of the orientation including around the resin is eliminated, and the improvement of the voltage holding ratio and the improvement of the optical characteristics can be promoted.

[Simultaneous Curing of Sealing Material and Column-shaped Resin] Further, in producing a liquid crystal electro-optical device having a column-shaped resin, a resin-liquid crystal mixture (liquid crystal mixture) is injected into a cell in advance by a substrate. This is performed in a vacuum cell or a heated capillary phenomenon method in an empty cell where the cells are bonded to each other. In this case, labor and time for evacuation and the like, large-scale equipment and the like are required. Further, since a columnar resin deposition / hardening step is required, the number of steps is increased as compared with a general liquid crystal electro-optical device.

In order to simplify the manufacturing process and shorten the manufacturing time, it is preferable to cure the uncured resin deposited in a column from the mixture with the peripheral sealing material of the substrate in the same process.

For example, a step of forming a sealing material around the first substrate, a step of dropping a mixture of a liquid crystal material and an uncured resin on the first substrate, and a step of dropping the mixture. Then, a liquid crystal electro-optical device may be manufactured by a step of bonding a second substrate to the substrate, a step of depositing the uncured resin from the mixture, and a step of curing the sealing material and the uncured resin.

At this time, it is effective to use an ultraviolet curable resin as the sealing material and the uncured resin, and to use ultraviolet rays as a curing means for the sealing material and the uncured resin.

With this configuration, the steps required to fabricate a liquid crystal electro-optical device using a columnar resin are as follows:
Substrate bonding-column-like resin deposition-ultraviolet irradiation (curing of a sealing material and a columnar resin) is performed, so that the liquid crystal injection step is not required and the ultraviolet irradiation step can be performed only once.

That is, when the substrates are bonded to each other, the liquid crystal mixture is dropped on one of the substrates and sandwiched between the two substrates to fill the cell with the liquid crystal mixture. Then, the resin is precipitated from the liquid crystal material to form a column, and after the resin is precipitated in the column, the entire surface of the cell including the sealing portion is irradiated with ultraviolet rays to cure the sealing portion and the column-shaped resin in one step. Can be done. Also, a re-gap step is not required. Therefore, the manufacturing process can be simplified and the manufacturing time can be reduced.

"Curing by ultraviolet light and heat"
In an active type liquid crystal electro-optical device, TFT or M
In the case where the IM elements are provided on a substrate, a light-shielding film for preventing light from being applied to the elements is provided on the substrate on the side facing the elements to stabilize the operation. Therefore, when a normal ultraviolet-curable resin is used to form a column-shaped resin, the uncured resin existing in the element portion remains uncured without the ultraviolet rays irradiated from the counter substrate side reaching the uncured resin. As a result, sufficient substrate strength may not be obtained.

When the temperature rises, such uncured resin dissolves in the liquid crystal material and acts as an impurity, which adversely affects the operation of the apparatus, such as instability of display. was there.

In order to cure the uncured resin in the portion having the region where the ultraviolet light is shielded, such as the light shielding film, and to prevent the mechanical strength and operation characteristics of the apparatus from being deteriorated, heat is applied in addition to the ultraviolet irradiation. The uncured resin may be cured. In this case, it is preferable to use an acrylic modified epoxy resin as a resin that cures both in ultraviolet light and heat.

That is, an acrylic modified epoxy resin that cures with ultraviolet light and heat is used as the resin material to be the column resin, and the resin in the portion where the ultraviolet light is shielded is mainly cured by heat, and the resin in the other portions is not cured. Cured by ultraviolet light.

By doing so, the resin deposited in a column at the portion where the irradiation of ultraviolet rays is not hindered is completely cured by the irradiation of ultraviolet rays. Since the other parts of the resin material are shielded from light, ultraviolet light cannot be used as a curing energy source.However, it is possible to cure the resin in this part by heating. It is possible to prevent a decrease in the target strength and the operation characteristics.

[Effects] As described above, according to the present invention, a resin can be scattered between substrates and the substrates on both sides can be fixed by the resin without impairing the alignment of the liquid crystal material. As a result, even if the liquid crystal cell has a large area, the distance between the substrates can be kept constant.

According to the present invention, an unnecessary change in the state of the liquid crystal molecules due to the electric charge in the device, which is a problem in the conventional liquid crystal electro-optical device, is positively caused by the electric charge existing in the device due to the electric charge from the reaction initiator. The problem can be solved by canceling it.

Further, according to the present invention, since the use of a charge transfer complex as in the prior art does not generate an excessive amount of charge for cancellation, optical stability of the device can be obtained for a long period of time. .

[0089]

BEST MODE FOR CARRYING OUT THE INVENTION

[0090]

[Embodiment 1] Embodiments 1 to 8 show examples in which a columnar resin is formed in a liquid crystal cell. FIG. 2 shows an example in which the present invention is applied to a liquid crystal electro-optical device using a ferroelectric liquid crystal.
Describe using.

10 cm square blue plate glass 1110, 1111
Indium-tin-oxide (abbreviated as ITO)
1112 and 1113 are formed by sputtering or vapor deposition 500 to
A film was formed to a thickness of 2000 °, here 1000 °, and patterned by a usual photolithography process. Polyimides 1114 and 1115 were applied on the substrate by spin coating and baked at 280 ° C. Hitachi Chemical L
Q5200, Toray LP-64, Nissan Chemical RN
-305 was used. The thickness was 100-300 °, here 100 °. This substrate was subjected to a rubbing treatment to obtain a uniaxial orientation treatment. On one substrate, a spacer 1118 made of a silica particle, which is a catalyzed chemical fiber ball, was sprayed, and on the other substrate, an epoxy resin sealing material 1119 was formed by screen printing. The two substrates were bonded to each other with a spacer having a distance between electrodes of about 1.5 μm to form a cell.

As the liquid crystal material 1116, a biphenyl-based ferroelectric liquid crystal mixture was used. _{C 8 H 17 O-C 6} H 4 -C as Formula ₆ H ₄ -COO-C ^* HCH
_{3 C 2 H 5 C 10 H} 21 O-C 6 H 4 -C 6 H 4 -COO-C * HCH
₃ C ₂ H ₅ is mixed at a ratio of 1: 1. The phase sequence shows an isotropic phase-smectic A phase-smectic C ^* -crystal. A commercially available ultraviolet-curable resin was used as the resin. The mixing ratio of the uncured resin in the mixture of the uncured resin and the liquid crystal material was set to 5% and 15%. The remaining 95% and 85% are liquid crystal material. The transition point of the liquid crystal material from the isotropic phase to the liquid crystal phase was lowered by 5 to 20 ° C. by mixing the resin.

The cell and the liquid crystal were heated to 100 ° C. and injected into the cell under vacuum. Thereafter, it was gradually cooled to room temperature at 2 to 20 ° C / hr, here 3 ° C / hr. When the alignment state at room temperature after slow cooling was observed with a polarizing microscope, the alignment of the liquid crystal material was uniaxial along the rubbing direction. That is,
A good extinction position could be confirmed under a polarizing microscope.

The resin was deposited so as to be interspersed between the liquid crystal materials. The resin did not show birefringence and could be observed in a black state under a polarizing microscope. In this state, the liquid crystal material and the uncured resin can be separated.

Next, the cell was irradiated with ultraviolet rays to cure the resin inside the cell. UV intensity is 3~30mW / cm ²
Here, the irradiation time was 10 mW / cm ² , and the irradiation time was 0.5 to 5 minutes.

The orientation of the liquid crystal material after the irradiation of the ultraviolet light almost coincided with that at the time of microscopic observation before the irradiation of the ultraviolet light, and was in a favorable alignment state.

Table 1 shows the results of measuring a contrast ratio by applying a square wave to this cell.

