JPH11160726A - Liquid crystal element and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal element which is simple in production process and is inexpensive and a process for producing the same and to provide the liquid crystal element with which the deterioration in display characteristics by a temp. change is suppressed and display quality is improved by a good alignment state. SOLUTION: Only the alignment layer 12 of an SLM(spatial light modulation element) 21 is subjected to a rubbing treatment and liquid crystals 13 are formed into a book shelf layer structure. Then, the degree of freedom in material selection of a photoelectric conversion semiconductor layer 22 which is not subjected to the rubbing treatment is widened and the surface energy is suppressed to a lower level. The alignment state of the liquid crystals 13 is thus improved and the improvement in tramsmittance, sensitivity, etc., is made possible.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a liquid crystal element suitable for use in an optical writing element for writing information by irradiating light, and a method of manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, a light-writing type liquid crystal element or a spatial light modulator (Spati) for writing information by irradiating light.
An element called an “Al Light Modulator” (hereinafter, these are collectively referred to as “SLM”) has been proposed.

The SLM includes a photoelectric conversion semiconductor layer and a liquid crystal, and is a kind of liquid crystal element configured to irradiate writing light to write information and irradiate reading light to display information. is there.

[0004] The SLMs can be classified into a transmission type in which readout light is emitted from the side opposite to the observation side and a reflection type in which readout light is emitted from the observation side.

[0005] Of these, the transmission type SLM is described in "J.
ownnal of Photopolymer Sc
ence and Technology, Volu
me5, Number 2, 1992, p. 397-4
05 "and JP-A-3-275723.

As shown in FIG. 1, the SLM 1 includes a pair of transparent glass substrates 2 and 3 arranged with a predetermined gap therebetween. Transparent electrodes 5 and 6 are formed.

On the surface side of one transparent electrode 5, 2
A photoconductive polymer film 7 as a photoelectric conversion semiconductor layer having a thickness of μm is formed, and an alignment film 12 is formed on the surface of the other transparent electrode 6. And these substrates 2,
Numeral 3 is attached with a sealing material (not shown), and a ferroelectric liquid crystal 9 is sandwiched between the substrates.

The above-mentioned photoconductive polymer film 7 and alignment film 12 are both subjected to a rubbing treatment in the manufacturing process, and require a heat treatment at around 300 ° C. for crystallization.

[0009]

In the SLM shown in FIG. 1, the photoconductive polymer film 7 is formed of polyimide which becomes a uniaxial alignment film by rubbing and heat treatment. And the charge transporting substance must be selected in consideration of heat resistance and chemical resistance. Therefore, there is a problem that the degree of freedom of the selection is narrowed, and as a result, the sensitivity is deteriorated. In addition, when a chiral smectic liquid crystal having a bookshelf layer structure capable of increasing the contrast is used, alignment defects may easily occur.

On the other hand, unlike an SLM, a liquid crystal element that does not use a photoelectric conversion semiconductor layer is a display element that displays an image by performing multiplexing driving using a matrix electrode including a plurality of scanning electrodes and a plurality of information electrodes. Are known.

Among them, a display element using a chiral smectic liquid crystal is promising as a high-definition display, but it is said that an alignment technique for aligning liquid crystal molecules without defects is difficult.

In particular, a high technology is required to align a chiral smectic liquid crystal in a bookshelf layer structure. This technology is described in, for example, “Liquid Crystal device” filed on Aug. 1, 1995 in the United States.
ce ", a serial No. No. 509,929 or EPO6995965.

However, it has not been enough to manufacture a display element having such a bookshelf layer structure at low cost and with good reproducibility. Specifically, it is to obtain a bookshelf layer structure by suppressing the occurrence of alignment defects, to improve the injection of liquid crystal, and to suppress the heat distribution generated by the current flowing during driving.

It is an object of the present invention to provide an inexpensive liquid crystal device having a simple manufacturing process and a method for manufacturing the same.

It is another object of the present invention to provide a liquid crystal element in which display characteristics are prevented from deteriorating due to a temperature change and display quality is good due to a favorable alignment state.

Another object of the present invention is to provide a photo-writing type liquid crystal element having good sensitivity.

Still another object of the present invention is to provide a light-writing type liquid crystal element having good translucency.

[0018]

SUMMARY OF THE INVENTION The present invention comprises a pair of transparent substrates arranged at a predetermined gap, a pair of transparent electrodes,
In a liquid crystal element including a photoelectric conversion semiconductor layer, an alignment film, and a liquid crystal sandwiched between the alignment film and the photoelectric conversion semiconductor layer, a rubbing process is performed only on the alignment film, and the photoelectric conversion semiconductor layer includes The rubbing treatment is not performed.

According to the present invention, in a liquid crystal device having a liquid crystal sandwiched between a pair of substrates, one of a pair of layers in contact with the liquid crystal is a charge-transporting photoelectric conversion semiconductor layer;
Only the other of the pair of layers is a uniaxial alignment film.

According to the present invention, in a liquid crystal device having a liquid crystal sandwiched between a pair of substrates, one of a pair of layers in contact with the liquid crystal is a photoelectric conversion organic semiconductor layer, and only the other of the pair of layers is a photoelectric conversion organic semiconductor layer. Is a uniaxial alignment film, and the liquid crystal is a chiral smectic liquid crystal having a bookshelf layer structure.

The present invention is also characterized in that the photoelectric conversion organic semiconductor layer has a maximum value in a differential coefficient (Δpotential / Δlight amount) -light amount characteristic of a light attenuation curve.

According to the present invention, in a method of manufacturing a liquid crystal element, a step of forming a transparent electrode on each of a pair of transparent substrates and a step of forming a photoelectric conversion organic semiconductor layer on one surface of the pair of transparent substrates are provided. Forming an alignment film on the other surface of the pair of transparent substrates, performing a rubbing process only on the alignment film of the photoelectric conversion organic semiconductor layer and the alignment film, and forming a surface of the photoelectric conversion organic semiconductor layer. Disposing a curable resin serving as a spacer, bonding the respective transparent substrates, curing the curable resin, and injecting a liquid crystal into a gap between the bonded pair of transparent substrates. And a step.

[0023]

Embodiments of the present invention will be described below.

A first embodiment of the present invention will be described with reference to FIGS.

An electro-optical device using a liquid crystal element according to the present embodiment is an SLM 21 composed of a light-writing type liquid crystal element.
And a writing light irradiation device 26. By irradiating light from the writing light irradiation device 26, the SLM 21
Information can be written to the

The SLM 21 includes a pair of transparent substrates 2 and 3 arranged with a predetermined gap therebetween. Transparent electrodes 5 and 6 are formed on the inner surfaces of the substrates 2 and 3, respectively. . Among them, a photoelectric conversion semiconductor layer (hereinafter, referred to as a photoelectric conversion layer) is formed on the surface of one transparent electrode 5, and a uniaxial film having a uniaxial alignment regulating force is formed on the surface of the other transparent electrode 6. An alignment film 12 is formed.

The ends of the substrates 2 and 3 are bonded together by a sealing material (not shown), and a liquid crystal 13 is held between the substrates 2 and 3. In addition,
The substrate gap is defined by an adhesive spacer and / or a non-adhesive spacer (not shown) as necessary.

Further, polarizing plates 30 and 31 are arranged on the outer surface side of each of the substrates 2 and 3 so that the polarization directions are orthogonal to each other.

The above-mentioned photoelectric conversion layer 22 employs a layer having a function of generating charge carriers (electrons and holes) by light irradiation and a function of transporting charges having a high mobility with respect to the carriers. In FIG. 2, 2
3 is a charge generation layer and 25 is a charge transport layer.

The surface 22f of the photoelectric conversion layer 22 which is in contact with the liquid crystal 13 has not been subjected to a uniaxial alignment treatment such as rubbing. On the other hand, a surface 12f of the uniaxial alignment film 12 which is in contact with the liquid crystal 13 is subjected to a uniaxial alignment treatment such as rubbing.

When the liquid crystal 13 is oriented, the liquid crystal molecules are preferentially arranged to form a smectic layer from the uniaxial orientation film 12 side, and the smectic layer is preferentially formed from the photoelectric conversion layer 22. Are not arranged like this.

That is, the layer starts to grow from the surface 12f side of the uniaxial alignment film 12 so that the liquid crystal molecules constitute a smectic layer, and the growth ends on the surface 22f side of the photoelectric conversion layer 22. In this way, a bookshelf layer structure with few orientation defects (a pseudo bookshelf layer structure is regarded as one of the bookshelf layer structures) is obtained.

Moreover, it is not necessary to pattern any of the transparent electrodes 5 and 6 using photolithography or the like. Therefore, the surfaces 12f and 22f that are in contact with the liquid crystal 13 are both flat surfaces, and assist in developing a good bookshelf layer structure.

Further, since the surfaces 12f and 22f in contact with the liquid crystal 13 are flat and the photoelectric conversion layer 22 is softer than a transparent electrode or the like and thicker than a known polyimide alignment film, the injection of the liquid crystal 13 is performed. And the manufacturing time of the SLM is shortened.

(Driving Method of Liquid Crystal Element) SLM2 shown in FIG.
Taking 1 as an example, the driving method of the SLM of the present invention will be described.

First, in order to apply a DC voltage between one transparent electrode 5 and the other transparent electrode 6, the transparent electrode 5 is held at a reference potential, and the switch Sw1 is connected to the terminals C and A.
And connect.

Next, the light irradiation device 26 is operated to write writing light having predetermined image information through the polarizing plate 30, the transparent substrate 2, and the transparent electrode 5 to the light receiving surface 22p of the photoelectric conversion layer 22.
Irradiation.

The photoelectric conversion layer 22 that has received the writing light mainly generates charges in the charge generation layer 23 according to the amount of received light. Since the writing light is image information light, the light amount has an in-plane distribution, and the charge generation layer 23 has a corresponding amount of charge distribution. Holes among the generated charges are transported through the charge transport layer 25 to the surface 22 f in contact with the liquid crystal 13.