[0098]

[Table 1]

As shown in Table 1, when the proportion of the resin in the mixture was high, the ON transmittance was slightly decreased due to the increase in the area of the non-switching portion. The contrast ratio was a quotient of these values, but there was no significant difference, and a good contrast ratio was obtained. Also, when seen from the substrate side with the naked eye, the presence of the resin could not be recognized at all. From these results, it was found that if the proportion of the uncured resin in the mixture was about 0.1 to 20%, it could be comparable to a conventional apparatus. That is, the ratio of the area of the display portion to the liquid crystal material may be 80 to 99.9%.

Next, in order to see the effect of the slow cooling, the change in the orientation state when the cooling rate was changed was observed. Table 2 shows the results.

[0101]

[Table 2]

As shown in Table 2, in this example, a portion where the liquid crystal material was not uniaxially oriented was formed at a slow cooling rate of 100 ° C./hr or more. At about 20 ° C./hr or less, it was possible to obtain a good uniaxial orientation having no practical problem. Thus, good uniaxial orientation could be obtained by slow cooling. After that, the polarizing plates 1120, 11
21 was pasted, and the cell was completed.

In this way, a cell having a uniform distance between electrodes could be manufactured. Even when the completed cell was made vertical, display unevenness and the like could not be recognized at all. There was no deformation of the substrate and the layer structure of the used ferroelectric liquid crystal was not broken.

After the substrate was peeled off and the liquid crystal was washed away with alcohol, the resin remaining on the substrate was observed with a scanning electron microscope. As shown in FIG. 27, the columnar resin fixing both substrates was removed. I was able to observe.

The shape of the resin changes depending on the phase transition sequence of the liquid crystal material, the slow cooling rate, and the like. The interval between the columnar resins was about 10 to 100 μm.

FIG. 3 shows the relationship between the ratio of the resin occupying the display area and the mixing ratio of the uncured resin in the mixture. FIG.
As can be seen, the two were almost identical. That is, it was found that most of the mixed uncured resin was cured in a column shape.

[Embodiment 2] ST is set as the operation mode of the liquid crystal.
An embodiment using the N type will be described. Nissan Chemical Industries SE-4110 or SE-4110 as an alignment film on a 15-inch diagonal substrate on which ITO was formed and patterned.
-610 was formed by an offset printing method using a stripe coater. The sintering temperature was 200 to 300 ° C, here 280 ° C. The film thickness was 600-1000 °, here 800 °. The two substrates were rubbed so that the angle formed by the rubbing directions when the upper and lower substrates faced each other was 240 °. 6.5 on one of the substrates
μm silica spacers are sprayed, seal printing is performed on the other substrate, and the pressure is applied with both processing surfaces facing inward,
Heated and fixed.

As a liquid crystal material, ZLI-22 manufactured by Merck was used.
93 and 0.1 to 3 of S-811 as a chiral agent.
% Here, 0.12% was added to adjust the pitch, and the ratio of the cell thickness to the pitch was changed from 0.50 to 0.55. Here, what added 5% of the ultraviolet curable resin to the liquid crystal was vacuum injected into the above-mentioned cell. After the injection, the cell was pressed to remove excess liquid crystal, heated at 120 ° C. for 1 hour, and then gradually cooled to room temperature.

In this cell, 3 to 30 mW / cm ^2, where 1
Ultraviolet rays of 0 mW / cm ² were irradiated to cure the resin inside. The resin was scattered throughout the cell. A TSTN panel was obtained by combining a polarizing plate and a color compensator.

Since the two substrates were fixed by the resin inside, they had a uniform area between the electrodes despite having a large area of 15 inches diagonally. When this cell is driven at a duty of 200, the contrast ratio is 1
As a result, a panel having a contrast ratio equivalent to that of a conventional device containing no resin was obtained.

Embodiment 3 A case where the present invention is applied to a birefringence control effect type liquid crystal electro-optical device will be described. As an alignment film, Nissan Chemical's SE-7511L, RN715 or Hitachi Chemical LQ-1800 was applied on a substrate with ITO using a spinner, and baked at 250 to 300 ° C, here 300 ° C. The film thickness is 500 to 1000 (here, 600)
Met. This alignment film is a highly hydrophobic alignment film that easily forms vertical alignment with the nematic liquid crystal. Using this substrate, a cell having an interelectrode distance of 6 μm was formed. Here, a mixture containing 5% of an ultraviolet curable resin with respect to Merck's ZLI-4318 nematic liquid crystal having a negative dielectric anisotropy was injected into the cell. The dielectric anisotropy of this liquid crystal material is
-2.0.

After the cooling, ultraviolet rays were irradiated to cure the dispersed resin. When a conoscopic image was observed with a polarizing microscope in this state, a cross image was observed, and it was found that the liquid crystal molecules were arranged perpendicular to the substrate surface. The contrast ratio when a drive voltage is applied to this cell is 80.
In addition, it was possible to make display unevenness extremely small. In this way, while maintaining the liquid crystal properties when the resin is not included in the alignment state and the contrast ratio,
Both substrates could be fixed with resin.

Example 4 A pair of glass substrates 30 cm square and 1.1 mm thick were each formed of indium, an electrode material.
Tin oxide (abbreviated as ITO) is formed by sputtering or vapor deposition at 500 to 2000 Å,
A film was formed to a film thickness of Å, and the electrode was patterned by a usual photolithography process. Polyimide was applied on this substrate by a spin coating method and baked at 280 ° C. Nissan Chemical's RN-305 and Toray's LP-64 were used here as the polyimide. Polyimide film thickness is 100-8
00 °, and 150 ° in this embodiment. The substrate was subjected to a rubbing treatment to perform a uniaxial orientation treatment. On one substrate, a silica fiber-made sphere made of catalyst chemicals was sprayed as a spacer, and on one substrate, a sealing material made of epoxy resin was formed by screen printing. The two substrates were attached to each other with a distance between the electrodes of about 1.5 μm to form a cell. In order to prevent a short circuit between the electrodes, an insulating film may be provided to cover the electrodes and the leads on the substrate, and an alignment film may be provided thereon.

The liquid crystal material used in this embodiment is CS1014, a ferroelectric liquid crystal manufactured by Chisso Corporation. The Ps of this liquid crystal is 5.4 nC / cm ² , and the phase sequence is I (isotropic phase) -N (nematic phase) -A (smectic A phase).
-C ^* (smectic C ^* phase).

The resin material used in this example is a commercially available ultraviolet-curable resin, and as a reaction initiator in the resin material, one having the highest reactivity among the ones which can obtain the best effect of the present invention is used. Irgacure 369 was used.

[0116] 95% of the liquid crystal material and 5% of a resin constituent material to which a reaction initiator is added as a resin material are mixed, and 100% is mixed so that the mixed resin material is more well mixed in the liquid crystal material.
The mixture was heated and stirred at ℃ until the liquid crystal showed an isotropic phase to uniformly mix the resin in the liquid crystal material to form a liquid crystal mixture. The addition amount of the reaction initiator is 3 with respect to the total amount of the reaction initiator and the resin constituent materials.
%Met.

The cell and the liquid crystal mixture were heated to 100 ° C., and after being poured into the above-mentioned cell under vacuum, the mixture was gradually cooled to room temperature at 2 to 20 ° C./hr, in this example, 2 ° C./hr. When the alignment state at room temperature after slow cooling is observed with a polarizing microscope, the resin material is scattered in the cell, and the liquid crystal is aligned in the rubbing direction of the alignment film in the same manner as the liquid crystal material to which no resin is added. And a good extinction position was obtained.

Ultraviolet light was applied to this cell at an intensity of 3 to 30 mW /
cm ^2, irradiation time 0.5～5Min, the resin was cured by performing the irradiation of 1min at intensity 20 mW / cm ² in the present embodiment. The liquid crystal was uniaxially aligned along the rubbing direction of the alignment film even after irradiation with ultraviolet light, and a good extinction position was obtained. The ratio of the area of the display portion of the cell to the resin material was about 5%. Although the cured resin could be observed with a microscope, its presence could not be confirmed with the naked eye. A polarizing plate and the like were added to this cell to produce a liquid crystal electro-optical device.

± 3 between the upper and lower electrodes of the liquid crystal electro-optical device.
When a current characteristic (hereinafter referred to as a current-voltage characteristic) when a voltage is continuously changed by applying a triangular wave of 0 V and 5 Hz is measured, as shown in FIG. Is changed by 180 °, that is, Ps is inverted.
Only peaks could be observed.

FIG. 6 shows the optical characteristics when the device is operated by applying a pulse of 1 μsec, 15 V between the electrodes of the device every 1 second (opening when no application is performed) (in the embodiment of the present specification). , Current-voltage characteristics and optical characteristics show relative values of each element). As is clear from the figure, when a voltage higher than the Ps peak voltage is applied, a sharp change in brightness (Bright, Dark) occurs, and the state is stable. Also, the memory property at the time of short circuit was good.

Even if the ratio of the resin in the liquid crystal mixture is changed from 0.1% to 20%, the ratio of the area occupying the display portion of the resin in the cured cell is 0% as in the case of the mixed resin. 0.1% to 20%, and were dispersed in the cell.
The cells after curing of the resin were divided in the thickness direction, and the liquid crystal was washed and removed with methanol, and the shape of the resin portion was observed with an SEM. That was confirmed.

The thus manufactured liquid crystal electro-optical device was free from display unevenness, flicker, and the like, and was a very high-performance device having stable optical characteristics. Further, an active matrix type liquid crystal electro-optical device in which a plurality of pixel electrodes and a thin film transistor connected to the pixel electrodes were formed on the inner surface of one substrate was manufactured by filling the liquid crystal mixture of this example in a cell, and high speed and high contrast were obtained. A device having a ratio was obtained. In addition, the distance between the substrates is kept constant by the resin, and despite the large area of 30cm □, the distance between the substrates is increased due to the bending of the substrate when the device is used upright and the substrate surface is pushed with a finger or the like. In this case, the distance between the substrates did not decrease, and there was no display irregularity, no disturbance in the layer structure of liquid crystal, and no alignment.

For comparison, characteristics were measured using the same cell structure, manufacturing conditions, and liquid crystal material without mixing the resin material, that is, the uncured resin material and the reaction initiator into the liquid crystal material. The liquid crystal and the cell are heated to 100 ° C. and injected into the cell under vacuum,
Cooled slowly. When the alignment state after slow cooling was observed with a polarizing microscope, the liquid crystal was uniaxially aligned along the rubbing direction of the alignment film, and a good extinction position was obtained. A polarizing plate and the like were added to this cell to produce a liquid crystal electro-optical device.

The liquid crystal electro-optical device has ± 30 V, 5 Hz
When the current-voltage characteristics were measured by applying a triangular wave of FIG.
The Ps peak and the increase / decrease of the current considered to be the movement of the electric charge in the device, that is, the second peak are measured.

FIG. 8 shows the optical characteristics when the device was operated by applying a 1 μsec, 15 V pulse every 1 second. Although the liquid crystal molecules are inverted by a voltage application to be in a dark state, this dark state is unstablely changed to a bright state side and then to a dark state side with time. The dark state was not very good.

When the apparatus is used upright, liquid crystal material accumulates in the lower part of the substrate, causing a portion where the substrate interval becomes large, and when pressed with a finger, the distance between the substrates is reduced, and the liquid crystal layer structure is reduced. Collapse and display unevenness have occurred.

Next, a liquid crystal material and a resin material
% And 5%, and the addition amount of the reaction initiator in the resin material is 0 to 10% with respect to the total amount of the resin constituent material and the reaction initiator.
Changed.

When the amount of the reaction initiator added was 0%, the liquid crystal was uniaxially aligned along the rubbing direction of the alignment film, and a good extinction position was obtained. However, the current-voltage characteristics were measured by applying a triangular wave voltage. Then, the Ps peak and the second peak are measured. 1μsec, 15V pulse for 1sec
FIG. 9 shows the optical characteristics when the operation is performed by applying the voltage every time. Although the liquid crystal molecules are inverted by a voltage application to be in a dark state, the dark state changes with time and shifts to a slightly bright state. Although the characteristics are slightly better than those of the above-described example (FIG. 8) in which the resin is not added, the instability remains. Also, the resin does not naturally cure.

In the case of the reaction initiator used in this example, when the addition amount was 0.3% or more, the resin was cured, the generation of the second peak was suppressed, and the characteristics were improved.

Example 5 The structure of the device, the ratio of liquid crystal and resin, the type of reaction initiator in the resin and the amount added are the same as in Example 4 in this example. As a liquid crystal material of the present example, CS1015 manufactured by Chisso and having a phase sequence of 6.6 nC / cm ² , which shows INAC ^* was used. Add the resin material to the liquid crystal material, and heat and stir to 90 ° C to mix well in the liquid crystal material.
The mixture was poured into a heated cell under vacuum, cooled slowly, and then cured by ultraviolet irradiation. The liquid crystal was uniaxially oriented along the rubbing direction, and a good extinction position was obtained. A polarizing plate or the like was added to the cell to obtain a liquid crystal electro-optical device.

The liquid crystal electro-optical device has ± 30 V, 5 Hz.
When the current-voltage characteristic is measured by applying a triangular wave of FIG.
, Only the Ps peak could be observed.

The optical characteristics when the device is operated by applying a 1 μsec, 15 V pulse every 1 sec (open when no voltage is applied) are the same as those of the fourth embodiment. And the light and dark states were stable without change over time. The memory property at the time of short circuit was also good.

The liquid crystal electro-optical device manufactured in this manner was free from display unevenness and flicker, and could be an extremely high-performance device having stable optical characteristics. Further, an active matrix type liquid crystal electro-optical device in which a plurality of pixel electrodes and a thin film transistor connected to the pixel electrodes were formed on the inner surface of one substrate was manufactured by filling the liquid crystal mixture of this example in a cell, and high speed and high contrast were obtained. A device having a ratio was obtained. In addition, the distance between the substrates is kept constant by the resin, and despite the large area of 30cm □, the distance between the substrates is increased due to the bending of the substrate when the device is used upright and the substrate surface is pushed with a finger or the like. In this case, the distance between the substrates did not decrease, and there was no display irregularity, no disturbance in the layer structure of liquid crystal, and no alignment.

For comparison, in the configuration of this example, the characteristics were examined by filling only the liquid crystal material in the cell without adding the resin constituent material and the reaction initiator. The liquid crystal was uniaxially aligned along the rubbing direction of the alignment film, and a good extinction position was obtained. However, when a triangular wave was applied between the electrodes and the current-voltage characteristics were measured, as shown in FIG. Two peaks were observed.

FIG. 12 shows the optical characteristics when the device was operated by applying a pulse of 1 μsec and 15 V every 1 second.
Shown in Although the liquid crystal molecules were inverted by the voltage application to be in a dark state, the liquid crystal molecules immediately changed to the light state in an unstable manner.

When the apparatus is used upright, liquid crystal material accumulates in the lower part of the substrate, causing a portion where the distance between the substrates increases, and when pressed with a finger, the distance between the substrates in that portion is reduced, and the layer structure of the liquid crystal is reduced. Collapse and display unevenness have occurred.