The electrons flow into the transparent electrode 5 having a relatively high potential. That is, the photoelectric conversion layer 22 depends on the amount of received light.
Will be reduced. Therefore, the effective voltage applied to the liquid crystal 13 is large in a portion where the amount of received light is large, and the effective voltage applied to the liquid crystal 13 is low in a portion where the amount of received light is small.

As described above, in a portion where the applied effective voltage exceeds the inversion (switching) threshold of the liquid crystal, the liquid crystal molecules are inverted from one stable state to the other. This is shown in FIG.

In a portion where the effective voltage applied to the liquid crystal 13 exceeds the threshold, the liquid crystal molecules are inverted, and the other stable state U
Orientation to 2. In a portion where the effective voltage applied to the liquid crystal 13 does not exceed the threshold, one stable state U1 remains.

Although the unit of the resolution in the plane of the photoelectric conversion layer 22 is substantially infinite for one charge, the resolution in the plane of the liquid crystal 13 is a domain unit. Restricted to domains. However, a portion having a size of about 100 μm × 100 μm may have 100 or more, and in some cases, 10,000 or more domains. Therefore, since the number of domains to be inverted changes in accordance with the amount of charge received by the portion, it appears that the portion has 256 or more gradations. Thus, the SLM 21 can perform analog gradation expression using the ferroelectric liquid crystal.

Next, the switch Sw1 is operated to short-circuit the terminals D and C. Then, since the transparent electrodes 5 and 6 have the same potential, an electric field is not substantially applied to the liquid crystal 13 from the outside. Here, since the liquid crystal 13 is in the chiral smectic phase, the liquid crystal molecules maintain the alignment state.

Then, the reading light is irradiated from the light irradiation device 26. The reading light is the same as the writing light,
The light is radiated to the SLM 21 through 0 and exits through the polarizing plate 31. The emitted light can be recognized by the observer OB.

As the writing light, energy (wavelength) that is absorbed by the photoelectric conversion layer 22 and generates an electric charge.
Is selected. On the other hand, the read light is energy (light having a wavelength) that is hardly absorbed by the photoelectric conversion layer 22.
Or a large amount of light that cannot be completely absorbed by the photoelectric conversion layer 22.

Polarizing plates 30, 31 arranged in crossed Nicols
Are aligned so as to be non-transmissive in state U1 and transparent in state U2, bright write information becomes bright read information and dark write information becomes dark read information. Conversely, the polarizers 30 and 31 are transmitted in the state U1,
If the position is adjusted to be non-transparent in the state U2, the bright information is inverted and converted into dark information, and the dark information is inverted and converted into bright information. Such inversion / non-inversion of the optical information can also be performed by changing the polarity of the applied voltage.

When the above operation is repeatedly performed, after the above-described process, the switch Sw1 is switched to short-circuit the terminals B and C, and a sufficiently large reverse electric field is applied to the liquid crystal. Due to such a reset operation, all the liquid crystals of the SLM 21 are in the state U.
Follow one. At this time, by irradiating light having no in-plane distribution of light amount as reset light, the liquid crystal 13 can be reset to the state U1 even with a relatively low reverse electric field.

Also, since the SLM 21 according to the present embodiment performs display using the memory properties of ferroelectric liquid crystal, the driving method is disclosed in Japanese Patent Application Laid-Open No. Sho 59-216126.
Japanese Patent Publication (Inventor: Shuzo Kaneko, Applicant: Canon) can also be used.

(Substrate) Next, the substrates 2 and 3 will be described.

The substrates 2 and 3 used in the present invention include:
A flexible or non-flexible substrate made of an inorganic material such as glass, quartz, or alumina, or an organic material such as a plastic film may be used. Note that one of the substrates may be a rigid substrate and the other may be a flexible substrate. Alternatively, the polarizing plate 30 and the substrate 2 and the polarizing plate 31 and the substrate 3 may be bonded and integrated.

(Transparent Electrodes) Next, the transparent electrodes 5 and 6 will be described.

The transparent electrodes 5 and 6 used in the present invention include tin oxide, indium tin oxide (ITO), zinc oxide,
A transparent conductive oxide such as iridium oxide is preferable.

(Uniaxial Alignment Film) Next, the uniaxial alignment film 12
Will be described.

As the uniaxial alignment film 12 used in the present invention, an inorganic alignment film made of obliquely deposited silicon oxide or the like,
A suitable material is an organic alignment film such as rubbed polyimide or polyamide. Also, as described in the above-mentioned US application serial no. The uniaxial alignment film described in the specification of Japanese Patent No. 509929 is also preferably used.

(Photoelectric Conversion Layer) Next, the photoelectric conversion layer 22 will be described.

The photoelectric conversion layer 22 used in the present invention includes a charge generation layer 23 and a charge transport layer 2 as shown in FIG.
5 may be a single photoconductive layer formed by mixing (containing) a charge generating substance and a charge transporting substance in a resin (the former is a laminated type, The latter is referred to as a single-layer type).

In the case of the laminated type shown in FIG.
The charge generation layer 23 is arranged so as to be in contact with the liquid crystal 13, and the charge transport layer 25 is arranged so as to be in contact with the liquid crystal 13.
The charge transport layer 25 may be disposed so as to be in contact with the transparent electrode 5, and the charge generation layer 23 may be disposed so as to be in contact with the liquid crystal 13.

(Charge Generating Layer) Here, the charge generating layer 23
Is a material in which particles of a photoconductive substance (charge generating substance) are dispersed in a resin. As the photoconductive substance (charge generating substance), for example, an electron donating portion and an electron accepting portion are included in a molecule. Compounds, azo pigments such as Sudan Red and Diane Blue, quinone pigments such as pyrenequinone and anthantrone, indigo pigments such as indigo and thioindigo, azurenium salt pigments, and phthalocyanine pigments such as copper phthalocyanine and titanyl phthalocyanine. In addition, as a resin for dispersing these particles,
Binder resins such as polyvinyl butyral, polystyrene, polyvinyl acetate, acrylic resin, polyvinyl pyrrolidone, ethyl cellulose, and cellulose acetate-butyrate are exemplified. The charge generation layer 23 has a thickness of 0.01
To 2.0 μm, more preferably about 0.01 to 0.2 μm.

(Charge Transporting Layer) The charge transporting layer 25 is formed by dissolving a charge transporting substance having a high carrier mobility in a resin having a film forming property. Here, as the charge transporting substance, for example, a polycyclic aromatic compound having a structure such as biphenylene, anthracene, pyrene, or phenanthrene in a main chain or a side chain, or a nitrogen-containing complex such as indole, carbazole, oxadiazole, or pyrazoline is used. Cyclic compounds, hydrazone compounds, styryl compounds, and the like. Examples of the resin having a film forming property include polyester, polycarbonate, polymethacrylate, polystyrene, and polyamide.

When a spacer is provided to keep the thickness of the liquid crystal layer of the SLM 21 constant, the charge transport layer 25
In order to accurately manage the gap size, the charge transport layer 25 preferably has a hardness of 2B or more (pencil height). Further, the thickness of the charge transport layer 25 is preferably about 0.1 to 1.8 μm, and the surface energy of the surface of the photoconductive layer 22 (the surface in contact with the liquid crystal layer 13A) is 30 dyn / cm ² or less. Is preferred.

Further, the transparent electrode 5 and the photoelectric conversion layer 22
And an intermediate layer between them. By providing such an intermediate layer, the transparent electrode 5 and the photoelectric conversion layer 22 are provided.
And the injection of extra charges from the transparent electrode 5 side can be prevented. Therefore, such an intermediate layer is called an adhesion layer or a charge injection prevention layer. The intermediate layer may be composed of only one layer, or may be composed of a plurality of layers.

Here, the thickness of the intermediate layer is 5 μm or less, preferably 1.0 μm or less, and more preferably 0.5 μm or less, even when there are a plurality of intermediate layers.
μm or less is preferred. The intermediate layer 24 is made of, for example, casein, polyvinyl alcohol, nitrocellulose, polyamide (nylon 6, nylon 66, nylon 610, copolymer nylon, N-alkoxymethylated nylon, etc.), polyimide, polyurethane, polyester,
It can be formed of a phenol resin or the like.

Next, a specific example of the photoelectric conversion layer 22 will be described. When the photoelectric conversion layer is formed of an azo pigment or i-type titanyl phthalocyanine, the transmittance is further improved, and good transmission characteristics are obtained in the visible region (all wavelengths).

That is, FIG. 4 is a diagram showing the transmission characteristics of the photoconductive layer 22 using the hydrazone compound for the charge transport layer 25 and the azo pigment for the charge generation layer 23. The light wavelength is about 550 nm. It can be understood that a sufficient transmittance can be obtained when the transmittance is 50% or more.

FIG. 5 is a graph showing the transmission characteristics of the photoconductive layer 22 in which the hydrazone compound is used for the charge transport layer 25 and i-type titanyl phthalocyanine is used for the charge generation layer 23. 40 transmittance at 400-700 nm
% Or more, and it can be understood that a sufficient transmittance can be obtained.

FIG. 6 is a graph showing the transmission characteristics of a mixed photoconductive layer using an azo pigment, and FIG. 7 is a graph showing the transmission characteristics of a mixed photoconductive layer using an i-type titanyl phthalocyanine. As can be seen from the figure, the transmittance is 40% or more in each case.

Further, the resolution can be further enhanced by reducing the thickness of the photoelectric conversion layer to 2 μm or less, more preferably 1 μm or less.

FIG. 8 shows that the photoconductive layer 22 has a thickness of 1
The comparison is made between the resolutions of μm, 2 μm, 3 μm, and 4 μm, and the resolution when a 0.2 μm-thick polysiloxane layer (intermediate layer) is interposed between the liquid crystal 13 and the photoconductive layer 22. From this figure, it can be understood that the resolution is higher when the photoconductive layer 22 is thinner and the intermediate layer is not interposed. The resolution was determined by transferring an image using a Cr mask and counting the number of discriminable lines per 1 mm.

In the above-described embodiment, the information is displayed by irradiating the reading light. However, the present invention is not limited to this, and the written information may be read by laser scanning or CCD.