Example 6 The structure of the device, the ratio between liquid crystal and resin, the type of reaction initiator in the resin and the amount added are the same as in Example 4 in this example. However, as the liquid crystal material of the present example, CS1017 manufactured by Chisso and having a phase sequence of 9.3 nC / cm ² , which shows INAC ^* was used. In order to better mix the added resin material in the liquid crystal, the resin was heated and stirred at 80 ° C., poured into a cell heated to 80 ° C. under vacuum, cooled slowly, and then cured by irradiation with ultraviolet rays.
The liquid crystal is uniaxially aligned along the rubbing direction of the alignment film,
A good extinction position was obtained. The device was completed by adding a polarizing plate and the like.

When the current when the voltage applied to the liquid crystal electro-optical device was continuously changed was measured, only the Ps peak could be observed as shown in FIG.

The optical characteristics when the device is operated by applying a 1 μsec, 15 V pulse every 1 sec (open when no voltage is applied) are the same as in the fourth embodiment. Occurred, the light and dark states were stable with no change over time. The memory property at the time of short circuit was also good.

The liquid crystal electro-optical device manufactured in this manner was free from display unevenness, flicker and the like, and could be an extremely high-performance device having stable optical characteristics. Further, an active matrix type liquid crystal electro-optical device in which a plurality of pixel electrodes and a thin film transistor connected to the pixel electrodes were formed on the inner surface of one substrate was manufactured by filling the liquid crystal mixture of this example in a cell, and high speed and high contrast were obtained. A device having a ratio was obtained. In addition, the distance between the substrates is kept constant by the resin, and despite the large area of 30cm □, the distance between the substrates is increased due to the bending of the substrate when the device is used upright and the substrate surface is pushed with a finger or the like. In this case, the distance between the substrates did not decrease, and there was no display irregularity, no disturbance in the layer structure of liquid crystal, and no alignment.

For comparison, a cell was prepared without mixing the resin constituent material and the reaction initiator in the liquid crystal material. The liquid crystal was uniaxially oriented along the rubbing direction, and a good extinction position was obtained. However, when a triangular wave was applied to this device and the current-voltage characteristics were examined, the Ps peak and the second peak were observed as shown in FIG. Was done.

The optical characteristics when this device was operated by applying a pulse of 1 μsec and 15 V every one second were almost the same as those in FIG. 12 of the fifth embodiment. Although the liquid crystal molecules were inverted by the voltage application to be in a dark state, the liquid crystal molecules immediately changed to the light state in an unstable manner.

When the apparatus is used upright, liquid crystal material accumulates in the lower part of the substrate, causing a portion where the distance between the substrates increases, and when pressed with a finger, the distance between the substrates in that portion is reduced, and the layer structure of the liquid crystal is reduced. Collapse and display unevenness have occurred.

[Embodiment 7] The structure of the device in this embodiment and the mixing ratio of the liquid crystal and the resin in the liquid crystal mixture are the same as in Embodiment 4. However, as the liquid crystal material of this example, a biphenyl-based ferroelectric liquid crystal having a phase sequence of 10.9 nC / cm ² showing IAC ^* was used. The resin material is a commercially available ultraviolet curable resin. As a reaction initiator in this resin, Ciba Geigy's Irgacure 184 was mixed so as to be 1% with respect to the total amount of the resin constituent material and the reaction initiator.

In order to better mix the added resin material in the liquid crystal, heat the mixture at 120 ° C. until the liquid crystal shows an isotropic phase.
Stir and inject under vacuum into the cell heated to 120 ° C.
After slow cooling, the resin was cured by irradiation with ultraviolet rays. The liquid crystal was uniaxially aligned along the rubbing direction of the alignment film as in the case of the liquid crystal material to which no resin was added, and a good extinction position was obtained. A liquid crystal electro-optical device was completed by adding a polarizing plate and the like.

When the current when the voltage applied to the liquid crystal electro-optical device was continuously changed was measured, only the Ps peak could be observed as shown in FIG.

FIG. 16 shows the optical characteristics when the device is operated by applying a 1 μsec, 15 V pulse every 1 second (open when no voltage is applied). As is apparent from the figure, when the voltage is applied, the reversal of light and dark occurs, and the optical characteristics, particularly the dark state, become good, and this state is also stable. Also, the memory property at the time of short circuit was good.

The thus manufactured liquid crystal electro-optical device was free from display unevenness and flicker, and could be an extremely high-performance device having stable optical characteristics. Further, an active matrix type liquid crystal electro-optical device in which a plurality of pixel electrodes and a thin film transistor connected to the pixel electrodes were formed on the inner surface of one substrate was manufactured by filling the liquid crystal mixture of this example in a cell, and high speed and high contrast were obtained. A device having a ratio was obtained. In addition, the distance between the substrates is kept constant by the resin, and despite the large area of 30cm □, the distance between the substrates is increased due to the bending of the substrate when the device is used upright and the substrate surface is pushed with a finger or the like. In this case, the distance between the substrates did not decrease, and there was no display irregularity, no disturbance in the layer structure of liquid crystal, and no alignment.

For comparison, a cell was prepared without adding a resin material to the liquid crystal material. The liquid crystal was uniaxially oriented along the rubbing direction, and a good extinction position was obtained. However, when the current-voltage characteristics were measured, a Ps peak and a second peak were observed as shown in FIG.

FIG. 18 shows the optical characteristics when the device was operated by applying a pulse of 1 μsec and 15 V every 1 second.
Shown in Although the liquid crystal molecules were inverted by the voltage application and turned into a dark state, this state change was gradual, and the dark state was not sufficiently stabilized.

When the apparatus is used upright, liquid crystal material accumulates in the lower part of the substrate, causing a portion where the distance between the substrates increases, and when pressed with a finger, the distance between the substrates in that portion is reduced, and the layer structure of the liquid crystal is reduced. Collapse and display unevenness have occurred.

Example 8 Indium tin oxide (abbreviated as ITO) was formed on a 10 cm square glass substrate by sputtering or vapor deposition to a thickness of 500 to 2000 Å, and in this embodiment, 1000 Å. The electrodes were patterned by a normal photolithography process. Nissan Chemical SE-
4110 or SE-610, here SE-4110
Offset printing with a stripe coater, 200 ~
300 ° C. In this example, the film was fired at 280 ° C. to form an alignment film. The film thickness is 600 to 1000 °, and 800 ° in this embodiment.
Met. This substrate is processed so that the rubbing direction is 90 ° when the electrode surfaces are opposed to each other.
5 μm silica particles were scattered, and a sealing material was screen-printed and bonded on the other substrate to form a cell for TN.

The liquid crystal material used was a cyanobiphenyl nematic liquid crystal having a positive dielectric anisotropy of 95%, and the resin material was a commercially available ultraviolet curable resin at a ratio of 5%. To better mix the resin in the liquid crystal,
The mixture was heated and stirred at 液晶 ° C. until the liquid crystal showed an isotropic phase, poured into the cell under vacuum, and gradually cooled, after which the resin was cured.

When a voltage of 10 V is applied to the completed liquid crystal electro-optical device, the voltage applied to the liquid crystal layer changes sharply and does not change with time. The optical characteristics also changed sharply from dark to bright with the voltage change, and there was no change with time. Further, even when the apparatus was used upright, the distance between the substrates was kept constant without being increased by the resin, and no display unevenness occurred.

The liquid crystal electro-optical device manufactured in this manner was free from display unevenness and flicker, and could be an extremely high-performance device having stable optical characteristics. Further, an active matrix type liquid crystal electro-optical device in which a plurality of pixel electrodes and a thin film transistor connected to the pixel electrodes were formed on the inner surface of one substrate was manufactured by filling the liquid crystal mixture of this example in a cell, and high speed and high contrast were obtained. A device having a ratio was obtained.