Further, when different information is repeatedly written, the amount of light to be written needs to be small enough to prevent the photoconductive layer 22 from causing optical memory. It is preferable to increase the amount of writing light to cause an optical memory.

FIG. 9 is a diagram showing the relationship between the amount of writing light and the presence or absence of a photo memory. Note that FIG.
FIG. 9A shows an example in which laser light is used as writing light and i-type titanyl phthalocyanine is used as a photoelectric conversion layer. FIG. 9B shows an example in which analog light is used as writing light and an azo pigment is used as a photoelectric conversion layer. This is an example used. In addition, as the charge transporting material, a hydrazone-based compound was used.

The photoelectric conversion layer is preferably designed so as to satisfy the following conditional expression in order to obtain good contrast.

[0073]

[Number 2] ^{A × T ≧ 1 × 10 4} [lux.sec] 0.1 ≦ when _{| V M / V D | ≦} 1.0 A [lux]: irradiation light intensity T [sec]: irradiation time V _D [V]: potential is shared by the photoelectric conversion layer of light non-irradiated portion V _M [V]: is shared by the photoelectric conversion layer and the potential of the light irradiation portion to be shared by the photoelectric conversion layer of light non-irradiated portion In this way, writing to the photoelectric conversion layer by optical information and information writing to the liquid crystal layer by applying a voltage to the liquid crystal can be performed independently, and the SLM can be easily handled.

When writing information by irradiating light, for example, a beam such as a laser or LED
In some cases, the light is modulated by a digital image signal from a scanner or the like, and this modulated beam is applied to the SLM to perform dot-shaped optical writing. Here, dot exposure in the case of performing such dot-shaped optical writing is pulse exposure of 20 to 100 μm at a luminance of 1 to 5 mW, and the luminance distribution is a Gaussian distribution.

However, such dot exposure is different from an ideal rectangle as shown in FIG. 10A, and actually has a gentle mountain shape as shown in FIG. 10B. In the case where optical writing is performed by a proper dot exposure, there is a problem that a dot image having a low resolution is obtained.

In order to solve this problem, it is preferable to design the photoelectric conversion layer so that the differential coefficient (Δpotential / Δlight amount) -light amount characteristic of the light attenuation curve has a maximum value. The normalized differential coefficient calculated from the light attenuation curve of the photoelectric conversion layer may be at least 3 or more, preferably 5 or more.

When the photoelectric conversion layer having such a structure is irradiated with dot-shaped light, a photocurrent flows due to an avalanche phenomenon utilizing the avalanche phenomenon of photocarriers, and the orientation state of the liquid crystal changes due to the photocurrent. Writing of high-resolution information is performed. Note that the photoelectric conversion layer according to the present invention has a characteristic in which a photocurrent does not flow at a low light amount, a photocurrent rapidly flows at a certain light amount or more, and shows a maximum value in a light attenuation curve shown in FIG. A photoelectric conversion layer having such a light decay curve is referred to as a light γ light attenuating photoelectric conversion layer.

Here, the high γ light attenuating photoelectric conversion layer is
Differentiating the potential V (normalized) on the light decay curve in the light decay region with the light amount E as an action variable (normalized),
As shown in FIG. 18, the derivative | ΔV / ΔE | (absolute value) initially shows a relatively small value including zero, then increases sharply, and converges to zero again through the local maximum value.

Then, the photoelectric conversion layer 22 having such characteristics is used for an SLM, and a luminance of 1 to 5 mW and 100 μm
When dot-shaped optical writing is performed with an extremely narrow pulse width of the following, the dot image (information writing) on the photoelectric conversion layer 22 is very close to (a) in FIG. It is convenient.

As described above, since the photoelectric conversion layer is a high γ light attenuating photoelectric conversion layer having an avalanche effect, especially when combined with a writing light emitting device that performs digital image processing, a high resolution light having excellent dot reproducibility can be obtained. Image information can be written.

The problem described above with reference to FIG. 10 is caused by a pair of transparent substrates arranged at a predetermined gap, a transparent electrode formed on each transparent substrate, and a transparent electrode formed on one transparent substrate. A photoelectric conversion layer, an alignment film formed on the other transparent substrate, and a liquid crystal sandwiched between the pair of transparent substrates, a light-writing type liquid crystal element for writing information by irradiating light, Photoelectric conversion layer,
With a function-separated type configuration having a charge generation layer and a charge transport layer,
While the ratio (C _CTL ) / (C _CGL ) of the electric capacity (C _CGL ) of the charge generation layer to the electric capacity (C _CTL ) of the charge transport layer is 1.0 or more, the rubbing treatment is performed only on the alignment film, and SLM characterized by not subjecting the conversion layer to rubbing
Can also be solved.

In order to sufficiently secure the withstand voltage of the photoelectric conversion layer of the liquid crystal display, it is more preferable that (C _CTL ) / (C _CGL ) be 2.5 or more, and (C _CTL ) / (C _CGL ) )
Is more preferably 5.0 or more.

When the SLM of this embodiment is irradiated with light,
With a function-separated type configuration having a charge generation layer and a charge transport layer,
The photoelectric conversion layer having a ratio (C _CTL ) / (C _CGL ) of the electric capacity (C _CGL ) of the charge generation layer to the electric capacity (C _CTL ) of the charge transport layer of 1.0 or more has a photocurrent due to an avalanche phenomenon. Flows. As a result, the alignment state of the liquid crystal changes, and high-resolution information is written.

In this case, suitable charge generating substances in the charge generating layer include azo pigments such as monoazo, bisazo and trisazo, phthalocyanine pigments such as metal phthalocyanine and non-metal phthalocyanine, indigo pigments such as indigo and thioindigo, and anthantrone. And polycyclic quinone pigments such as pyrenequinone, perylene anhydrides such as perylene anhydride and perylene imide, squarylium dyes, pyrrolopyrrole pigments, pyrylium and thiapyrylium salts, and triphenylmethane dyes.
e, Se-As, CdS, crystalline Si, a-Si or the like may be used.

In particular, azo-based pigments having a high degree of freedom in material selection are preferable, and among them, a charge generating material represented by the following general formula is preferable.

[0086]

Embedded image In the formula, X represents a halogen atom such as a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom. R1, R2, R3, R
4, R5 is a halogen atom such as a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, a nitro group, a cyano group, an optionally substituted methyl, ethyl, n-propyl, iso
-Represents an alkyl group such as propyl and butyl, an alkoxy group such as methoxy, ethoxy and propoxy, an aralkyl group such as benzyl and phenethyl, an aryl group such as phenyl and naphthyl, and an alkylamino group such as dimethylamino and diethylamino. Or different. m and n represent 1 or 2, and may be the same or different. Examples of the substituent in the above expression include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, an alkyl group such as a nitro group, a cyano group, methyl, ethyl, n-propyl, iso-propyl and butyl, methoxy, ethoxy and propoxy. And the like, an aralkyl group such as benzyl and phenethyl, an aryl group such as phenyl and naphthyl, and an alkylamino group such as dimethylamino and diethylamino.

The above-mentioned charge generating material is prepared by using a suitable solvent with a binder resin (binder resin), for example, polyvinyl acetal, polystyrene, polyester, polyvinyl acetate, methacrylic resin, acrylic resin, polyvinylpyrrolidone and cellulose resin. It can be formed by applying a solution dispersed in a resin such as a resin having a hole transporting property or an electron transporting property and drying the applied solution.

The thickness of the charge generation layer at this time is usually 0.01
To 2.0 .mu.m, particularly preferably 0.1 to 1.8 .mu.m. The weight ratio P / B of the charge generation material (P) to the binder resin (B) is preferably from 4/1 to 1/10.

On the other hand, the charge transport layer is formed by applying a solution in which a charge transport material is dissolved in a solution of a resin having film forming properties, and drying the solution. Charge transport materials are broadly classified into electron transport materials and hole transport materials. As electron transport materials,
2,4,7-trinitrofluorenone, 2,4,5,7
Electron-accepting substances such as tetranitrofluorenone, chloranil, tetracyanoquinodimethane, and alkyl-substituted diphenoquinone, and those obtained by polymerizing these electron-accepting substances; and hole transporting materials such as pyrene and anthracene. Ring aromatic compounds, carbazole, indole, oxazole, thiazole, oxadiazole, pyrazole, pyrazoline, heterocyclic compounds such as thiadiazole and triazole, p-diethylaminobenzaldehyde-N, N-diphenylhydrazone and N, N-diphenylhydrazino- Hydrazone-based compounds such as 3-methylidene-9-ethylcarbazole, α-phenyl-4′-
N, N-diphenylaminostilbene and 5- [4-
Styryl compounds such as (di-p-tolylamino) benzylidene] -5H-dibenzo [a, d] cycloheptene;
Benzidine compounds, triarylmethane compounds, triarylamine compounds such as triphenylamine and tolylamine, or polymers having a group consisting of these compounds in the main chain or side chain (for example, poly-N-vinylcarbazole and polyvinyl Anthracene).

Examples of the resin having a film forming property include polyester, polycarbonate, polymethacrylate, and polystyrene.

At this time, the thickness of the charge transport layer is preferably 1.0 μm or less, particularly preferably 0.2 μm or less.

The surface energy of the surface of the photoelectric conversion layer 22 (the surface in contact with the liquid crystal 13) is 30 dyn / cm ^2.
The following is preferred.

In the present invention, the ratio (C _CTL ) / (C C) of the electric capacity (C _CGL ) of the charge generation layer 23 of the photoelectric conversion layer 22 to the electric capacity (C _CTL ) of the charge transport layer 25 is used.
_{When CGL} is 1.0 or more, the avalanche phenomenon using the avalanche phenomenon of the optical carrier occurs. That is, as shown in FIG. It has a characteristic that a photocurrent flows rapidly. Therefore, when such a photoelectric conversion layer 22 is irradiated with light, a photocurrent flows due to the avalanche phenomenon, whereby the alignment state of the liquid crystal is changed and writing of high-resolution information is performed.

Here, in order to sufficiently secure the withstand voltage of the photoelectric conversion layer 22 of the liquid crystal display, (C _CTL ) / (C _CGL ) is set to 2.
More preferably, it is 5 or more. More preferably (C
( _CTL ) / (C _CGL ) is preferably 5.0 or more. In the present invention, the electric capacity (C
_CGL) and the ratio (C _CTL) / (C _CGL electric capacitance (C _CTL) of the charge transport layer), dielectric constant (epsilon) and the thickness of each layer (d _CGL, calculated from d _CTL), dielectric constant ( ε) is 1K
Values above Hz were used.

On the other hand, (C _CTL ) / (C _CGL ) largely depends on the value of the dielectric constant of each layer, and this dielectric constant is particularly affected by the charge generation material (P) and the binder resin (B) themselves and It is greatly affected by the weight ratio P / B and the film thickness. Therefore, these optimal choices are one of the important factors of the present invention. Further, the charge transport material described above may be added as needed.

(Liquid Crystal) Next, the liquid crystal 13 will be described.

As the liquid crystal 13 used in the present invention, a chiral smectic liquid crystal exhibiting a chiral smectic phase, particularly a chiral smectic liquid crystal having ferroelectricity, is suitable. In particular, a liquid crystal having a phase transition series not exhibiting a cholesteric phase is preferable, and a chiral smectic liquid crystal layer structure may be a quasi-bookshelf having a layer inclination substantially close to a bookshelf state.

Examples of the liquid crystal exhibiting a bookshelf layer structure or a quasi bookshelf layer structure include, for example,
A fluorine-containing liquid crystal compound comprising a fluorocarbon terminal chain and a hydrocarbon terminal chain, wherein the terminal chain is bonded by a central nucleus, and a liquid crystal containing a compound having a smectic intermediate layer or a latent smectic intermediate phase. Can be used.

Further, a ferroelectric polymer liquid crystal and “Liquid Crystal D” filed on Aug. 1, 1994
US Patent Application Serial N titled "device"
o. The liquid crystal disclosed in Japanese Patent No. 283141 can also be used.

(Light Irradiation Apparatus) Next, the light irradiation apparatus 26 will be described.

As the light irradiation device 26 used in the present invention, an image forming device such as a camera, a projector, and a film scanner, and an image forming device such as a laser light scanner, a CRT, and an LED array are preferable.

The image forming apparatus is an apparatus that forms an image of reflected light from a subject on an SLM, or an apparatus that forms an image of light passing through an image carrier such as a negative film on the SLM.

When an optical shutter or an electric shutter used in a normal camera is used, the photoelectric conversion layer 22 replaces the film.

The image forming apparatus scans a laser beam or the like to form a latent image on the photoelectric conversion layer of the SLM.

When an image is formed by laser light,
A laser such as an argon laser (514, 488 nm), a helium-neon laser (633 nm), or a semiconductor laser (780 nm, 810 nm, etc.) is used as a light source, and supports image signals, character signals, code signals, and line drawing signals. The laser is scanned to expose the photoelectric conversion layer of the SLM.

Incidentally, analog recording such as an image,
Digital recording such as characters, codes, and line drawings is performed by modulating the laser light intensity.
This is performed by F control. When forming an image with halftone dots,
Laser light ON / OFF by dot generator
Control.

(Method of Manufacturing Liquid Crystal Element) Next, a method of manufacturing the liquid crystal element of the present invention will be described.

[0108] Two substrates 2 and 3 made of glass, quartz or a plastic film are prepared, and a transparent conductive film such as ITO is formed on the surface thereof by vacuum evaporation or sputtering. At this time, the thickness of the transparent conductive film is appropriately selected from the range of 10 nm to 1 μm. Alternatively, a transparent conductive film may be formed on one mother board, and then divided into two substrates with a transparent electrode. In any case, the substrates 2 and 3 shown in FIG.

Next, as shown in FIG.
A charge generation layer 23 and a charge transport layer 25 are formed as a photoelectric conversion layer 22 on the surface of (a) (photoelectric conversion layer forming step). As a forming method, a solution containing a charge generating substance and a charge transporting substance in a resin having a film forming property is formed by a method such as spin coating, roll coating, dipping, casting, spraying, beam, blade, wire bar coating, and the like. Then, the layers 23 and 25 are formed on the substrate surface.

In forming the charge transport layer,
Instead of using the solution as described above, one or several kinds of photoconductive substances may be directly deposited. In that case, methods such as vacuum deposition, sputtering, chemical vapor deposition (CVD), and ion plating may be used. No uniaxial orientation treatment such as rubbing is performed on the surface 22f of the photoelectric conversion layer 22 thus formed.

As shown in FIG. 11C, an alignment film 12 is formed on one of the substrates 3 and the alignment film 12 is subjected to a rubbing process to form a uniaxial alignment film.

Next, a sealant is provided on at least one end of both substrates 2 and 3 except for a portion serving as a liquid crystal injection port.
The two are bonded together to cure the sealant. At this time, it is also preferable to disperse and arrange at least one of a non-adhesive spacer and an adhesive spacer in a portion to be an image display area as needed. In this case, it is preferable to form the cell by disposing the spacers on the surface of the photoelectric conversion layer and then bonding the two substrates together.

Next, the SLM is injected under a reduced pressure or normal pressure from the injection port by heating the liquid crystal in the state of an isotropic phase. After the SLM is arranged between the substrates, the SLM is gradually cooled to a state where a chiral smectic layer is exhibited.

After the liquid crystal is injected, the cell is cooled, but it is preferable to cool the cell at a slow cooling rate of 1 ° C./min or less at least near the phase transition point from the isotropic phase to the SmA phase.

The transition of the liquid crystal molecules from the surface 12f side of the uniaxial alignment film 12 to the smectic phase is better in the photoelectric conversion layer 2
The transition from the surface 22f side of No. 2 to the smectic phase occurs preferentially, and the liquid crystal shows a good bookshelf layer structure with little alignment failure. Thus, the liquid crystal element shown in FIG. 11D is obtained. In addition, in (d), 27 is a spacer.

The above-mentioned sealant is used for at least one of the photoelectric conversion layer 22, the alignment film 12, and the transparent electrode.
One of them may be partially removed and then applied directly to the surface of the glass substrate or the surface of the electrode. In this case, a stronger adhesion can be obtained.

Although the basic structure of the SLM according to the embodiment of the present invention has been described above, additional functions or means may be provided in this structure.

FIG. 12 is a cross-sectional view for illustrating a configuration of an SLM according to another embodiment. In FIG.
Reference numeral 1 denotes an SLM. In this SLM 51, a substrate 2
A color filter CF is disposed between the transparent electrode 5 and the transparent electrode 5. The color filter CF includes a colored layer patterned into three colors of RGB and a transparent layer for protecting and flattening the colored layer. Here, as the charge generation layer 23,
It is preferable to use an azo pigment sensitive to analog light.

When writing is performed, analog light is used as writing light, and writing is performed sequentially with R light, G light, and B light. Other configurations are the same as those of the above-described embodiment. By providing the color filter CF in this manner, a color image can be obtained.

In the above embodiment, the three SLMs 51 are arranged in a stripe or mosaic.
A color display was made possible by forming color filters, but three SLMs were used, and an SLM formed with an R color filter, an SLM formed with a G color filter, and a B color filter were used. SLM formed
, And color display may be performed by these three SLMs.

Next, an SLM according to still another embodiment of the present invention will be described with reference to FIG.

The SLM 41 according to this embodiment has PET films 42 and 43 as transparent substrates. In addition,
The thickness of these PET films 42 and 43 is 100 μm
It is about.

As the liquid crystal 13, a film-type polymer type ferroelectric liquid crystal is used. The liquid crystal 13 is formed of a mixture of a ferroelectric low-molecular liquid crystal and a thermoplastic amorphous polymer. Here, as a low-molecular liquid crystal,
Use one with a bookshelf structure. Further, as the thermoplastic amorphous polymer, a polymer having no optical anisotropy such as polystyrene and polycarbonate is used.

First, transparent electrodes 5 and 6 are formed by depositing ITO on the surfaces of PET films 42 and 43 at room temperature and performing patterning. The ITO may be applied by a sol-gel method.

A polyimide film is printed on one of the PET films 43 to a thickness of 100 °, and is fired at a temperature of 150 ° C. to form the alignment film 12. The surface of the alignment film 12 is subjected to a rubbing treatment with a nylon cloth.

The photoconductive layer 22 as a photoelectric conversion layer is formed on the other PET film 42. The surface energy of the photoconductive layer 22, specifically, the photoconductive layer 22
Is a stacked type, the surface energy of the charge transport layer 25 is set to 30 dyn / cm ² or less. In addition, since the liquid crystal itself has a memory property, the surface of the photoconductive layer 22, specifically, when the photoconductive layer 22 is a stacked type, the surface of the charge transporting layer 25 does not necessarily have to be hard, and the Any hardness (pencil hardness) is acceptable.

Thereafter, a particle size of 2 is formed on the surface of the photoconductive layer 22.
A μm spacer is scattered, and a polymer type ferroelectric liquid crystal is applied to the other film. Then, these films are heated to 100 ° C. and then pressed, and the protruding liquid crystal is wiped off. Furthermore, it is gradually cooled to room temperature and sealed with an epoxy adhesive.

The above-mentioned spacer is a non-adhesive and / or adhesive spacer, and may not be necessary in the case of a small-screen SLM in which ferroelectric liquid crystal is applied to a uniform thickness. . Further, the photoconductive layer 22 may be of a mixed type.

Next, an example of the present embodiment will be described. Example 1 A liquid crystal composition having the following formulation was prepared as a ferroelectric liquid crystal.

This composition has a spontaneous polarization at 25 ° C. of 26 n
C / cm ² , inclination angle δ = 0 of the smectic layer at 20 ° C.
° and the apparent tilt angle is 27 °.

[0131]

Embedded image First, an ITO film was formed to a thickness of 70 nm on each of the surfaces of two glass substrates by sputtering, and an end portion serving as a seal portion was removed by patterning to form a transparent electrode.