For comparison, a device was prepared without adding a resin to the liquid crystal material. When a voltage of 10 V was applied to this liquid crystal electro-optical device, the voltage between the electrodes (the liquid crystal layer) changed greatly with time, and the optical characteristics also changed with the time.

Example 9 Examples 9 to 12 show examples in which a reaction initiator was mixed in a liquid crystal material. Indium tin oxide (abbreviated as ITO), which is an electrode material, is applied to a 10 cm square glass substrate by sputtering or vapor deposition.
A film was formed to a thickness of 2000 to 2000 Å, and 1000 Å in this embodiment, and the electrodes were patterned by a normal photolithography process.
Polyimide is applied on this substrate by spin coating,
It was baked at 80 ° C. Nissan Chemical's RN as polyimide
-305, Toray LP-64 was used. The polyimide film thickness was 100 to 800 °, and in this example was 150 °.
The substrate was subjected to a rubbing treatment to perform a uniaxial orientation treatment. On one of the substrates, a catalyst chemical sphere made of silica particles was sprayed as spacers, and on one of the substrates, an epoxy resin sealing material was screen-printed. The two substrates were attached to each other with a distance between the electrodes of about 1.5 μm to form a cell.

The liquid crystal material used in this example is CS1014, a ferroelectric liquid crystal manufactured by Chisso Corporation. The Ps (spontaneous polarization) of this liquid crystal is 5.4 nC / cm ² , and the phase sequence is I (isotropic phase) -N (nematic phase) -A (smectic A phase) -C ^* (smectic C ^* phase). is there. As a reaction initiator, Irgacure 369 manufactured by Ciba-Geigy was used from among those having the best effects of the present invention.

The above-mentioned reaction initiator is added to the liquid crystal in an amount of from 0.1 to 3%.
%, In this example, 3% was added. In order to better mix the added initiator in the liquid crystal, the reaction initiator was heated and stirred at 100 ° C. until the liquid crystal showed an isotropic phase. Into the mixture. (Hereinafter referred to as liquid crystal mixture)

The cell and the liquid crystal mixture were heated to 100 ° C. and injected under vacuum into the cell. After this, 2-20 ° C / h
r In this example, the temperature was gradually cooled to room temperature at 2 ° C./hr. When the alignment state at room temperature after the slow cooling was observed with a polarizing microscope, the liquid crystal was uniaxially aligned along the rubbing direction, and a good extinction position was obtained, as in the case of the liquid crystal material to which no reaction initiator was added.

With respect to this liquid crystal electro-optical device, ±
When the current-voltage characteristics when the applied voltage was continuously changed by applying a triangular wave of 20 V and 5 Hz were measured, FIG.
At a certain voltage value such as 9 (shown in an arbitrary unit), only the peak at which the liquid crystal molecules change the direction of spontaneous polarization by 180 °, that is, the inversion (hereinafter referred to as Ps peak) was observed.

FIG. 2 shows the optical characteristics when the device was operated by applying a pulse of 1 μmsec and 15 V every 1 second.
0 is shown. As is clear from the figure, when a voltage equal to or higher than the Ps peak voltage is applied, inversion of light and dark (Bright and Dark) occurs, and a steep light and dark state still occurs and the state is stable.

Example 10 The structure of the device, the liquid crystal material and the reaction initiator used in this example are the same as in Example 1. However, the amount of the reaction initiator added in this example is 1% in the liquid crystal material. To better mix the added initiator in the liquid crystal, heat and stir at 100 ° C. until the liquid crystal shows an isotropic phase, and uniformly mix the initiator in the liquid crystal as in Example 9. Thus, a liquid crystal mixture was prepared.

The cell and the liquid crystal mixture were heated to 100 ° C. and injected into the cell under vacuum. After this, 2-20 ° C / h
r, in this example, as in Example 9, it was gradually cooled to room temperature at 2 ° C./hr. Observation of the alignment state at room temperature after slow cooling with a polarizing microscope shows that, like the liquid crystal material without the addition of a reaction initiator,
The liquid crystal was uniaxially oriented along the rubbing direction, and a good extinction position was obtained.

When a current-voltage characteristic was measured by applying a triangular wave of ± 20 V and 5 Hz between the electrodes of the liquid crystal electro-optical device in the same manner as in the ninth embodiment, only the Ps peak was found at a certain voltage value as in the ninth embodiment. The observed characteristics.

FIG. 2 shows the optical characteristics when the device was operated by applying a pulse of 1 μm sec. 15 V every 1 second.
It is shown in FIG. As is clear from the figure, when a voltage equal to or higher than the Ps peak voltage is applied, inversion of light and dark occurs, and a dark state occurs once.
This state changes to the bright state side over time.

The apparatus was irradiated with ultraviolet light to supply more electric charge from the reaction initiator. At this time, the irradiation intensity of the ultraviolet light was 20 mW / cm2, and the irradiation time was 1 min. Observation of the current-voltage characteristics shows that P
Only the s peak was confirmed. As in the case of Example 9, the optical characteristics showed a sharp change in light and dark, and this state was stable without a change over time.

Embodiment 11 The liquid crystal material used in this embodiment is a biphenyl-based material having a Ps of 10.9 nC / cm.
Phase series 2 is I (isotropic phase) -A (smectic A phase)-
It is a ferroelectric liquid crystal showing C ^* (smectic C ^* phase). As a reaction initiator, Irgacure 184 manufactured by Ciba-Geigy was used, and the amount added was 1% in the liquid crystal material.

In order to better mix the added initiator in the liquid crystal, the mixture was heated and stirred at 120 ° C. until the liquid crystal showed an isotropic phase, and the reaction initiator was uniformly mixed in the liquid crystal. Was prepared.

A cell having the same structure as in Example 9 was prepared, and this cell and the liquid crystal mixture were heated to 120 ° C. and injected into the cell under vacuum. Thereafter, the temperature was gradually cooled to room temperature at 2 to 20 ° C./hr, in this example, 2 ° C./hr. When the alignment state at room temperature after the slow cooling was observed with a polarizing microscope, the liquid crystal was uniaxially aligned along the rubbing direction of the alignment film, and a good extinction position was obtained, as in the case of the liquid crystal material to which no reaction initiator was added.

In this liquid crystal electro-optical device, ±
When the current-voltage characteristics when a triangular wave of 20 V and 5 Hz was applied were measured, only the Ps peak at a certain voltage value similar to the above-described example could be observed.

FIG. 2 shows the optical characteristics when the device was operated by applying a pulse of 1 μm sec and 15 V every 1 second.
It is shown in FIG. Although the darkness is reversed by application of a voltage, the dark state changes to the bright state over time. This dark state was not very good.

The device was irradiated with ultraviolet light to supply more charge from the initiator. At this time, the irradiation ultraviolet light intensity was 20 mW / cm ² , and the irradiation time was 1 min.
When the current-voltage characteristics of this liquid crystal electro-optical device were measured, Ps at a certain voltage value similar to that before irradiation with ultraviolet light was obtained.
Only peaks could be observed.

[0174] In this apparatus, 1 µms
FIG. 23 shows the optical characteristics when operating by applying a pulse of ec, 15 V every 1 sec. Then, when the voltage is applied, light / dark inversion occurs, and it can be seen that the optical characteristics, particularly the dark state, are good and this state is also stable.

Example 12 A 10 cm square glass substrate was coated with indium tin oxide (ITO) as an electrode material.
500 to 200 by sputtering or vapor deposition.
A film was formed to a thickness of 0 °, in this example, 1000 °, and the electrodes were patterned by a usual photolithography process. On this substrate, Nissan Chemical's SE-4110 or SE-610 was offset-printed with a stripe coater, and 200 to 3
00 ° C. In this example, the film was fired at 280 ° C. to form an alignment film.
The film thickness was 600 to 1000 °, and 800 ° in this example. This substrate is treated so that the rubbing direction is 90 ° when the electrode surfaces are opposed to each other, and 6.5 μm is formed on one substrate.
m silica particles were scattered, and a sealing material was printed on the other substrate and bonded to form a cell for TN.