As a dispersion, a compound 4 of the following structural formula
Part, benzal resin (weight average molecular weight 24000) 2
And 34 parts of cyclohexanone and glass beads having a diameter of 1 mm were dispersed in a hot-water bath for 20 hours using a sand mill, and then 60 parts of butanol was added.

[0133]

Embedded image Next, the dispersion liquid is spin-coated on the surface of the substrate,
Drying was performed at 15 ° C. for 15 minutes to form a 0.2 μm thick charge generation layer.

Next, a hydrazone compound 1 of the following structural formula
0 parts and 10 parts of bisphenol Z-type polycarbonate (weight average molecular weight 39000) are dissolved in a mixed solvent composed of 40 parts of dichloromethane and 20 parts of monochlorobenzene to prepare a solution, and this solution is spun on the surface of the charge generation layer. Coating was performed by a coating method, and the coating was dried at 120 ° C. for 60 minutes to form a charge transport layer having a thickness of 0.85 μm.

[0135]

Embedded image On one of the substrates, a polyimide alignment film was formed to a thickness of 200 ° by a printing method, and was heated in an oven at a temperature of 220 ° C. for 1 hour.
b. Thereafter, a rubbing treatment was performed on the surface of the alignment film by applying a load to the nylon cloth using a nylon cloth with sufficient strength to have a uniaxial alignment regulating force.

Next, an IPA solution in which spacer beads having a particle size of 2.0 μm are dispersed is applied to the surface of the substrate on the alignment film side by a spinner, and oven-dried in an oven at a temperature of 110 ° C. for 5 minutes. Was.

Further, an epoxy-based sealing material was applied (printed) to the periphery of the substrate on the orientation film side, and after leveling and drying, the substrates were bonded together.

After that, the substrate bonded was heated in an oven at a temperature of 140 ° C. for 1.5 hours to inject a liquid crystal. At the time of the injection, the temperature was heated to 95 ° C., and the injection was performed. The cooling rate was 1 ° C./min.

After injecting the liquid crystal, heat to 110 ° C.
The mixture was gradually cooled to 90 ° C. at a cooling rate of / min, and then allowed to cool to room temperature.

Next, evaluation was performed as shown in FIG.

[0141] As the writing light irradiation device, using the semiconductor laser 60 and optical fiber 61, as in FIG. 14 (a), irradiated with infrared laser light L _W of wavelength 780nm to SLM21 through the mask 62, the image Information was written. The mask 62 is shown in FIG. 14B, and the energy density of the laser beam is 0.03.
μm / cm ² .

Thereafter, as shown in FIG. 14C, the SLM 2 is disposed between the polarizing plates 30 and 31 arranged in crossed Nicols.
1 Place was irradiated with white reading light L _R in SLM21, the image shown in FIG. (D) is displayed.

When the state of the energy density is changed,
The contrast of the displayed image also changed. In addition, the polarizing plate 3
When the direction of 0, 31 was changed, a positive-negative inverted image was displayed. <Example 2> As the photoelectric conversion layer used in the present invention,
It is desirable to design the SLM so as to exhibit the following characteristics in order to improve the contrast of the displayed image.

When light is locally irradiated on the photoelectric conversion layer, a potential difference occurs between the light-irradiated portion and the non-irradiated portion. This is called an optical memory property.

The potential difference (optical memory property) is thus obtained.
When a voltage is externally applied to the SLM provided with the photoconductive layer in which the image is generated, the contrast of the displayed image is determined according to the potential difference (optical memory property).

Therefore, the present inventor obtained a conditional expression representing an optical memory property for producing a good contrast from the product of the irradiation light intensity and the light irradiation time and a potential difference by the following measuring method.

First, as shown in FIG. 15A, a sample SP in which the photoconductive layer 122 of the present invention is provided on the transparent electrode 105 is provided with a band-shaped opening 12 in the center as shown in FIG.
Irradiation light intensity is A from the light shielding mask 127 having 7a.
[Lux] light is irradiated for T [sec]. Next, the product of the irradiation light intensity A and the light irradiation time T is 1 × 10 ⁴ [lux · sec].
After the above, the sample SP was set in a commercially available electrostatic copying paper test apparatus (manufactured by Kawaguchi Electric Co., Ltd., Electrostatic Paper Analyzer / EPA-8100), and corona charging was applied.

Since the light-irradiated portion corresponding to the opening 127a of the mask 127 of the photoconductive layer 122 has optical memory properties, as shown in FIG. the V _M [V] decreased compared with unirradiated portion, contrast is caused by the value of the V _M [V].

[0149] Therefore, taking the ratio of the potential drop V _M and V _D, was calculated such good contrast as shown below to produce the condition.

[0150]

Equation 3] ^{A × T ≧ 1 × 10 4} [lux.sec] 0.1 ≦ when _{| V M / V D | ≦} 1.0 A [lux]: irradiation light intensity T [sec]: irradiation time V _D [V]: potential is shared in the photoconductive layer of the light unirradiated portion V _M [V]: is shared on the photoconductive layer of the potential and the light irradiation portion to be shared on the photoconductive layer of the light non-irradiated portion Therefore, when fabricating a high-contrast SLM, it is preferable to determine the material and layer thickness of each layer so as to satisfy the above-described conditions.

A specific example for that will be described.

First, an ITO film having a thickness of 700 ° was applied and hardened on the surface of many glass substrates by a sol-gel method, and was patterned to form a transparent electrode.

As a dispersion, 4.2 parts of a compound having the following structural formula, 2 parts of polymethyl methacrylate (weight average molecular weight: 11,000), and 35 parts of cyclohexanone and glass beads having a diameter of 1 mm were dispersed in a sand mill for 12 hours. After that, what added MEK60 part was prepared.

[0154]

Embedded image Next, the dispersion liquid was spin-coated on the surfaces of the four substrates, and 9
After drying at 0 ° C. for 15 minutes, a charge generation layer having a thickness of 0.10 μm was formed.

Next, the compounds of the following structural formulas (1) to (4)
Prepared, 10 parts of one of them, and bisphenol Z-type polycarbonate (weight average molecular weight 3500
0) 10 parts were dissolved in a mixed solvent consisting of 40 parts of dichloromethane and 20 parts of monochlorobenzene to prepare four types of solutions, and the solutions were coated on the surfaces of the charge generation layers on the four substrates by spin coating. After drying at 120 ° C. for 60 minutes, a charge transport layer 25 having a thickness of 0.9 μm was formed.

[0156]

Embedded image Then, the samples of each of the substrates having the different structures of the compounds (1) to the photoconductive layer having a four charge transport layer formed by (4), by the method of FIG. 15 V _M and V _D The ratio was determined. The AT product in this case is 5 × 10
⁴ [lux · sec]. Table 1 shows the results.

[0157]

[Table 1] From this table, that the value of V _M / V _D satisfies the conditional expressions described above, the compound (1) to (3) substrate samples 1 to 3 charge transport material, the substrate sample 4 Did not satisfy the conditional expression.

Next, a polyimide alignment film was printed to a thickness of 200 ° on the four substrates on which only ITO was formed, and baked in an oven at a temperature of 220 ° C. for 1 hour. Thereafter, a rubbing treatment was performed on the surface of the alignment film using a nylon cloth. Thereafter, an IPA solution in which spacer beads having a particle size of 2.0 μm were dispersed was applied to the surface of the alignment film side substrate 3 by a spinner, and oven-dried at 110 ° C. for 5 minutes using an oven.

Further, an epoxy-based sealing material is applied (printed) to the periphery of the substrate having the alignment film, and after leveling and drying,
One substrate with an alignment film and four types of substrates with a photoconductive layer were bonded together. As the ferroelectric liquid crystal, the same liquid crystal composition as used in Example 1 was prepared.

After that, the four kinds of cells to which the substrates were bonded were heated in an oven at a temperature of 140 ° C. for 1.5 hours, and the liquid crystal 13 was injected. At the time of the injection, the temperature was heated to 95 ° C., and the injection was performed. The cooling rate was 1 ° C./min.

After the liquid crystal was injected, the mixture was heated to 110 ° C., and then gradually cooled to 90 ° C. at a rate of 0.1 ° C./min.
Furthermore, it was allowed to cool to room temperature to produce an SLM. SLMs each having a photoconductive layer using compounds (1) to (3) as a charge transporting substance are referred to as SLM samples S1 to S3, and an SLM including a photoconductive layer 22 using compound (4) as a charge transporting substance. Was set as a comparative SLM sample CS1.

Next, the present inventor determined that each of the samples S1 to S3
14 with respect to the SLM according to the comparative sample CS1.
As shown in (a), a semiconductor laser 60 and an optical fiber 61 are used, and a laser beam (wavelength 7
80 nm of infrared light) and emitted light. In addition,
The mask 62 was as shown in FIG. 3B, and the energy density of the laser beam was 0.5 μJ / cm ² . After the light input, information was written by applying a DC voltage of 40 [V].

Thereafter, as shown in FIG. 19C, the SLM 21 was disposed between the crossed Nicols of the polarizing plates 30 and 31, and the reading light _LR was irradiated.

As a result, in the liquid display device provided with the SLMs of the samples S1 to S3, image information as shown in FIG. Further, in these liquid display elements, reversal of the positive negative was observed depending on the orientation of the polarizing plates 30 and 31. On the other hand, the contrast of the SLM of the comparative sample CS1 was low. <Example 3> First, an ITO film was formed by sputtering on the surface of each of eight glass substrates, followed by patterning to form a transparent electrode.

As the dispersion, Compound 4 having the following structural formula was used.
Part, benzal resin (weight average molecular weight 24000) 2
And 34 parts of cyclohexanone and glass beads having a diameter of 1 mm were dispersed in a sand mill for 20 hours, and then 60 parts of butanol was added.

[0166]

Embedded image Next, the dispersion was spin-coated on the surface of the substrate and dried at 80 ° C. for 15 minutes to form a charge generation layer.

Next, the compounds of the above structural formulas (1) to
10 parts of (4) and 10 parts of bisphenol Z-type polycarbonate (weight average molecular weight 39000) were dissolved in a mixed solvent composed of 40 parts of dichloromethane and 20 parts of monochlorobenzene to prepare four kinds of solutions.
The seed solution was coated on the surface of the charge generation layer by spin coating, and dried at 120 ° C. for 60 minutes to form a film having a thickness of 0.8 μm.
Four substrate samples on which the charge transport layer was formed were formed.

Then, the 4 prepared in the same manner as described above,
For one sample, V _M and V _D by the method of FIG.
Was determined. The AT product in this case is 2.5 × 10 ⁵ [lu
x · sec]. Table 2 shows the results.

[0169]

[Table 2] From this table, that the value of V _M / V _D satisfies the conditional expressions described above, the compound (1) to (3) substrate samples 5 to 7 and a charge transport material, the substrate samples 8 It turns out that the conditional expression is not satisfied.

Next, a polyimide alignment film was formed on the four substrates with ITO, and the four substrates with alignment films were bonded to substrate samples 5 to 8, and then the cells with the substrates bonded were placed in an oven. 1.5 hours at a temperature of 140 ° C
r, and the liquid crystal 13 was injected.

After injecting the liquid crystal, the mixture was heated to 110 ° C., then gradually cooled to 90 ° C. at a rate of 0.1 ° C./min, and allowed to cool to room temperature, thereby producing four SLM samples. An SLM having a photoconductive layer using compounds (1) to (3) as a charge transporting material was prepared as SLM sample S.
4 to S6, and an SLM having a photoconductive layer using the compound (4) as a charge transport material was used as a comparative sample CS2.

Next, the present inventor used a camera strobe instead of the laser 60 shown in FIG.
The strobe flash was emitted through a negative film in place of 2, and light was input. Then, after this light input, a DC voltage of 50 [V] was applied to write information. Thereafter, as shown in FIG. 3C, each SLM sample was placed between the crossed Nicols polarizing plates 30 and 31, and the readout light _LR was irradiated.

As a result, the liquid display device provided with the SLMs of the samples S4 to S6 depends on the orientation of the polarizing plates 30 and 31.
Inversion of the positive / negative was observed, and the contrast due to the density of the film was clearly reproduced. However, the contrast of the SLM of the comparative sample CS2 was low. Example 4 The same liquid crystal composition as in Example 1 was prepared as a liquid crystal. Further, in the same manner as in Example 1, 20 substrates with an ITO film were prepared. Ten of them were provided with the same uniaxial alignment film as in Example 1.

Of the remaining ten sheets, five had the same charge generation layer as in Example 1. Then, as shown in FIG. 16 (a), biphenylene is used as a charge transporting material, and it is dispersed in five types of resins to form a photoelectric conversion layer having five types of charge transporting layers, and the surface energy is measured. did.

In the same manner as in Example 1, the five substrates and the five substrates with an alignment film were attached to each other, and liquid crystal was injected.
(No. 11 to No. 15) were produced.

On the other hand, on five substrates with ITO films, FIG.
In the five kinds of resins shown in (b), titanyl as a charge generating substance and anthracene as a charge transporting substance are dispersed to form five types of photoelectric conversion layers each having a single layer, and the surface energy is measured. did.

The five types of sample substrates and the substrate with an alignment film were attached to each other, and liquid crystal was injected to produce five types of SLM samples (Nos. 16 to 20).

Observation of the orientation of the ten SLM samples (No. 11 to No. 20) thus produced revealed that the SLM samples (Nos. 11, 12, 13, 16, 16
17, 18) showed good orientation.

In addition, SLM samples (Nos. 19 and 20)
Although some defects were observed, it is considered that such defects are not practically problematic.

Since the SLM samples (Nos. 14 and 15) suffered from poor orientation, defects were not reduced without additional means such as reheating and then gradually cooling to reorient.

Here, the method used for measuring the above-mentioned surface energy will be described. This method is a method of measuring surface energy based on a macroscopic surface state of each substrate of a liquid crystal element.

Examples of the reagent having a contact angle of a droplet include A: α-bromonaphthalene, B: methylene iodide,
C: Use water or the like. Then, after measuring the contact angle by each of A, B, C, etc., as an example, Journal of the Adhesion Society of Japan, Vol. 8, N
o. 3 (1972) P131-Kitazaki et al. It is determined by the calculation formula described in "Expansion of Fowkes equation and evaluation of surface tension of polymer solid".

As shown in FIG. 16A, when the photoconductive layer is of a laminated type, the surface energy is 30 dyn / cm.
^It can be seen that it is preferable to use PTFE, polyvinylidene fluoride, or polycarbonate which is ² or less.

As shown in FIG. 16B, when the photoconductive layer is of a mixed type, the surface energy is 30 dyn.
/ Cm ² or less, it is preferable to use polytrifluoroethylene, polyacrylamide, or polycarbonate. Example 5 An SLM according to this example was manufactured as follows. First, a 700 ° -thick ITO film was applied and cured on the surfaces of two glass substrates by a sol-gel method, and then patterned to form a transparent electrode.

Next, a dispersion liquid (described in detail below) is spin-coated on the surface of one of the substrates and dried at 90 ° C. for 15 minutes to form a single layer containing only a charge generating substance having a thickness of 0.55 μm. A photoconductive layer was formed.

The dispersion was prepared by mixing 4 parts of a mixed crystal phthalocyanine of titanyl phthalocyanine and vanadyl phthalocyanine with a polyester resin (trade name: Almatix P-
645, 8 parts by Mitsui Toatsu Chemicals Co., Ltd., melamine resin (trade name: Kobanma 1R, Mitsui Toatsu Chemicals Co., Ltd.) 2
Part and 100 parts of cyclohexanone and glass beads having a diameter of 1 mm were dispersed in a sand mill for 70 hours.

When a light decay curve as shown in FIG. 18 was obtained for this photoconductive layer, the differential coefficient | ΔV / ΔE | showed a maximum value with respect to the light amount E, and the value was 3.7.

On the other hand, a polyimide alignment film was printed on the other substrate to a thickness of 200 ° and baked in an oven at a temperature of 220 ° C. for 1 hour. Thereafter, a rubbing treatment was performed on the surface of the alignment film using a nylon cloth.

Next, an IPA solution in which spacer beads having a particle size of 2.0 μm were dispersed was applied to the surface of the alignment film by a spinner, and oven-dried at a temperature of 110 ° C. for 5 minutes using an oven. Furthermore, an epoxy-based sealing material was applied (printed) to the periphery of the alignment film, and after leveling and drying, the substrate with the alignment film and the non-rubbed substrate with a photoconductive layer were bonded.

After that, the substrate thus bonded was heated in an oven at a temperature of 140 ° C. for 1.5 hours, and the liquid crystal 13 was injected. In addition, at the time of injection, heat the temperature to 95 ℃,
An injection was made. The cooling rate was 1 ° C./min.

Then, after injecting the liquid crystal, the mixture was heated to 110 ° C.
The sample was gradually cooled to 90 ° C. at a rate of 0.1 ° C./min, and then allowed to cool to room temperature to produce an SLM.

An epoxy-based sealing material was used. The same liquid crystal composition as that used in Example 1 was used as the ferroelectric liquid crystal 13.

Next, the present inventor uses a semiconductor laser 60 and a laser scanning unit 61 as shown in FIG. 14A to apply a laser beam (wavelength of 780 nm) to the SLM manufactured as described above. (Infrared ray) and direct current voltage 40
[V] was applied to perform writing (of a character image).

Then, as shown in FIG. 17B, the SLM is placed between the crossed Nicol polarizing plates 30 and 31.
21 was arranged, and the reading light _LR was irradiated. as a result,
In the SLM of this embodiment, the reversal of the positive / negative was observed depending on the direction of the deflecting plates 30 and 31, and the dot reproducibility was very clear as shown in FIG. Example 6 An SLM according to this example was manufactured as follows. First, ITO films were formed by sputtering on the surfaces of two glass substrates, respectively, and were patterned to form transparent electrodes. Next, a dispersion liquid (described in detail below) was spin-coated on the surface of one of the substrates, and dried at 80 ° C. for 15 minutes to form a photoconductive layer having a thickness of 0.65 μm.

The dispersion was composed of α-type copper phthalocyanine 1
0 parts, 0.3 parts of tetranitrated copper phthalocyanine and polyester resin (trade name: Almatics P-64)
5, 40 parts of Mitsui Toatsu Chemical Co., Ltd., melamine resin (trade name: Uban 20-HS, Mitsui Toatsu Chemical Co., Ltd.) 1
0 parts and 200 parts of cyclohexanone and glass beads having a diameter of 1 mm were dispersed in a sand mill for 20 hours.

Next, when a light attenuation curve was obtained for this photoconductive layer, the derivative | ΔV / ΔE | showed a maximum value with respect to the light amount E, and the value was 5.1. Thereafter, an SLM was manufactured in the same manner as in Example 5 described above.

Next, the present inventor applied a DC voltage of 45 (V) to the SLM manufactured as described above, as shown in FIG.
The writing of the character image was performed.

Then, as shown in FIG. 18B, the SLM is placed between the crossed Nicol polarizers 30 and 31.
21 was arranged, and the reading light _LR was irradiated. as a result,
The SLM of this embodiment depends on the directions of the polarizing plates 30 and 31.
Positive and negative inversions were observed, and the dot reproducibility was much clearer than in Example 5.

Next, a comparative example with respect to the fifth and sixth embodiments of the present invention will be described.

An SLM according to a comparative example was manufactured as follows. First, ITO films were formed by sputtering on the surfaces of two glass substrates, respectively, and were patterned to form transparent electrodes. Next, a dispersion (described in detail below) was spin-coated on the surface of one of the substrates, and dried at 80 ° C. for 15 minutes to form a photoconductive layer having a thickness of 0.6 μm.

The dispersion was prepared by adding 5 parts of a charge generating substance having the following structural formula and 5 parts of a charge transporting substance to 5 parts of a polycarbonate resin (trade name: Z-200) and 4 parts of monochlorobenzene.
0 part, mixed solvent diameter 1mm consisting of 80 parts of dichloromethane
And dispersed in a sand mill for 40 hours.