As the liquid crystal material used, a cyanobiphenyl nematic liquid crystal having a positive dielectric anisotropy was used. As a reaction initiator, 3% of Irgacure 369 is contained in the liquid crystal.
In order to better mix the added initiator in the liquid crystal, heat and stir at 90 ° C. until the liquid crystal shows an isotropic phase, uniformly mix the initiator in the liquid crystal, and mix the liquid crystal. Was prepared and injected into the cell.

When a voltage of 10 V is applied to the liquid crystal electro-optical device, the voltage applied to the liquid crystal layer changes sharply and does not change with time. The optical characteristics also changed sharply from dark to bright with the voltage change, and there was no change with time.

Comparative Example 1 The structure of the device and the liquid crystal material in this comparative example are the same as in Examples 9 and 10. However, no reaction initiator was added to the liquid crystal material of this comparative example.

The cell and the liquid crystal material were heated to 100 ° C. and injected into the cell under vacuum. After this, 2-20 ° C / hr,
In this example, the temperature was gradually cooled to room temperature at 2 ° C./hr. When the alignment state at room temperature after slow cooling was observed with a polarizing microscope, the liquid crystal was uniaxially aligned along the rubbing direction, and a good extinction position was obtained.

When the current-voltage characteristics of the liquid crystal electro-optical device are measured, the Ps peak and the increase or decrease of the current (hereinafter, referred to as a second peak), which are considered to be the movement of charges in the device, are measured as shown in FIG. Normally, this second peak exists close to the Ps peak, so it is difficult to determine the voltage to be applied during operation of the device.

FIG. 2 shows the optical characteristics when the device was operated by applying a pulse of 1 μmsec and 15 V every 1 second.
It is shown in FIG. Although the liquid crystal molecules are inverted by a voltage application to be in a dark state, this dark state is unstablely changed to a bright state side and then to a dark state side with time.

Comparative Example 2 The structure of the device and the liquid crystal material in this comparative example are the same as in Example 11. However, no reaction initiator was added to the liquid crystal material of this comparative example.

As in Example 11, liquid crystal was injected into the above cell under vacuum. When the current-voltage characteristics of this liquid crystal electro-optical device were measured, the Ps peak and the
A second peak was measured.

FIG. 2 shows the optical characteristics when the device was operated by applying a pulse of 1 μm sec, 15 V every 1 second.
6 is shown. The light / dark state is reversed by the application of the voltage, but the state change is gradual.

Comparative Example 3 The structure of the device and the liquid crystal material in this comparative example are the same as in Example 12. However, no reaction initiator was added to the liquid crystal material of this comparative example. This liquid crystal was injected as in Example 12.

When a voltage of 10 V was applied to the liquid crystal electro-optical device, the voltage applied to the liquid crystal changed with time, and the optical characteristics also changed with the time.

[Embodiment 13] This embodiment shows an example in which the liquid crystal material is oriented again after the resin is cured. Indium tin oxide (abbreviated as ITO), which is an electrode material, is placed on a 10 cm square glass substrate by sputtering or vapor deposition.
A film was formed to a thickness of 2000 to 2000 Å, and 1000 Å in this embodiment, and the electrodes were patterned by a normal photolithography process.
Polyimide is applied on this substrate by spin coating,
It was baked at 80 ° C. Nissan Chemical's RN-305 and Toray's LP-64 were used as the polyimide to be the alignment film. The polyimide film thickness is 100 to 800 °, and in this embodiment, 150
Was Å. The substrate was subjected to a rubbing treatment to perform a uniaxial orientation treatment. On one substrate, a silica fiber-made sphere made of catalyst chemicals was sprayed as a spacer, and on one substrate, a sealing material made of epoxy resin was formed by screen printing. The two substrates were attached to each other with a distance between the electrodes of about 1.5 μm to form a cell.

The liquid crystal material used in this example is CS1014, a ferroelectric liquid crystal manufactured by Chisso Corporation. The Ps of this liquid crystal is 5.4 nC / cm ² , and the phase sequence is I (isotropic phase) -N (nematic phase) -A (smectic A phase).
-C (smectic C ^* phase).

The resin material used in this example is a commercially available mixture of a urethane oligomer and an acrylic monomer.

The liquid crystal material 95% and the uncured resin material 5
% (Weight ratio), and the mixture was heated and stirred at 90 ° C. until the liquid crystal showed an isotropic phase so that the mixed resin was better mixed in the liquid crystal material, and the resin was uniformly mixed in the liquid crystal material. (Hereinafter referred to as a liquid crystal mixture).

The cell and the liquid crystal mixture were heated to 90 ° C., poured into the above-described cell under vacuum, and gradually cooled to room temperature at 2 to 20 ° C./hr, in this example, 2 ° C./hr. When the alignment state at room temperature after slow cooling is observed with a polarizing microscope, the resin material is scattered in the cell, and the liquid crystal is aligned in the rubbing direction of the alignment film in the same manner as the liquid crystal material to which no resin is added. And a good extinction position was obtained.

Ultraviolet light was applied to this cell at an intensity of 3 to 30 mW /
cm ^2, irradiation time 0.5～5Min, 1min at an intensity 20 mW / cm ² in this embodiment was cured by irradiating the resin. The liquid crystal was uniaxially aligned along the rubbing direction of the alignment film even after ultraviolet irradiation, and a good extinction position was obtained.

An optical characteristic was measured by applying a triangular wave of ± 30 V to the cell. Careful observation of the operating state revealed that a small amount of light escaped from around the resin when the dark state was displayed. At this time, the bright state value (indicated by an arbitrary value) is 35.
26, dark state value 1.131, contrast 31.1
6. The voltage holding ratio when a pulse of ± 20 V and 60 μm was applied to this cell was measured and found to be 45.0%. Observation after aging of this cell, light leakage around the resin was significantly improved by visual observation. At this time, the light state value was 40.08, the dark state value was 0.924, the contrast was 43.39, and the voltage of this cell was When the retention was measured, it was 49.0%, and the actual characteristics were significantly improved.

[Embodiment 14] This embodiment shows an example in which the liquid crystal material is oriented again after the resin is cured. The configuration of the device, the liquid crystal material, and the resin material in this example were the same as those in Example 13.

The liquid crystal material 85% and the uncured resin material 1
5% was mixed and the mixture was heated and stirred at 90 ° C. until the liquid crystal showed an isotropic phase to make the mixed resin better mixed in the liquid crystal material to form a liquid crystal mixture.

The cell and the liquid crystal mixture were heated to 90 ° C., and after being injected into the above-described cell under vacuum, the mixture was gradually cooled to room temperature at 2 to 20 ° C./hr, in this example, 2 ° C./hr. When the alignment state at room temperature after slow cooling is observed with a polarizing microscope, the resin material is scattered in the cell, and the liquid crystal is aligned in the rubbing direction of the alignment film in the same manner as the liquid crystal material to which no resin is added. And a good extinction position was obtained.

Ultraviolet light was applied to this cell at an intensity of 3 to 30 mW /
cm ^2, irradiation time 0.5～5Min, the resin was cured by performing the irradiation of 1min at intensity 20 mW / cm ² in the present embodiment. The liquid crystal was uniaxially aligned along the rubbing direction of the alignment film even after ultraviolet irradiation, and a good extinction position was obtained.

An optical characteristic was measured by applying a triangular wave of ± 30 V to the cell. Careful observation of the operating state revealed that a small amount of light escaped from around the resin when the dark state was displayed. At this time, the bright state value (indicated by an arbitrary value) is 22.
89, dark state value is 3.491, contrast is 6.6,
The voltage holding ratio was 61.0%. Observation after aging of this cell, light leakage around the resin was significantly improved by visual observation. At this time, the light state value was 31.48, the dark state value was 3.162, the contrast was 10, and the voltage holding ratio was 7
1.0%, and the actual characteristics were also greatly improved.

[Embodiment 15] This embodiment shows an example in which a sealing material and an uncured resin are simultaneously cured. The liquid crystal material used in this example is CS1014, a ferroelectric liquid crystal manufactured by Chisso Corporation. The Ps of this liquid crystal is 5.4n
C / cm ² , and the phase sequence is I (isotropic phase) -N (nematic phase) -A (smectic A phase) -C (smectic C ^* phase).

The resin material used in this example is a commercially available mixture of a urethane oligomer and an acrylic monomer.
The above materials are mixed in a weight ratio of 95% of the liquid crystal and 5% of the uncured resin, so that the mixed resin and the liquid crystal are mixed better.
The resin was heated and stirred at 90 ° C. until the liquid crystal showed an isotropic phase to uniformly mix the resin in the liquid crystal material (hereinafter referred to as a liquid crystal mixture).

An indium tin oxide (abbreviated as ITO), which is an electrode material, is formed on a 10 cm square glass substrate by sputtering or vapor deposition to a thickness of 500 to 2000 Å, and in this embodiment, 1000 Å. The electrodes were patterned in the photolithography process described above. Polyimide was applied on this substrate by a spin coating method and baked at 280 ° C. Nissan Chemical's RN-305 and Toray's LP-64, here, Toray's LP-64, were used as the polyimide to be the alignment film. The polyimide film thickness is 100 to 800 °, and in this embodiment, 150
Was Å. The substrate was subjected to a rubbing treatment to perform a uniaxial orientation treatment. On one of the substrates, catalyzed chemical spheres, which are silica particles, were scattered as spacers, and on the other substrate, an ultraviolet-curable resin was used as a sealant by screen printing.

Heating both substrates above the transition point of the liquid crystal mixture,
An appropriate amount of an isotropic liquid crystal mixture was dropped on a substrate on which a seal was screen-printed. By pressing the substrate on which the other spacer was sprayed so as to sandwich the liquid crystal mixture between the substrates, a cell having a substrate interval of 1.5 μm was produced. When the cell was gradually cooled to room temperature and the liquid crystal material and the uncured resin were separated, the liquid crystal could be colored and observed under a polarizing microscope. And a good extinction position was obtained, and the resin could be observed scattered in the cell.

Next, ultraviolet light was applied to the entire surface of the cell including the sealing portion at an intensity of 3 to 30 mW / cm ² and an irradiation time of 0.5 to 30 mW / cm ² .
5 min, 1 mi at an intensity of 20 mW / cm ² in this embodiment
n, irradiation was performed to cure the resin scattered on the seal portion and the display portion. Even after the resin was cured, the liquid crystal was uniaxially oriented along the rubbing direction of the alignment film as in the case before the resin was cured, and a good extinction position was obtained.

[Embodiment 16] This embodiment shows an example in which a resin is cured by ultraviolet irradiation and heating. As a switching element, a TFT (thin film transistor) and a pixel electrode, a signal electrode, a scanning electrode and the like of ITO (indium tin oxide) connected to the TFT were formed on a glass substrate of 10 cm square.

On another substrate, ITO was provided as a counter electrode. Each TFT is opposed to a substrate having a TFT of the substrate.
A light-shielding film made of Cr, Al, an oxide film thereof, or the like was provided on ITO corresponding to a portion facing the element. Polyimide was applied to the substrate by spin coating, baked to form an alignment film, and rubbed to perform a uniaxial alignment process.

A spacer was sprayed on one substrate, and a sealing material made of epoxy resin was formed on the other substrate by screen printing. The two substrates were attached to each other with a distance between the electrodes of about 3 μm to form a cell.

The liquid crystal material used in this example is CS1014, a ferroelectric liquid crystal manufactured by Chisso Corporation. The Ps of this liquid crystal is 5.4 nC / cm ² , and the phase sequence is I (isotropic phase) -N (nematic phase) -A (smectic A phase).
-C (smectic C ^* phase).

The resin material used in this example is a commercially available acrylic-modified epoxy resin, which is cured by ultraviolet rays and completely cured by heat. The resin curing temperature at this time is desirably higher than the temperature at which the liquid crystal exhibits an isotropic phase.

The above materials are mixed in a weight ratio of 95% of liquid crystal and 5% of uncured resin. (Hereinafter referred to as a liquid crystal mixture). In this case, the mixture may be heated to a temperature at which the resin does not cure because of better mixing of the liquid crystal and the resin, preferably until the liquid crystal mixture exhibits an isotropic phase.

The cell and the liquid crystal mixture were heated to 90 ° C., injected into the cell under vacuum, and cooled to room temperature. When the alignment state of the cooled cell at room temperature was observed with a polarizing microscope, the resin material was scattered in the cell, and the liquid crystal material was rubbed in the same manner as the liquid crystal material to which no resin was added. Uniaxial orientation was obtained along the direction, and a good extinction position was obtained.

Ultraviolet light was applied to this cell at an intensity of 3 to 30 mW /
cm ^2, irradiation time 0.5～5Min, 1min at an intensity 20 mW / cm ² in this embodiment was cured by irradiating the resin. The cell was further placed in a 160 ° C. oven for 2.5
h, and the resin was completely cured.

After the resin is cured by irradiation with ultraviolet rays and completely cured by heating, the liquid crystal is uniaxially oriented along the rubbing direction of the alignment film, and a good extinction position is obtained, and the resin is scattered. This was observed.

When the optical characteristics of this cell were measured, sufficient characteristics as an electro-optical device having a contrast ratio of 100 could be obtained.

Next, the substrate of this cell was peeled off, the liquid crystal was washed off with alcohol, and the residual state of the resin cured in a column was observed by SEM. As a result, the resin was observed in the same manner as observed with an optical microscope. It was observed that the columns existed on the substrate as the same as the columns, and that the element portions also existed as the same columns.

A cell was prepared under the same conditions except that the thermosetting was not performed, and the surface of the substrate was observed by SEM. As a result, most of the resin on the substrate could be observed as a column-cured resin. In addition, only traces of the resin could be slightly observed in the opposite portion, and the resin was not cured in a column shape.

[0216]

As described above in detail, by using a resin material as in the present invention, the upper and lower substrates can be bonded in a column shape. This can ensure the maintenance of the distance between the substrates, which has been a problem particularly in a large-area liquid crystal electro-optical device, and suppresses the collapse of the liquid crystal layer structure and the occurrence of display unevenness.
The device can be used upright.

Further, according to the present invention, the addition of an uncured resin material, that is, a resin constituent material such as a monomer or an oligomer, and a reaction initiator to a liquid crystal material causes a problem in a conventional liquid crystal electro-optical device. Charge inside the device
I was able to cancel positively. As a result, instability of the state of the liquid crystal molecules due to undesired charges is eliminated, and stable optical characteristics can be obtained.

As a result, it was possible to obtain a high-performance liquid crystal electro-optical device by eliminating flickering of display, change in gradation or color tone over time, display unevenness, and the like of the liquid crystal electro-optical device. In particular, in a liquid crystal electro-optical device using a ferroelectric liquid crystal, in the case of a simple matrix type, it was possible to improve the memory performance, increase the contrast, and increase the speed. Also, in the case of the active matrix type, especially in the case of the TFT drive type, high contrast and high speed could be achieved. Also in a liquid crystal electro-optical device using a nematic liquid crystal, the contrast ratio and the display state could be improved.

Further, even if only the reaction initiator is added to the liquid crystal without adding the resin constituent material, the unnecessary state change of the liquid crystal molecules due to the electric charge inside the device, which has been a problem in the conventional liquid crystal electro-optical device, can be prevented. The problem can be solved by positively canceling the charge itself present in the device by the charge from the reaction initiator, stabilizing the optical characteristics of the device, and enabling time-division driving without flicker or tone change. A high-performance liquid crystal electro-optical device was obtained.

Further, according to the present invention, since the use of a charge-transfer complex as in the prior art does not generate an excessive amount of charge for cancellation, optical stability of the device can be obtained for a long time. The present invention greatly contributes to the characteristic stability of the liquid crystal electro-optical device.

[Brief description of the drawings]

FIG. 1 shows an outline of a conventional liquid crystal cell.

FIG. 2 shows a basic structure of a liquid crystal cell of the present invention.

FIG. 3 is a diagram showing the relationship between the ratio of the resin occupying the display area and the mixing ratio of the uncured resin in the mixture, obtained in Example 1.

FIG. 4 is a schematic configuration diagram of a liquid crystal electro-optical device according to the present invention.

FIG. 5 shows current-voltage characteristics of the liquid crystal electro-optical device of Example 4.

FIG. 6 shows optical characteristics when a pulse voltage is applied to the liquid crystal electro-optical devices of Examples 4 and 5 and 6.

FIG. 7 shows a current-voltage characteristic of a liquid crystal electro-optical device of a comparative example in Example 4.

FIG. 8 shows optical characteristics when a pulse voltage is applied to a liquid crystal electro-optical device of a comparative example in Example 4.

FIG. 9 shows optical characteristics when a pulse voltage is applied to a liquid crystal electro-optical device of another comparative example in Example 4.

FIG. 10 shows current-voltage characteristics of the liquid crystal electro-optical device of Example 5.

11 shows current-voltage characteristics of a liquid crystal electro-optical device of a comparative example in Example 5. FIG.

FIG. 12 shows optical characteristics when a pulse voltage is applied to the liquid crystal electro-optical devices of Comparative Examples in Example 5 and Example 6.

FIG. 13 shows current-voltage characteristics of the liquid crystal electro-optical device of Example 6.

FIG. 14 shows current-voltage characteristics of a liquid crystal electro-optical device according to a comparative example of Example 6.

FIG. 15 shows current-voltage characteristics of the liquid crystal electro-optical device of Example 7.

FIG. 16 shows optical characteristics when a pulse voltage is applied to the liquid crystal electro-optical device of Example 7.

17 shows current-voltage characteristics of a liquid crystal electro-optical device according to a comparative example of Example 7. FIG.

FIG. 18 shows optical characteristics when a pulse voltage is applied to a liquid crystal electro-optical device of a comparative example of Example 7.

FIG. 19 shows current-voltage characteristics of Examples 9 and 10.

FIG. 20 shows optical characteristics when a pulse voltage is applied to the liquid crystal electro-optical device after irradiation with ultraviolet light in Examples 9 and 10.

FIG. 21 shows optical characteristics when a pulse voltage is applied to the liquid crystal electro-optical device before irradiation with ultraviolet light in Example 10.

FIG. 22 shows optical characteristics when a pulse voltage is applied to the liquid crystal electro-optical device before irradiation with ultraviolet light in Example 11.

FIG. 23 shows optical characteristics when a pulse voltage is applied to the liquid crystal electro-optical device after ultraviolet light irradiation in Example 11.

FIG. 24 shows current-voltage characteristics of Comparative Examples 1 and 2.

FIG. 25 shows optical characteristics when a pulse voltage is applied to the liquid crystal electro-optical device of Comparative Example 1.

FIG. 26 shows optical characteristics when a pulse voltage is applied to the liquid crystal electro-optical device of Comparative Example 2.

FIG. 27 shows a fine pattern SE formed on a substrate.
An M photograph is shown.

[Explanation of symbols]

 100, 101 Transparent conductive film 102, 103 Substrate 104, 105 Liquid crystal aligning means 106 Spacer 107 Seal portion 108 Columnar resin 109 Resin lump 110 Liquid crystal material 111 Reaction initiator 112, 113 Polarizing plate 1100, 1101 Translucent substrate 1102, 1103 Electrode 1104, 1105 Alignment means 1106 Liquid crystal material 1107 Spacer 1108 Sealing material 1110, 1111 Translucent substrate 1112, 1113 Electrode 1114, 1115 Alignment means 1116 Liquid crystal material 1117 Resin 1118 Spacer 1119 Sealing material 1120, 1211 Polarizing plate

──────────────────────────────────────────────────続 き Continuation of the front page (31) Priority claim number Japanese Patent Application No. 5-139397 (32) Priority date May 18, 1993 (May 18, 1993) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-177195 (32) Priority date May 20, 1993 (1993.5.20) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-128484 (32) Priority Date May 21, 1993 (May 21, 1993) (33) Countries claiming priority Japan (JP) (56) References JP-A-60-69632 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G02F 1/1339 500 G02F 1/13 101 G02F 1/1334

Claims (10)

(57) [Claims] 1. An electrode and an electrode on at least one inner surface
A mixture containing a liquid crystal material, a resin material, and a reaction initiator is filled between a pair of substrates having an alignment film.
Plus, of separating the liquid crystal material and the resin material of said mixture
Allowed to cleave the initiators, liquid crystal electro-optical, which comprises forming a resin spacer
Method for manufacturing the device. 2. A space between a pair of substrates having electrodes on the inner surface.
Filled with a mixture having a heated liquid crystal material and an initiator.
And slowly cooling the mixture to cleave the reaction initiator to form a resin spacer.
Method for manufacturing the device. 3. The method according to claim 1, wherein the ultraviolet irradiation is performed.
Liquid crystal characterized by further cleaving the reaction initiator
Method for manufacturing electro-optical device. 4. An uncured resin is precipitated from a mixture of a liquid crystal material and an uncured resin between a pair of translucent substrates, the liquid crystal material is oriented, and the uncured resin is cured. And a liquid crystal electro-optical device. 5. A mixture of a liquid crystal material and an uncured resin between a pair of substrates is heated until the liquid crystal material in the mixture shows an isotropic phase, and the mixture is gradually cooled. Curing, heating the liquid crystal material, and gradually cooling the liquid crystal material, a method for manufacturing a liquid crystal electro-optical device. 6. A space between a pair of substrates having electrodes on an inner surface thereof, filled with a mixture of a liquid crystal material and an uncured resin that cures with any of ultraviolet light and heat, and causing the resin to precipitate out of the mixture. A method for manufacturing a liquid crystal electro-optical device, wherein the precipitated resin is cured by ultraviolet light and heating. 7. The method according to claim 6, wherein the resin is an acrylic modified epoxy resin. 8. A sealing material for bonding the pair of substrates and a mixture of a liquid crystal material and an uncured resin are held between the pair of substrates, at least one of which has a light-transmitting property. A method for manufacturing a liquid crystal electro-optical device, comprising: depositing a cured resin in a column shape; and curing the sealing material and the uncured resin in the same step. 9. A sealing material is formed around the first substrate, a mixture of a liquid crystal material and an uncured resin is dropped on the first substrate, and a second surface is dropped on the surface where the mixture is dropped. A method of manufacturing a liquid crystal electro-optical device, comprising: bonding a substrate; precipitating the uncured resin from the mixture; and curing the sealing material and the uncured resin. 10. The liquid crystal electro-optical device according to claim 9, wherein an ultraviolet curable resin is used as said seal material and said uncured resin, and ultraviolet light is used as a curing means for said seal material and said uncured resin. Production method.