[0202]

Embedded image Next, when a light decay curve was obtained for this photoconductive layer, the derivative coefficient | ΔV / ΔE | did not show a maximum value with respect to the light amount E, and the value was almost 1. And after this,
An SLM was manufactured in the same manner as in Example 5 described above.

Next, a DC voltage of 70 (V) was applied to the SLM manufactured as described above, as shown in FIG.
To write a character image using laser light (wavelength 810 nm).

Then, as shown in FIG. 17B, the SLM is placed between the crossed Nicol polarizers 30 and 31.
The place was irradiated with reading light L _R. As a result, in the SLM of this comparative example, depending on the orientation of the polarizing plates 30 and 31, positive / negative inversion was observed, but an unclear portion was observed around the dot.

As described above, by forming the photoconductive layer as a photoconductive layer having a maximum value in the differential coefficient (Δpotential / Δlight quantity) -light quantity characteristic of the light decay curve, the photoconductive layer is irradiated with light. In this case, a photocurrent flows, and the orientation state of the liquid crystal is changed by the photocurrent, so that high-resolution information can be written. This eliminates the need for a complicated optical system such as a reflection type, a light shielding film, a dielectric mirror, and the like, and can simplify the structure. High-resolution information writing with excellent reproducibility becomes possible. <Embodiment 7> In this embodiment, a transparent electrode was formed by applying and curing an ITO film having a thickness of 700 ° on the surface of 22 glass substrates by a sol-gel method, followed by patterning.

As a dispersion, 2 parts of a compound having the following structural formula were mixed with 2 parts of a polycarbonate resin (trade name: Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 20 parts of tetrahydrofuran, and glass beads having a diameter of 1 mm. What was dispersed by a sand mill for 60 hours was prepared.

[0207]

Embedded image Next, this dispersion was spin-coated on the surface of the substrate,
Drying was performed at 15 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.65 μm.

Then, 5 parts of a triarylamine compound having the following structural formula

[0209]

Embedded image And a solution of 5 parts of polycarbonate (trade name: Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in 70 parts of chlorobenzene, coated on the surface of the charge generation layer by spin coating, and then dried at 120 ° C. for 60 minutes. 0.025μm
Was formed. The substrate having the photoconductive layer was used as a substrate sample S21.

Next, the thickness of the charge generation layer (CGL) and the charge transport layer (CTL) and the ratio (P / B) of the charge generation material to the binder resin in the charge generation layer are shown in Table 1 below. Other than that, ten types of photoconductive layers 22 were formed in the same manner as the substrate sample S21, and the substrate samples S22 to S27,
Comparative substrate samples CS21, CS22, and CS23 were used.

[0211]

[Table 3] Table 3 also shows the ratio C _CTL / C _CGL of the electric capacity of the charge generation layer and the electric capacity of the charge transport layer in each of the substrate samples. Here, in order to obtain the electric capacity of the layer used for each sample, 4192A, an LF impedance analyzer (manufactured by Yokogawa-Hewlett-Packard Co., Ltd.) was used.
Al substrate / CGL (or CTL) film (3-6 μm) / A
A dielectric constant measurement sample having a structure of u (evaporation) was prepared and measured.

As is clear from Table 1, the values of C _CTL / C _CGL of the photoconductive layers of the substrate samples S21 to S28 are at least 1.0 or more, and the comparative substrate sample C
The values of C _CTL / C _CGL of S21 to CS23 were 1.0 or less.

Next, the relationship between the amount of light and the photocurrent in the photoconductive layers of the substrate samples S21 to S28 and the photoconductive layers of the comparative substrate samples CS21 to CS23 was determined. FIG.
19 shows the relationship between the light amount and the photocurrent in the substrate samples S21, S23, and S25 and the comparative substrate sample CS22. As is clear from FIG. 19, C _CTL /
Those having a C _CGL value of at least 1.0 _exhibited an avalanche effect. On the other hand, C _CTL / C _CGL
A value of 1.0 or less showed a large dark current, a linear light-current characteristic, and no avalanche effect.

Therefore, by changing the thickness of the charge generation layer and the charge transport layer and the ratio (P / B) of the charge generation material to the binder resin, the induction point of the photocurrent and γ
It is clear that the control of (slope of photocurrent) is possible.

On the other hand, a polyimide alignment film having a thickness of 200 ° was printed on 11 substrates with ITO, and baked in an oven at a temperature of 220 ° C. for 1 hour. Thereafter, a rubbing treatment was performed on the surface of the alignment film using a nylon cloth.

Next, an IPA solution in which spacer beads having a particle size of 2.0 μm are dispersed is applied to the surface of the substrate with an alignment film by a spinner, and oven-dried in an oven at 110 ° C. for 5 minutes. Was. Furthermore, an epoxy-based sealing material is applied (printed) to the periphery of the substrate with an alignment film, and after leveling and drying, the substrate with an alignment film and a substrate sample S21
To S28 and CS21 to CS23, respectively.

Thereafter, the cell on which the substrates were bonded was heated in an oven at a temperature of 140 ° C. for 1.5 hours, and when the same liquid crystal as in Example 1 was injected, the temperature was raised to 95 ° C. After that, it was gradually cooled at a cooling rate of 1 ° C./min.

Then, it was heated again to 110 ° C.,
The sample was gradually cooled to 90 ° C. at a temperature lowering rate of ° C./min, and further allowed to cool to room temperature, thereby producing an SLM.

Next, the present inventor uses a semiconductor laser 60 and a laser scanning unit 61 as shown in FIG. 14A to apply laser light (wavelength of 780 nm) to the thus manufactured SLM. (Infrared ray) and direct current voltage 40
[V] was applied to perform writing (of a character image).
The energy density of the laser beam was 0.5 μJ / cm ²
And

Thereafter, as shown in (b) of the figure, the SLM is placed between the crossed Nicol polarizing plates 30 and 31.
21 was arranged, and the reading light _LR was irradiated. as a result,
In the SLM having the substrate samples S21 to S28, the reversal of the positive / negative was observed depending on the orientation of the polarizing plates 30 and 31, and the dot reproducibility was very clear.
In the SLM using 1 to CS23, the periphery of the dot was unclear. <Embodiment 8> In the present embodiment, first, an ITO film was formed by sputtering on the surfaces of two glass substrates, and patterning was performed to form a transparent electrode.

As the dispersion, 4 parts of 4,10-dibromoanthanthrone and benzal resin (weight average molecular weight 2
4000), 34 parts of cyclohexanone, and glass beads having a diameter of 1 mm were dispersed in a sand mill for 20 hours, and then 60 parts of butanol was added.

Next, this dispersion was spin-coated on the surface of one of the substrates and dried at 80 ° C. for 15 minutes to form a film having a thickness of 0.6.
A 5 μm charge generation layer was formed.

Next, 10 parts of a compound having the following structural formula, and bisphenol Z-type polycarbonate (weight average molecular weight 3
9000) was dissolved in a mixed solvent consisting of 80 parts of dichloromethane and 80 parts of monochlorobenzene to prepare a solution. This solution was coated on the surface of the charge generation layer by spin coating, and then heated at 120 ° C. for 10 minutes. The substrate was dried to form the charge transport layer 25 having a thickness of 0.025 μm.
And The capacitance ratio (C _CTL / C _CGL ) of the substrate sample S29 was 17.75.

[0224]

Embedded image Thereafter, the sample S29 is made in the same manner as in the above-described embodiment 7.
Was used to produce an SLM.

Next, the present inventor applied a DC voltage of 50 (V) to the SLM manufactured as described above as shown in FIG.
The writing of the character image according to m) was performed.

Then, as shown in (b) of the figure, the SLM is placed between the crossed Nicol polarizing plates 30 and 31.
21 was arranged, and the reading light _LR was irradiated. as a result,
The SLM of this embodiment depends on the directions of the polarizing plates 30 and 31.
Positive and negative reversals were observed, and the dot reproducibility was very clear.

As described above, according to this embodiment, a photocurrent flows through the photoconductive layer at the time of light irradiation by using a photoconductive layer having a function-separation type avalanche effect. The orientation state changes, and high-resolution information can be written. Thus, when combined with a writing light irradiation device that performs image processing in a digital manner, high-resolution information writing with excellent dot reproducibility becomes possible.

In the above, the case where a transparent conductive film that is not patterned in a stripe shape is used as an electrode has been described. However, the present invention relates to a pair of transparent electrodes that are arranged in a stripe shape so as to be driven by multi-braxing. It is also suitably used for a liquid crystal element in which liquid crystal is injected into a cell in which a uniaxial alignment film and a non-rubbing photoelectric conversion layer are respectively provided on the substrate surface.

[0229]

According to the present invention, a liquid crystal element having a bookshelf layer structure with few defects without using complicated steps can be provided at a low cost with an excellent display quality. In addition, since there is a degree of freedom in selecting a charge generating substance and a charge transporting substance, deterioration of display characteristics due to a change in temperature is suppressed, and display quality can be improved by a favorable alignment state. Further, the sensitivity can be improved.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a structure of a conventional liquid crystal element.

FIG. 2 is a schematic view illustrating a structure of a liquid crystal element of the present invention.

FIG. 3 is a schematic view illustrating the operation of the liquid crystal element of the present invention.

FIG. 4 is a view showing spectral transmittance characteristics of constituent materials of an organic semiconductor layer used in the present invention.

FIG. 5 is a view showing spectral transmittance characteristics of constituent materials of an organic semiconductor layer used in the present invention.

FIG. 6 is a view showing spectral transmittance characteristics of constituent materials of another organic semiconductor layer used in the present invention.

FIG. 7 is a view showing spectral transmittance characteristics of a constituent material of still another organic semiconductor layer used in the present invention.

FIG. 8 is a view showing the relationship between the thickness of a photoelectric conversion layer used in the present invention and the resolution.

FIG. 9 is a view showing evaluation results of a photoelectric conversion layer used in the present invention.

FIG. 10 is a view showing distribution characteristics of an exposure light amount in a digital exposure system.

FIG. 11 is a schematic view illustrating a manufacturing process of a liquid crystal element used in the present invention.

FIG. 12 is a schematic diagram showing a structure of a liquid crystal element according to another embodiment of the present invention.

FIG. 13 is a schematic view showing a structure of a liquid crystal element according to still another embodiment of the present invention.

FIG. 14 is a schematic diagram for explaining an information writing operation and an information reading operation of the liquid crystal element of the present invention.

FIG. 15 is a schematic diagram for explaining a method for measuring optical memory properties.

FIG. 16 is a diagram illustrating characteristics of various liquid crystal elements.

FIG. 17 is a view showing characteristics of a photoelectric conversion layer used in a liquid crystal element according to another embodiment of the present invention.

FIG. 18 is a view showing characteristics of a photoelectric conversion layer of a liquid crystal element according to still another embodiment of the present invention.

FIG. 19 is a graph showing characteristics of a photoelectric conversion layer used in the present invention.

[Explanation of symbols]

2, 3 glass substrate (transparent substrate) 5, 6 transparent electrode 12 uniaxial alignment film 9, 13 ferroelectric liquid crystal 21, 41, 51 SLM (liquid crystal element) 22 photoconductive layer (photoconductive semiconductor layer) 23 charge generation layer (Layer containing charge generating substance) 25 Charge transporting layer (layer containing charge transporting substance) 26 Writing light irradiation device

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G09F 9/35 302 G02F 1/137 510 (31) Priority claim number Japanese Patent Application No. Hei 9-260472 (32) Priority Niigata 9 (1997 ) September 25 (33) Countries claiming priority Japan (JP)

Claims (41)

[Claims] A pair of transparent substrates, a pair of transparent electrodes, a photoelectric conversion semiconductor layer, an alignment film, and a liquid crystal sandwiched between the alignment film and the photoelectric conversion semiconductor layer. And a rubbing treatment is applied only to the alignment film, and the rubbing treatment is not applied to the photoelectric conversion semiconductor layer. 2. The liquid crystal device according to claim 1, wherein a surface energy of the photoelectric conversion semiconductor layer is 30 dyn / cm ² or less. 3. The liquid crystal according to claim 1, wherein the photoelectric conversion semiconductor layer has a laminated structure of a layer containing a charge generating substance and a layer containing a charge transporting substance. element. 4. The liquid crystal device according to claim 1, wherein the photoelectric conversion semiconductor layer is a single layer and contains the charge generating substance and the charge transporting substance. 5. The liquid crystal device according to claim 1, wherein the liquid crystal is a chiral smectic liquid crystal. 6. The liquid crystal according to claim 1, wherein the liquid crystal has a phase transition sequence without a cholesteric phase and has a bookshelf layer structure. element. 7. a step of forming a transparent electrode on each of a pair of transparent substrates, a step of forming a photoelectric conversion semiconductor layer on one of the transparent substrates, a step of forming an alignment film on the other transparent substrate, and the alignment film A rubbing process, a step of bonding the pair of transparent substrates, and a step of injecting a liquid crystal into a gap between the pair of transparent substrates. A method for producing a liquid crystal element, wherein a rubbing treatment is not performed. 8. A liquid crystal element including a liquid crystal sandwiched between a pair of substrates, wherein one of the pair of layers in contact with the liquid crystal is a charge-transporting photoelectric conversion semiconductor layer, and the other of the pair of layers is Only a uniaxial alignment film. 9. The liquid crystal device according to claim 8, wherein the surface energy of the photoelectric conversion semiconductor layer is 30 dyn / cm ² or less. 10. The liquid crystal device according to claim 8, wherein the liquid crystal is a chiral smectic liquid crystal having a phase transition series without a cholesteric phase. 11. The liquid crystal device according to claim 8, wherein the liquid crystal is a chiral smectic layer having a bookshelf layer structure. 12. The liquid crystal element according to claim 8, wherein the charge-transporting photoelectric conversion semiconductor layer is not subjected to a rubbing treatment. 13. The liquid crystal device according to claim 8, wherein the charge-transporting photoelectric conversion semiconductor layer is an organic semiconductor. 14. The liquid crystal element according to claim 8, wherein the uniaxial alignment film is a rubbed film. 15. The liquid crystal device according to claim 8, wherein a charge generation layer is provided between the photoelectric conversion semiconductor layer and an electrode. 16. The photoelectric conversion semiconductor layer is a non-rubbed organic semiconductor, the liquid crystal is a chiral smectic liquid crystal having a bookshelf layer structure, having a phase transition series without a cholesteric phase, The liquid crystal element according to claim 8, wherein the uniaxial alignment film is a rubbed polyimide film. 17. A liquid crystal element including a liquid crystal sandwiched between a pair of substrates, wherein one of the pair of layers in contact with the liquid crystal is a photoelectric conversion organic semiconductor layer, and only the other of the pair of layers is uniaxial. A liquid crystal element, which is an alignment film, wherein the liquid crystal is a chiral smectic liquid crystal having a bookshelf layer structure. 18. The liquid crystal device according to claim 17, wherein the photoelectric conversion organic semiconductor layer has a surface energy of 30 dyn / cm ² or less. 19. The liquid crystal device according to claim 17, wherein the photoelectric conversion organic semiconductor layer has an optical memory property, and the optical memory property is represented by the following conditional expression. [Number 1] ^{A × T ≧ 1 × 10 4} [lux.sec] 0.1 ≦ when _{| V M / V D | ≦} 1.0 A [lux]: irradiation light intensity T [sec]: irradiation time V _D [V]: voltage V _M which is shared by the photoelectric conversion organic semiconductor layer of the light unirradiated portion [V]: photoelectric conversion organic potential and light irradiation portion to be shared by the photoelectric conversion organic semiconductor layer of the light non-irradiated portion Difference from potential assigned to semiconductor layer 20. The liquid crystal device according to claim 19, wherein the photoelectric conversion organic semiconductor layer contains an organic charge generating substance and a charge transporting substance. 21. The liquid crystal device according to claim 19, wherein the photoelectric conversion organic semiconductor layer has a laminated structure of a layer containing a charge generating substance and a layer containing a charge transporting substance. 22. The liquid crystal device according to claim 19, wherein the photoelectric conversion organic semiconductor layer has a single-layer structure containing a charge generating substance and a charge transporting substance. 23. The liquid crystal device according to claim 19, wherein the photoelectric conversion organic semiconductor layer has an intermediate layer. 24. The liquid crystal device according to claim 19, further comprising a color filter between the pair of substrates. 25. The liquid crystal device according to claim 19, wherein the liquid crystal is a ferroelectric liquid crystal. 26. The photoelectric conversion organic semiconductor layer has a charge generation layer and a charge transport layer, and has a capacitance (C _CGL ) of the charge generation layer and a capacitance (C _CTL ) of the charge transport layer. 18. The liquid crystal device according to claim 17, wherein the ratio (C _CTL ) / (C _CGL ) is 1.0 or more. 27. The electric capacity (C _CGL ) of the charge generation layer
And the ratio (C _CTL ) of the electric charge (C _CTL ) of the charge transport layer
27. The liquid crystal device according to claim 26, wherein / (C _CGL ) is 2.5 or more. 28. The electric capacity (C _CGL ) of the charge generation layer
And the ratio (C _CTL ) of the electric charge (C _CTL ) of the charge transport layer
28. The liquid crystal device according to claim 27, wherein / (C _CGL ) is 5.0 or more. 29. The liquid crystal device according to claim 26, wherein said photoelectric conversion organic semiconductor layer has an intermediate layer between said photoelectric conversion organic semiconductor layer and said electrode. 30. The liquid crystal device according to claim 26, wherein the charge generation material in the charge generation layer is an azo pigment represented by the following general formula [1]. Embedded image (Wherein, X represents a hydrogen atom or a halogen atom. R1, R
2, R3, R4, and R5 are a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group which may have a substituent,
It represents an alkoxy group, an aralkyl group, an aryl group, or an alkylamino group, which may be the same or different. m
And n represent 1 or 2, and may be the same or different. ) 31. The liquid crystal device according to claim 26, further comprising a color filter. 32. The liquid crystal device according to claim 26, wherein the liquid crystal is a ferroelectric liquid crystal. 33. The liquid crystal device according to claim 17, wherein the photoelectric conversion organic semiconductor layer has a maximum value in a differential coefficient (Δ potential / Δ light amount) -light amount characteristic of a light attenuation curve. 34. The liquid crystal device according to claim 33, wherein a value of a differential coefficient calculated from a normalized light attenuation curve of the photoelectric conversion organic semiconductor layer is at least 3 or more. 35. The liquid crystal device according to claim 33, wherein the photoelectric conversion organic semiconductor layer contains an organic charge generating substance and a charge transporting substance. 36. The liquid crystal device according to claim 33, wherein the photoelectric conversion organic semiconductor layer has a laminated structure of a layer containing a charge generating substance and a layer containing a charge transporting substance. 37. The liquid crystal device according to claim 33, wherein the photoelectric conversion organic semiconductor layer has a single layer structure containing the charge generating substance alone or the charge generating substance and a charge transporting substance. 38. The liquid crystal device according to claim 33, wherein the photoelectric conversion organic semiconductor layer has an intermediate layer. 39. The liquid crystal device according to claim 33, further comprising a color filter. 40. The liquid crystal device according to claim 33, wherein the liquid crystal is a ferroelectric liquid crystal. 41. A method of manufacturing a liquid crystal element, comprising: forming a transparent electrode on each of a pair of transparent substrates; forming a photoelectric conversion organic semiconductor layer on one surface of the pair of transparent substrates; Forming an alignment film on the other surface of the transparent substrate, rubbing only the alignment film among the photoelectric conversion organic semiconductor layer and the alignment film, and forming a surface on the surface of the photoelectric conversion organic semiconductor layer. A step of disposing a curable resin to be a substrate, a step of bonding the respective transparent substrates, a step of curing the curable resin, and a step of injecting a liquid crystal into a gap between the pair of bonded transparent substrates. A method for manufacturing a liquid crystal element, comprising: