JP2000282040A - Liquid crystal composite display device and method of manufacturing the same - Google Patents

Abstract

(57) [Problem] To provide a liquid crystal display element which enables a low drive voltage and has excellent light transmittance-voltage hysteresis characteristics at the time of voltage rise and fall. A water-insoluble polymer / liquid crystal composite film composed of a water-insoluble polymer and a nematic liquid crystal, and at least one of two sheets having conductive portions opposed to each other with both sides sandwiching the composite film are light-transmissive. a liquid crystal composite display device having an optical modulation function consisting of a conductive substrate having, among its liquid crystal display characteristics, the external driving electric field E _0.9 delta _T (external driving voltage V _0.9 delta _T /
d) is 0.15 to 4.5 AC (V / μm), and the hysteresis characteristic value H is 0.0 to 0.35 AC (V / μm).
A liquid crystal composite display element characterized by the following.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal composite display device and a method for manufacturing the same. More specifically, a liquid crystal composite display device using a polymer / liquid crystal composite film in which a polymer matrix is formed in a three-dimensional network in a continuously penetrated liquid crystal phase. A liquid crystal composite display device that is excellent in enabling low voltage driving, excellent in light transmittance-voltage hysteresis display characteristics when voltage rises and falls, and excellent in adhesion between a conductive substrate and a polymer / liquid crystal composite film. The present invention relates to a light modulation element, a display (display) device, a reflective display, a liquid crystal composite display element suitable for a light control element, and a method of manufacturing the same.

[0002]

2. Description of the Related Art In recent years, with the growing demand for portable, thin, light and compact information devices and low power consumption of information devices, liquid crystal display devices (liquid crystal displays) have been used as calculators, watches, personal computers and the like as display media for characters and images. ) Is noticeable. In a liquid crystal display method, TN (Twisted) is used.
Nematic) method, wristwatch,
Widely used for calculators, etc.
(Super Twisted Nematic) method has been used as a liquid crystal display device of a notebook personal computer, a word processor or the like. A general TN and STN-liquid crystal display device is a device in which liquid crystal is sealed in a liquid crystal cell in which a predetermined seal or the like is provided between two glass plates having transparent electrodes, and furthermore, both surfaces are sandwiched by polarizing plates. It is.

However, there are problems such as (1) a narrow viewing angle due to the necessity of two polarizing plates, (2) a large dependency on cell thickness, and difficulty in increasing the area. In such a case, there is a limit to a reduction in thickness and weight, an increase in area, a reduction in driving voltage (low power consumption), and the like.

Therefore, recently, in the field of use for such a display element, as a display element that solves the above-mentioned problems, a polymer that does not require a polarizing plate (film) and does not require an alignment treatment has been used. Attention has been paid to a liquid crystal composite display device using a mixture of a material and a low-molecular liquid crystal, and research and development are being vigorously pursued. The application of this liquid crystal display element to a switchable light modulation display element, a dimming element, a display device, and the like that responds by an electric field (electric field) is being studied.

As a method of manufacturing a liquid crystal composite display element, the following technology is disclosed. For example, (a) polymer /
Emulsion method using water-soluble polymer as constituent material of matrix polymer in liquid crystal composite film, and (b) phase separation method using water-insoluble polymer as constituent material of matrix polymer in composite film Is done. The former (a) emulsion method is disclosed in, for example, Japanese Patent Publication No. 58-501631. In this method, a water-soluble polymer (polyvinyl alcohol (hereinafter abbreviated as PVA), gelatin) is used as a matrix polymer in a composite film, and a nematic liquid crystal having a positive dielectric anisotropy is mixed and emulsified in an aqueous solution of the PVA. This is a method for producing a polymer / liquid crystal composite film by evaporating water. In addition, Japanese Patent Publication No. Sho 61-50212
No. 8 discloses a method of preparing a composite film from an aqueous solution by mixing a liquid crystal emulsion with latex. On the other hand, the phase separation method (b) is a solvent casting method in which the liquid crystal and the matrix polymer are mixed with a common good solvent for the liquid crystal and the matrix polymer, and the liquid crystal is phase-separated from the matrix polymer in the process of evaporating the solvent. (JP-A-2-55
No. 318, JP-T-61-502128) and a monomer which is a precursor of a matrix polymer (resin) before curing is mixed with a liquid crystal, and irradiated with ultraviolet (UV) or electron beam (EB). There is disclosed a method (Japanese Patent Application Laid-Open No. 1-252689) in which a liquid crystal is formed and a phase is separated during the conversion of a monomer into a matrix polymer (resin).

A liquid crystal display device using a water-soluble polymer as a matrix polymer in a liquid crystal composite film in the emulsion method (a) described above has the following two problems from the viewpoint of its display characteristics or liquid crystal device. The point is pointed out. Liquid crystal display devices using water-soluble polymers have lower stability such as heat resistance and moisture resistance than non-water-soluble polymers, so the alignment state of the liquid crystal is disturbed when an electric field is applied, resulting in phase separation. A change in the state occurs, and the display characteristic of the hysteresis characteristic of the light transmittance-temperature with the increase and decrease of the temperature change deteriorates.
In addition, since the water-soluble polymer has a higher polarity than the water-insoluble polymer, the polymer and the liquid crystal have a strong tendency to be mixed with each other due to repetition of an external stimulus such as an electric field. In addition to the application of heat as an external stimulus, the display element of (1) is insufficient in electric field change, that is, display characteristics such as hysteresis characteristics of light transmittance-applied voltage when voltage rises and falls.

In general, a change in light transmittance with respect to an applied rise and fall voltage (light transmittance in a rise and fall of a voltage—a hysteresis curve of applied voltage) of these liquid crystal composite display elements decreases when the voltage increases and when the voltage increases. The path of the trajectory is different from that in the case of going, and so-called hysteresis is involved. The transmittance-applied voltage hysteresis curve is from 0 (V) to Vrms (V).
(Effective voltage) and when Vr
When the voltage is reduced from ms (V) to 0 (V), a hysteresis curve is drawn without following the same locus.

On the other hand, liquid crystal composite display elements are generally driven in a time-division (multiplex) manner. This is because according to this method, the number of wirings for connecting the electrodes of the liquid crystal display element and the drive circuit can be reduced, and the productivity is excellent.

When such a driving method is applied to a liquid crystal display element, the same is applied to the case where the transmittance-applied voltage hysteresis curve of the liquid crystal display element increases and decreases. It is assumed that the trajectory is followed. When driving a liquid crystal composite display element having a large hysteresis in the transmittance-applied voltage hysteresis curve, the ratio of the effective voltage value of the applied voltage specifying the ON pixel to the driving voltage specifying the OFF pixel is absorbed by the voltage width of the hysteresis. This results in a display in which the difference between the transmittance of the ON pixel and the transmittance of the OFF pixel cannot be obtained. Therefore, the hysteresis characteristic of light transmittance-applied voltage when the voltage rises and falls is an important display characteristic that is indispensable, like the low drive voltage property of a display element such as a display.

A technology enabling low voltage driving characteristics, which are important characteristics required for practical use of a liquid crystal composite display device, and hysteresis characteristics of light transmittance-applied voltage (time-division driving characteristics) when voltage rises and falls. Is disclosed in JP-A-5-24130.
JP, JP-A-6-167723, JP-A-8-1
No. 580, for example. However, in the above-mentioned method (b), in which the liquid crystal is phase-separated together with the film formation in the process of converting from a photopolymerizable monomer to a matrix polymer (resin) typified by the UV curing method, the Even if the alignment control power cannot be sufficiently exerted and the irradiation conditions are optimized by UV curing, in the light scattering state at the end of curing, the UV curing energy is sufficient energy required for conversion from monomer to polymer. Due to the fact that low-molecular weight photopolymerizable monomers and oligomers of the polymerized uncured component remain untransmitted, display characteristics due to repetition of an external stimulus such as electric field and heat of the liquid crystal composite display element, that is, in the rise and fall of the voltage There is a problem that hysteresis of light transmittance-applied voltage (heat) is large and satisfactory performance cannot be obtained. . In the case of applying the composite film to a display device,
It is particularly desired to suppress the occurrence of the hysteresis phenomenon because it causes gradation display defects and image sticking.

On the other hand, in a liquid crystal display device manufactured by a solvent casting method, when a display device having a light modulation function is manufactured, a matrix polymer is previously polymerized. Since there is no possibility that low-molecular-weight monomers and oligomers may be mixed, the display characteristics are considered to be less susceptible to the above-mentioned methods. In addition, the phase separation state of the matrix polymer in the composite film becomes stable, and the display characteristics (light transmittance during voltage rise / fall-hysteresis characteristics of applied voltage) due to repetition of an external stimulus such as electric field and heat of the liquid crystal display element are stabilized. It is considered to be suitable for the display quality (resolution) of a uniform liquid crystal display element because of its performance. However, as a characteristic of the liquid crystal composite display element, there is a trade-off between the reduction of the drive voltage and the reduction of the hysteresis of the transmittance-applied voltage when the voltage rises and falls, and these properties are still sufficiently satisfied in the solvent casting method. I haven't done anything.

As an improvement thereof, Japanese Patent Application Laid-Open No. 9-2183
In Japanese Patent Publication No. 98, a matrix polymer is changed from a water-soluble polymer to a water-insoluble polymer, and recording is performed using a water-insoluble polymer having a specific structural skeleton as a component particularly among the water-insoluble polymers. A polymer material for a polymer / liquid crystal composite film for a display medium is disclosed. That is, in order to improve the conventional problems caused by the method (a), a water-insoluble polymer is used as a matrix polymer, and among them, heat resistance (glass transition temperature Tg or decomposition temperature) is high, and In a liquid crystal composite display device using a symmetrical fumaric acid diester having a symmetric side-chain ester group having excellent phase separation properties with liquid crystal as a constituent component, like an imide-based material having excellent heat resistance, a polymer and a liquid crystal are used. Since a clear interface is formed at the boundary, the phase separation structure is stabilized, and as a result, the display thermal stability over time is improved. On the other hand, at the interface between the polymer and the liquid crystal, the interaction between the polymer and the liquid crystal is relatively strong, and therefore, a liquid crystal using a smectic liquid crystal having a memory property that does not cause display loss at high temperature or high humidity. The composite display element has been disclosed as a recording display element having high display stability, excellent thermal stability over time, and excellent reliability and stability.

However, since a polymer having high phase separation characteristics from liquid crystal and high thermal stability is used as the polymer material used for the above-mentioned liquid crystal composite display element, the light transmittance-temperature hysteresis characteristic with a change in temperature is used. Although it was improved in, the phase separation structure was clarified, and at the interface between the polymer and the liquid crystal, the action of regulating the orientation of the polymer with respect to the liquid crystal (anchoring force) worked strongly, and 50 V or more was required to obtain sufficient transparency. However, there is a problem that a low driving voltage characteristic which is important in practical use of a display device is not provided. Considering the application of the liquid crystal composite display device to an active matrix drive type flat panel display, the liquid crystal composite display device manufactured by this solvent casting method has a withstand voltage of an LSI circuit used for a drive (driver) circuit. Therefore, there is a problem that practical application becomes considerably difficult.

As described above, a non-aqueous polymer / liquid crystal composite film formed by a phase separation method by evaporating a solvent using a water-insoluble polymer that does not cause compatibilization at the interface between the polymer and the liquid crystal. in becomes liquid crystal composite display device, as compared with the general liquid crystal composite display device of the external drive voltages required (V _0.9 Δ _T) is as high as 50 (V) above, together with their characteristics, the light in the lifting of the voltage There is a problem of display characteristics that the hysteresis characteristic value H of the transmittance-applied voltage is large, and a drive circuit such as a general-purpose inexpensive time-division drive cannot be used. It had been. Therefore, in the conventional liquid crystal composite display device, balanced and satisfactory display characteristics such as low-voltage drivability and hysteresis characteristics of light transmittance-applied voltage at rising and falling of voltage have not been obtained.

[0015]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a liquid crystal composite display device comprising a water-insoluble polymer / liquid crystal composite film formed by a conventional phase separation method as described above. voltage (electric field) of _{(E 0.9 Δ T = V 0.9} Δ T /
d) It is still another object of the present invention to provide a liquid crystal composite display element having a liquid crystal display characteristic in which the reduction of the hysteresis characteristic value H of transmittance-voltage at the time of voltage rise and fall is balanced.
A second object of the present invention is to provide a method for manufacturing the liquid crystal composite display device.

[0016]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the problems of the prior art, and as a result, have found that a specific water-insoluble polymer constituting a water-insoluble polymer / liquid crystal composite film has a specific property. By selecting a polymer containing an asymmetric fumaric acid diester having a structure as a component, the phase separation at the interface between the polymer and the liquid crystal is sharpened, the polymer is formed without causing compatibilization, and the polymer is used for the liquid crystal. The present invention was completed based on the finding that by reducing the alignment regulating action (anchoring force), the driving electric field can be reduced, and the reduction of the transmittance-voltage hysteresis characteristic value H during voltage rise / fall can be improved in a well-balanced manner. It led to. That is, the present invention is as follows (1) to (9).

(1) A water-insoluble polymer / liquid crystal composite film composed of a water-insoluble polymer and a nematic liquid crystal, and at least one of two sheets having conductive portions opposed to each other with both sides sandwiching the film. a liquid crystal composite display device having an optical modulation function consisting of a conductive substrate having a transparency, of its liquid crystal display characteristics, the external driving electric field E _0.9 delta _T (external driving voltage V _{0.
9 Δ T} / d) is 0.15~4.5AC (V / μm), the hysteresis characteristic value H 0.0~0.35AC (V
/ Μm).

(2) The water-insoluble polymer contains at least 10% by weight to 1% by weight of an asymmetric fumaric acid diester as a constituent component.
The liquid crystal composite display device described above, which is a polymer containing 00% by weight.

(3) A polymer containing an asymmetric fumaric acid diester of a water-insoluble polymer as a constituent is represented by the following general formula (1):

[0020]

Embedded image

(Wherein, R ¹ represents a branched alkyl group having 3 to 12 carbon atoms or a cycloalkyl group having 3 to 14 carbon atoms; R ² represents an alkyl group having 1 to 14 carbon atoms; A cycloalkyl group having 3 to 14 carbon atoms, 7 to 20 carbon atoms
R ¹ ≠ R ² , which may have a hetero atom and / or a substituent, and represents a different hydrocarbon group. A) a polymer having a repeating unit of an asymmetric fumaric acid diester represented by the formula (1), having a weight average molecular weight of 20,000:
The liquid crystal composite display device described above, wherein the number is from 1,500,000.

(4) The polymer containing an asymmetric fumaric acid diester as a component is a copolymer obtained by polymerizing an asymmetric fumaric acid diester and didiisopropyl fumarate or disec-butyl fumarate, The above liquid crystal composite display device having a molecular weight of 20,000 to 1,500,000.

(5) A polymer comprising an asymmetric fumaric acid diester as a constituent component is obtained by polymerizing an asymmetric fumaric acid diester having a hydroxyalkyl group or a cyanoalkyl group with diisopropyl fumarate or disec-butyl fumarate. The above liquid crystal composite display element, which is a copolymer and has a weight average molecular weight of 20,000 to 500,000.

(6) The polymer containing the asymmetric fumaric diester as a component is a copolymer obtained by polymerizing an asymmetric fumaric diester and a vinyl monomer, and has a weight average molecular weight of 20,000 to 1 , 500,000.

(7) The liquid crystal composite display device described above, wherein the weight ratio of the water-insoluble polymer to the nematic liquid crystal in the composite film is 40/60 to 5/95.

(8) The above-mentioned liquid crystal composite display device comprising a nematic liquid crystal containing a halogen atom.

(9) A conductive base material is prepared by using a coating solution obtained by dissolving a nematic liquid crystal and a water-insoluble polymer in a non-water-soluble solvent which is a good solvent common to the nematic liquid crystal and the water-insoluble polymer. Is applied to one surface, and the water-insoluble solvent is evaporated to solidify the water-insoluble polymer to form a matrix polymer and the liquid crystal and the water-insoluble polymer in the matrix polymer. , And further comprising a step of sandwiching one of the conductive substrates.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The liquid crystal composite display device of the present invention is:
A water-insoluble polymer is used as a matrix polymer, and a water-insoluble polymer / liquid crystal composite film is disposed on both sides such that conductive portions are opposed to each other. And a liquid crystal composite display element comprising: That is, it has a sandwich structure sandwiched between conductive base materials so that the contacting sides of both surfaces of the liquid crystal composite film having a light modulation function become conductive parts.

The conductive substrate used in the present invention may be any material that imparts sufficient conductivity to apply a vertical electric field to the water-insoluble polymer / liquid crystal composite film. For example, as a conductive base material, conductive inorganic oxides such as ITO (Indium Tin Oxide: indium tin oxide), copper (C
u), silver (Ag), gold (Au) and aluminum (A
1). Conductive metals such as l); and metals such as conductive organics such as carbon black and organic conductors are deposited on one surface. In addition, a metal conductor such as ITO and aluminum can be obtained as a metal-deposited conductive substrate by a vacuum deposition method or the like on a resin substrate such as polyethylene terephthalate (PET) or a glass substrate having scratch resistance, These can be used more preferably. The conductive substrate having a conductor on the surface,
According to the film thickness, a conductive film, a conductive film, a conductive substrate, or the like can be used. Alternatively, the conductive portion of the conductive substrate may be a conductive-containing layer by dispersing a conductive powder such as carbon black in a resin. The conductive substrate can be formed by a method such as vacuum deposition, sputtering, CVD, ion plating, coating, plating, immersion, and electrolytic polymerization.

Depending on the specifications of the display element, the conductive substrate may be transparent or opaque, depending on how information is read by transmitted light or reflected light. The liquid crystal composite display element can have a shape of a card, a film, or the like, but the conductive base material also plays a role of a support in order to strongly support the liquid crystal composite display element. The material and thickness of the support are not particularly limited, but, for example, when flexibility is required, a plastic film, a sheet,
When a card or the like is used and strength is required, a plastic sheet, a glass substrate, or the like is used. When reading the information displayed on the water-insoluble polymer / liquid crystal composite film with transmitted light, it is preferable to use a pair of transparent conductive base materials so as to transmit light. Further, a combination of a conductive base material having no light transmittance and a transparent conductive base material having light transmittance may be used. In this case, the conductive substrate preferably has a light transmittance of at least 75% or more.

When information displayed on the water-insoluble polymer / liquid crystal composite film is read by reflected light, one of the conductive base materials may be made light-reflective. To make the conductive substrate light-reflective, for example, a metal conductive film such as aluminum,
Alternatively, it can be a substrate, and a white I
An impervious ITO vapor-deposited substrate such as a TO vapor-deposited PET or an ITO vapor-impermeable non-transparent (cloudy) glass substrate having no light transmittance can also be used. In this case, a conductive substrate having a light transmittance of 10% or less can be preferably used.

The water-insoluble polymer / liquid crystal composite film of the present invention comprises:
It exerts an optical modulation function by applying an electric field. In addition, the water-insoluble polymer acts to fix the liquid crystal domain shape when phase-separated from the liquid crystal, and the matrix polymer, which is a constituent material of the composite film, is a water-insoluble polymer, It is a water-insoluble polymer that does not affect display characteristics.

The water-insoluble polymer used as the matrix polymer, which is a constituent material of the liquid crystal composite display device of the present invention, is not compatible with the liquid crystal. The liquid crystal composite display element has a low driving electric field (voltage) property with a good phase separation property, and reduces the alignment regulating force (anchoring force) of the liquid crystal especially when an electric field is applied. In addition, it contributes to the reduction of the hysteresis characteristic value H of the transmittance-applied voltage when the voltage rises and falls.

The liquid crystal composite display device of the present invention, among the liquid crystal display characteristics, the external driving electric field E _0.9 delta _T (external driving voltage V _0.9
Delta _T / d) is 0.15~4.5AC (V / μm), the hysteresis characteristic value H 0.0~0.35AC (V
/ Μm). (Note, _0.9 delta _T represents all subscripts.) Where an external driving electric field E ₀₉ △ _T is a liquid crystal composite display element 2
Maximum transmittance of the liquid crystal composite display device when the above voltage boosting drive Vrms / sec relative to (△ T), water-insoluble polymer / liquid crystal composite film external driving voltage V ₀₉ △ _T indicating 90% transmission the thickness d ([mu] m) with a value obtained by dividing E ₀₉ △ _T (external driving voltage) and V _0.9 Δ _T / d, the value 0.15~4.5A
C (V / μm). In addition, the hysteresis characteristic value (H) is obtained by driving the liquid crystal composite display element to step up / down at 2 Vrms / sec or more, and changing the total transmittance of the liquid crystal display element (△
T) Hysteresis rise / fall voltage width ΔV when 50% changes
_0.5 △ hysteresis value obtained by dividing the film thickness d ([mu] m) of the composite film _T becomes intermediate indication index characteristics _{H (H = △ V 0.5 △} T
/ D), and the hysteresis characteristic H is 0.0 to 0.0.
35 AC (V / μm).

The polymer containing an asymmetric fumaric diester as a constituent in the present invention is obtained by polymerizing a polymer of an asymmetric fumaric diester or a monomer composition containing the same. It is a polymer having a structural unit based on an asymmetric fumaric diester of 10% by weight or more. A fumaric acid diester polymer containing the asymmetric fumaric diester represented by the general formula (1) as a constituent unit is preferably used, and the repeating unit of the asymmetric fumaric diester in the water-insoluble polymer is 10% by weight. The content is more preferably at least 25% by weight, further preferably at least 50% by weight. When the amount of the asymmetric fumaric acid diester contained as a repeating unit in the water-insoluble polymer is less than 10% by weight, the driving electric field necessary for driving the liquid crystal display element increases, and the balance with the reduction of the hysteresis characteristic value is obtained. It is not preferable because it cannot be removed.

Further, by containing the asymmetric fumaric acid diester which is a repeating unit to give a polymer obtained by polymerizing the asymmetric fumaric acid diester, the water-insoluble polymer / liquid crystal composite film and the conductive group Good adhesion to the material.

More specifically, the asymmetric fumaric acid diester polymer has two different side chain ester groups (R ¹ ≠).
R ² ) A polymer containing an asymmetric fumaric diester as a constituent, and is a fumaric diester polymer having a repeating unit derived from the asymmetric fumaric diester. The polymer containing the asymmetric fumaric acid diester as a constituent component has a different ester group in the side chain, whereby the symmetry is broken, the thermal molecular mobility of the polymer main chain is increased, and the heat resistance is slightly reduced. , Which weakens the interaction of the polymer's alignment regulating force (anchoring force) with the liquid crystal, which contributes to a lower driving electric field, and maintains a clear and stable phase separation structure at the interface between the polymer and the liquid crystal. It is possible to maintain a good light transmittance-hysteresis characteristic of an applied voltage and to lower the driving electric field. A polymer containing an asymmetric fumaric acid ester having a side chain ester group represented by the general formula (1) in which R ¹ ≠ R ² is a symmetrical fumarate in which the side chain ester group is R ¹ = R ^2. It is an effective material for effectively reducing the alignment regulating force as compared with a polymer containing an acid ester as a component.

Here, in the general formula (1), R ¹ represents a branched alkyl group or a cycloalkyl group, R ² represents a linear or branched alkyl group, a cycloalkyl group or an aryl group, and R ¹ and R ² represent Must be different. The branched alkyl group represented by R ¹ has 3 carbon atoms.
To 12 and may further have a hetero atom and / or a substituent. The cycloalkyl group preferably has 3 to 14 carbon atoms, may be a single ring, or may have a bridged ring.
It may have a substituent containing a hetero atom. When R ¹ has a substituent, a substituent containing a hetero atom, that is, a halogen atom (F, Cl), sulfur (S), nitrogen atom (N), silicon atom (Si), alkoxy group (methoxy group) Ethoxy group, propoxy group, butoxy group, etc.), cyano (CN) group, hydroxy (OH) group and the like.

Specific examples of the branched alkyl group represented by R ¹ include isopropyl group (iP), sec-butyl group (sB), t-butyl group (tB), sec-amyl group (sA), isopentyl group , A neopentyl group, a t-pentyl group, a sec-hexyl group, a 4-methyl-2-pentyl group, a sec-heptyl group, and a sec-octyl group. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group (cH), an adamantyl group, and a dimethyladamantyl group. Specific examples of the branched alkyl group containing a hetero atom include a hexafluoroisopropyl group, a perfluoroisopropyl group,
-Butoxy-2-propyl group, methoxyethyl group, 4-
Examples thereof include a cyanocyclohexyl group and a 4-hydroxycyclohexyl group.

Examples of the alkyl group represented by R ² include a linear or branched alkyl group having 1 to 14 carbon atoms.
Further, it may have a hetero atom and / or a substituent. The cycloalkyl group represented by R ² preferably has 3 to 14 carbon atoms, may be a single ring or may have a bridged ring, and may further have a hetero atom and / or It may have a substituent. The branched alkyl group and the cycloalkyl group represented by R ² may have a hetero atom and / or a substituent as in the case of R ¹ , but when an asymmetric fumaric acid diester is synthesized, R ¹ ≠ R ² . The aryl group represented by R ² preferably has 7 to 20 carbon atoms,
Although a single ring is preferred, it may be a polycyclic or fused ring,
It may have a hetero atom and / or a substituent. R
Examples of the substituent having ² substituents include a substituent containing a hetero atom, a halogen atom (F, Cl), a sulfur (S), a nitrogen atom (N), a phosphorus (P), a silicon atom (Si), and an alkoxy group. (Methoxy, ethoxy, propoxy, butoxy, etc.), cyanoalkyl (cyano, cyanoethyl, cyanobutyl), hydroxyalkyl ｛hydroxy, hydroxyethyl, hydroxyethylthioethyl (HO—CH ₂₎ CH ₂ —S—CH ₂ CH ₂ —), a hydroxybutyl group｝, and a silicon (Si) -containing group (eg, a trimethylsilyl group, a trimethylsiloxypropyl group, etc.).

Examples of the alkyl group of R ² include a methyl group (Me), an ethyl group (Et), and an n-propyl group (hereinafter referred to as n-propyl group).
-Is omitted), butyl group, amyl group (pentyl group),
Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like. R ²
Specific examples of the branched alkyl group is similar to the R ^1, an isopropyl group (iP), sec-butyl group (sB), t-
Butyl group (tB), sec-amyl group (sA), isopentyl group, neopentyl group, t-pentyl group, sec-
A hexyl group, a 4-methyl-2-pentyl group, a sec-heptyl group, and a sec-octyl group. Further, specific examples of the cycloalkyl group include a cyclopentyl group,
Examples include a cyclohexyl group (cH), an adamantyl group, and a dimethyladamantyl group. Specific examples of the aryl group, phenyl group (-.phi), benzyl group (-CH ₂ -
φ), 1-phenyl-1-ethyl group (—CH (φ) -C
H ₃ ), a 3-phenylpropyl group {—CH ₂ CH ₂ CH ₂ —
φ｝, 1-phenyl-2-propyl group [｛-CH (CH
₃ ) —CH ₂ —φ｝ = 1Ph2P], 1-phenyl-1-
Propyl group [{-CH (φ) -CH ₂ CH ₃ } = (1Ph
1P)]. Further, specific examples of a linear alkyl group, a branched alkyl group, a cycloalkyl group, and an aryl group in which R ² has a hetero atom and / or a substituent include a trifluoromethyl group, a trifluoromethylethyl group, and a hexafluoroisopropyl group. , Perfluoroisopropyl group, perfluorobutylethyl group, perfluorooctylethyl group, 2-chloroethyl group, 1-butoxy-2-propyl group, methoxyethyl group, trimethylsiloxypropyl group, 2-cyanoethyl group, 2-hydroxyethyl Group, 4-hydroxybutyl group and the like.

R ¹ is particularly preferred and includes isopropyl, sec-butyl, t-butyl, cyclopentyl and cyclohexyl. As R ² ,
Preferable examples include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, and an aryl group. As the aryl group, a 1-phenyl-2-ethyl group, 1-phenyl-2-
A propyl group is preferable. In R ² , a trifluoromethyl group, a trimethylsilyl group, a cyano group, or a hydroxy group further having a hetero atom and / or a substituent in the above-mentioned alkyl group, cycloalkyl group, and aryl group is preferred. What contains is more preferably used.

As specific examples of the asymmetric fumaric acid diester, isopropyl methyl fumarate (indicated by using the symbol = to clarify the distinction between R ¹ and R ^2; the same applies hereinafter) Isopropyl fumarate ethyl, fumarate Isopropyl propylate, isopropyl fumarate = butyl, isopropyl fumarate = sec-butyl, isopropyl fumarate = t-butyl, isopropyl fumarate = isoamyl, isopropyl fumarate = sec-amyl, isopropyl fumarate = sec-hexyl, fumarate Isopropyl acid = 4
-Methyl-2-pentyl, isopropyl fumarate = 2-
Ethylhexyl, isopropyl fumarate = octyl, isopropyl fumarate = cyclohexyl, isopropyl fumarate = nonyl, t-butyl fumarate = sec-butyl, t-butyl fumarate = cyclohexyl, tfumarate
And asymmetric fumaric acid diesters containing an alkyl group such as -butyl = 4-methyl-2-pentyl, t-butyl fumarate = 2-ethylhexyl, isopropyl fumarate = cyclohexyl, and isopropyl fumarate = cyclopentyl. Also, isopropyl fumarate = 2-phenyl-1
And aryl group-containing asymmetric fumaric acid diesters such as -ethyl, isopropyl fumarate = 3-phenylpropyl, isopropyl fumarate = 1-phenyl-2-propyl, and isopropyl fumarate = 1-phenyl-1-propyl. Further, isopropyl fumarate = (trimethylsilyl) propyl, t-butyl fumarate = (trimethylsilyl) propyl, cyclohexyl fumarate = (trimethylsilyl) propyl, isopropyl fumarate = (3-
And asymmetric fumaric acid diesters containing silicon atoms such as tris (trimethylsiloxy) silyl) propyl and isopropyl fumarate = 3-((pentamethyl) disiloxanyl) propyl. Further, N, N-dimethylaminoethyl fumarate = isopropyl, t-butyl fumarate =
1-butoxy-2-propyl, 2-cyanoethyl fumarate = isopropyl, 2-hydroxyethyl fumarate = isopropyl, glycidyl fumarate = isopropyl, isopropyl fumarate = diethylphosphomethyl, 2-methylthioethyl fumarate = isopropyl, fumarate Heteroatom-containing fumaric acid diesters such as isopropyl acid = 2-hydroxyethylthioethyl = isopropyl. Further, there may be mentioned halogen atom-containing fumaric acid diesters such as perfluorooctylethyl fumarate = isopropyl, trifluoromethyl fumarate = isopropyl, pentafluoroethyl fumarate = isopropyl and fumarate hexafluoroisopropyl = isopropyl.

Among the above-mentioned asymmetric fumaric acid diesters, isopropyl fumarate = ethyl, isopropyl fumarate = butyl, isopropyl fumarate = butyl, isopropyl fumarate = amyl, isopropyl fumarate = se
Preferred examples include c-butyl, isopropyl fumarate = t-butyl, isopropyl fumarate = cyclohexyl, isopropyl fumarate = cyclopentyl, isopropyl fumarate = 1-phenyl-2-propyl (1Ph2PiPF), and isopropyl fumarate = perfluoroisopropyl. Can be Among them, isopropyl fumarate = 2-hydroxyethyl and isopropyl fumarate = 2-cyanoethyl are particularly preferable from the viewpoint of performance.

In obtaining a polymer containing an asymmetric fumaric acid diester as a component, the asymmetric fumaric acid diester may be used alone or as a combination of two or more asymmetric fumaric acid diester monomers. Is also good. The bonding mode of the asymmetric fumaric acid diester polymer of the present invention may be any bonding mode such as a random copolymer, an alternating copolymer, a block copolymer, and a graft polymer.

As described above, the water-insoluble polymer used in the present invention may be a polymer using only an asymmetric fumaric acid diester monomer component, or a polymer other than the asymmetric fumaric acid diester. May be copolymerized with the above monomer. As a copolymerization component other than the asymmetric fumaric acid diester component, a symmetrical fumaric acid diester (R ¹ = R ² ) is preferred because it has the best copolymerizability. A water-insoluble polymer containing only a symmetrical fumaric acid diester component does not contribute to lowering the driving voltage of a liquid crystal composite display device, but it is copolymerized to provide phase separation from the liquid crystal and low hysteresis characteristics when the voltage rises and falls. Preferred examples of the component include:

The symmetric fumaric acid diester includes:
Diethyl fumarate, diisopropyl fumarate (iPiP
F), dibutyl fumarate (BuBuF), dicyclohexyl fumarate (cHcHF), di-1-phenyl-2-propyl fumarate, disec-butyl fumarate, di-t-butyl fumarate, di-2-ethylhexyl fumarate and the like. No. Among them, diisopropyl fumarate and disec-butyl fumarate are particularly desirable.
As long as the effects of the present invention are not impaired, the symmetrical fumaric acid diester can be used even if only one type is used as a copolymer component.
More than one species may be used in combination.

Other monomer components copolymerizable with the asymmetric fumaric diester other than the symmetric fumaric diester include vinyl monomers. As the vinyl monomer, a copolymer obtained by polymerizing an asymmetric fumaric acid diester and a vinyl monomer has a phase separation property from liquid crystal, a film forming property when compounded with liquid crystal, and a mechanical property. Any material can be used as long as it can impart strength, and is not particularly limited as long as it can be copolymerized with the asymmetric fumaric acid diester. Specifically, the following vinyl monomers can be preferably exemplified.

The vinyl monomer is a vinyl comonomer mainly composed of an olefinic hydrocarbon, for example, vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, 2,2-dimethylpentane. Vinyl carboxylate such as vinyl acrylate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutanoate; vinyl acetamide such as N-vinyl acetamide; p-tert-butyl Aromatic vinyl monomers such as vinyl benzoate, N, N-dimethylamino vinyl benzoate and vinyl benzoate; styrene, o-, m-, p-chloromethylstyrene, α-methylstyrene and their nuclear substitution Α-substituted styrene derivatives such as isomers; o-olefins such as vinyl chloride and vinyl fluoride; p-chlorostyrene O-, m-, and p-halogenated styrenes such as styrene; halogen-nucleus-substituted styrenes; ethyl vinyl ether, hydroxybutyl monovinyl ether, t
vinyl ethers such as ert-amyl vinyl ether and cyclohexane dimethanol methyl vinyl ether: α,
naphthalene derivatives such as β-vinylnaphthalene; alkyl vinyl ketones such as methyl vinyl ketone and isobutyl vinyl ketone; dienes such as butadiene and isoprene; methyl (meth) acrylate, ethyl (meth) acrylate;
(Meth) acrylates such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and phenyl (meth) acrylate; dimethyl itaconate;
Known copolymerization components such as itaconate such as diethyl itaconate, dibutyl itaconate and diisopropyl itaconate can be preferably exemplified. Further, in order to improve the phase separation from the liquid crystal, a fluorine-containing monomer may be blended as a vinyl monomer. One of the above-mentioned vinyl monomers may be used alone, or two or more thereof may be used in combination. The bonding mode of the polymer of these asymmetric fumaric diesters and vinyl monomers may be any bonding mode such as a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. There may be.

In order to produce a liquid crystal composite display element comprising a water-insoluble polymer / liquid crystal composite film and a conductive base material having conductive portions disposed on both sides of the composite film, one conductive material is used. Since a step of sandwiching the base material is required, the water-insoluble polymer / liquid crystal composite film composed of the water-insoluble polymer and the liquid crystal needs uniform mechanical properties and further mechanical strength. Therefore, the polymer of the asymmetric fumaric acid diester or the polymer containing the asymmetric fumaric acid diester in the composite film is desirably of high molecular weight, and has a weight average molecular weight of 20,000.
0 to 1,500,000, more preferably 30,00
0 to 1,000,000. If the molecular weight of the polymer is less than 20,000, the mechanical strength and the chemical stability tend to be inferior and the heat resistance also deteriorates, such being undesirable. The above range is particularly preferable from the viewpoints of film formability, adhesion of the film to the conductive substrate, and defects of the film. Also,
When the molecular weight of the polymer is smaller than 20,000 or larger than 1,500,000, it becomes difficult to form a uniform and smooth water-insoluble polymer / liquid crystal composite film, and the workability is reduced. It is not preferable because it is inferior and also has poor processability.

The matrix polymer used for the water-insoluble polymer / liquid crystal composite film is a polymer obtained by polymerizing the above-mentioned monomer composition containing an asymmetric fumaric acid diester. Other polymers as shown in the following may be blended and used as long as the performance of the present invention is not impaired. Examples of the other polymers include vinyl chloride resins, styrene resins, and methacrylate resins. Acrylate-based resin, methacrylate-acrylate-based copolymer (resin), itaconate-based resin, polycarbonate-based resin, polyester-based resin, epoxy-based resin, polyamide-based resin, and polythiol-based resin. As the matrix polymer used for the liquid crystal composite display element,
One or more of the other polymers may be blended.

The method for producing the above-mentioned polymer is not particularly limited, and it can be produced by a known method. For example, the above-mentioned fumaric acid diester monomer and, if necessary, another monomer component are mixed with each other in the presence of a radical polymerization initiator.
It is obtained by polymerizing at about 150 ° C. for about 1 to 100 hours. Examples of the polymerization initiator include benzoyl peroxide, diisopropyl peroxydicarbonate, t
-Butylperoxy-2-ethylhexanoate, t-
Butylperoxypivalate, t-butylperoxydiisobutyrate, lauroyl peroxide, dimethyl 2,2′-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN) and the like.

When forming the water-insoluble polymer / liquid crystal composite film, the water-insoluble polymer of the present invention and the liquid crystal are uniformly dissolved in a water-insoluble solvent, and then the solvent is evaporated. It can be obtained as a uniform polymer / liquid crystal composite film having a film forming ability with a film thickness of 1 μm or more. When the polymer and the liquid crystal are used as solutes, the concentration of the solution is preferably 4 to 20% by weight, and the viscosity at evaporation is 50 to 1%.
Approximately 000 cps (centipoise) is preferable because the coating can be easily controlled.

Mixing ratio of water-insoluble polymer / liquid crystal (weight ratio)
Is preferably 40/60 to 5/95 (weight / weight), and more preferably, the mixing ratio is 30/70 to 50/95.
It is 10/90. When the mixing ratio of the liquid crystal is less than 40/60, not only the transparency at the time of turning on the voltage is insufficient, but also a large driving voltage is required to make the film transparent, and the practicality is lost. When the mixing ratio (weight ratio) is larger than 5/95, the amount of the liquid crystal used is not sufficient.
It is not preferable because the mechanical strength of the film is reduced. The thickness of the composite film is not particularly limited, but the thickness of the obtained composite film is preferably about 4 to 15 μm from the viewpoint of functions and effects.

The method of forming a water-insoluble polymer / liquid crystal composite film from the solvent solution of (water-insoluble polymer / liquid crystal) obtained as described above includes spin coating, screen coating, wire bar coating, Methods such as blade coating, spray coating, knife coating, screen coating, doctor coating, roll coating, gravure coating, and electrodeposition coating can be used. Further, the film can be formed to have a uniform film thickness by a known coating and drying means.

The water-insoluble solvent used for forming the water-insoluble polymer / liquid crystal composite film dissolves the water-insoluble polymer and has good film-forming properties when formed into a composite film. It is preferable that the liquid crystal and the liquid crystal are uniformly separated in a sea-island state. Specific examples of water-insoluble solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ester solvents such as butyl cellosolve acetate, methyl cellosolve acetate, ethyl acetate, and butyl acetate; and tetrahydrofuran (THF); Decalin, butyl chloride,
Solvents such as trichlorotrifluoroethane and trifluorotoluene can be mentioned. These solvents may be used alone or in combination of several kinds.

The liquid crystal used for the composite film in the present invention may be a nematic liquid crystal or a mixture of nematic liquid crystals that exhibits a liquid crystal state at around normal temperature. Since the use of a water-insoluble polymer provides good phase separation from liquid crystal, any conventionally known nematic liquid crystal can be used.
When selecting a liquid crystal, a liquid crystal having a large refractive index anisotropy (Δn) is more desirable in terms of contrast.

Nematic liquid crystals preferably used in the present invention include, for example, azo, azoxy, Schiff base, phenyl benzoate, phenyl cyclohexylate, phenylpyridine, phenyloxazine, biphenyl, and terphenyl. Known nematic liquid crystals such as phenyl-based and phenylcyclohexane-based liquid crystals can be used. Specifically, for example, EDH manufactured by BDH
44, E-63, E-7, E-8, ZLI-2061,
ZLI-3926, ZLI-1132, ZLI-178
0, ZLI-2183, RN001 manufactured by Roddick,
LV-R2, RDP80616, RDP10248, P
A commercially available mixed liquid crystal that is nematic in a room temperature region, such as DN00775 and RD007775, and a mixture of a plurality of commercially available liquid crystal materials are suitably used.

When a display element is combined with an active element, it is necessary to use a highly reliable liquid crystal skeleton. In the case of a commercial product, for example, TL20 manufactured by Merck & Co. is used.
2, TL204, TL205, TL212, TL21
3. It is more desirable to use a halogen-based biphenyl liquid crystal represented by TL215 or the like. A dye can be included in the liquid crystal to improve contrast or color tone. When a dichroic dye is added, it can be used not only as a composite film of a scattering-transmission type but also as a composite film that switches between light absorption (coloring) and a transparent state due to the guest-host effect of the dye. .

In a field in which a display quality, a high response speed, a low driving voltage, and a low hysteresis are required as a liquid crystal composite display element, a water-insoluble polymer / liquid crystal composite film using a nematic liquid crystal is sandwiched. A liquid crystal composite display element, which is a pair of light-transmitting conductive substrates, is preferably used as a conductive substrate on which electrodes are arranged so as to face each other.

[0061]

The present inventors have found that the hysteresis characteristic of the light transmittance-applied voltage when the driving electric field and the voltage applied to the liquid crystal composite display device using a water-insoluble polymer rises and falls is that of the matrix polymer and the liquid crystal. It was found that it depends on the state of the interface and strongly depends on the type of matrix polymer that determines the alignment regulating force (anchoring force) for the liquid crystal. Furthermore, the present inventors changed the type and amount of the matrix polymer and the liquid crystal for the purpose of changing the state of the interface, and determined the driving electric field (voltage) of the liquid crystal composite display element and the hysteresis of the light transmittance-applied voltage when the voltage was increased and decreased. It has been found that the characteristic value H is also reduced.

The matrix polymer is a water-insoluble polymer which has no compatibility with liquid crystal and is excellent in transparency and film-forming ability even when a film is formed using only the matrix polymer. Particularly preferably, a polymer obtained by polymerization of an asymmetric fumaric diester has a lower glass transition temperature than a polymer obtained by polymerization of a symmetric fumaric diester. Since the compound is easily dissolved in a basic solvent, a uniform solution can be prepared, and a uniform solution of liquid crystal and a water-insoluble polymer can be prepared. Even when a nematic liquid crystal is present in the water-insoluble polymer, the water-insoluble polymer is immiscible with the liquid crystal and hardly stained by a dichroic dye, so that a high contrast is obtained when a liquid crystal composite display device is used. can get.

[0063]

According to the present invention, by using a specific polymer material as the matrix polymer of the water-insoluble polymer / liquid crystal composite layer, phase separation without compatibilization with the liquid crystal at the interface is realized. In addition, the electro-optical characteristics of the water-insoluble polymer / liquid crystal composite film have both a low driving electric field and a low hysteresis between the transmittance and the applied voltage when the voltage rises and falls, enabling low voltage driving even in the phase separation method. In addition, it is possible to provide a liquid crystal composite display device capable of improving a high driving voltage characteristic and a hysteresis characteristic of a display device manufactured using a casting solvent which has not been realized although the possibility has been discussed. Further, by using a polymer obtained by polymerizing the asymmetric fumaric acid diester, the adhesion between the water-insoluble polymer / liquid crystal composite film and the conductive substrate is improved as a secondary effect. Therefore, a liquid crystal composite display element having excellent adhesion between the conductive base material and the polymer / liquid crystal composite film can be manufactured, and a light modulation element, a display (display) device, a reflective display, A liquid crystal composite display element suitable for an optical element can be provided. Further, the manufacturing method of the present invention is a method that can easily manufacture the above-mentioned liquid crystal composite display element.

[0064]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to specific examples. Next, the measuring method used was shown. 1. <Measurement method of display characteristics> 1-1 Measurement conditions; light modulation characteristics (light transmittance-dependence of applied voltage) of the liquid crystal composite display element in a direction perpendicular to the manufactured liquid crystal composite display element and light transmission with rise and fall of voltage The rate of hysteresis was evaluated. The measurement was performed using a He-Ne laser (λ =
632.8 nm) as a light source, and a change in transmitted light intensity with respect to a change in applied electric field was detected by a photodiode. The evaluation was performed with a distance from the display element to the photodiode of 305 mm and a light spot diameter of 2 mm. For this measurement, two function generators were used. A function generator 1 generates a triangular Fm-modulated wave, and a function generator 2 oscillates with a 1 kHz Fc carrier to obtain an AM (Amplitude Mo) as shown in FIG.
Using a waveform, data was taken into a personal computer and evaluated. FIG. 2 shows the change over time in the light transmittance of the composite film corresponding to the application and removal of the voltage. FIG.
Is a hysteresis curve of the light transmittance in the rise and fall of the voltage used in this measurement. Modulation frequency (Fm) is 1H
z, a rectangular wave having a carrier (Fc) frequency of 1 kHz is used, and the driving voltage (applied voltage) is set to 100 AC (Vr).
ms) (effective AC voltage). That is, according to this hysteresis curve, the modulation frequency (Fm) is the reciprocal of the time required to increase the applied voltage from 0 V to 100 V and further reduce it to 0 V. Therefore, the rising / falling speed of the external drive voltage is 2Fm × Vrms (V / sec).
c) Since Fm is 1 Hz, the round trip time is
1.0 sec, and the display element is set to 200 Vrms / sec.
The pressure is raised and lowered at c.

1-2. Where <outside the calculation method of driving electric field E _0.9 delta _T>, the external driving electric field E _0.9 delta _T of the display characteristics, the transmittance change of the element when the boost driving the display device in 200 Vrms / sec to ([Delta] T) V showing 90% transmittance
_0.9 ΔT is _converted to the thickness d (μm) of the water-insoluble polymer / liquid crystal composite film.
The value obtained by dividing m) external driving electric field _{(E 0.9 Δ T = V 0.9} Δ T /
d). The evaluation of the calculated low-driving electric field E _0.9 delta _T was as follows. Numerical range of evaluation content (external driving electric field E _0.9 delta _T; Evaluation Code
Circumference) ◎; ~3.0 ○; 3.1~4.5 △ ; 4.6~6.0 ×; 6.1~

1-3. Was pressed lift at a lifting speed of the external drive voltage of 200 Vrms / sec <Calculation Method of the hysteresis characteristic values H>, the hysteresis voltage width when the total light transmittance variation of elements ([Delta] T) is changed 50% ΔV _0.5 Δ _T Then
The hysteresis characteristic value H is the hysteresis rise / fall voltage width ΔV
_0.5 The delta _T becomes divided by the thickness d ([mu] m) of the composite film becomes the relationship shown by the following formula, to obtain the hysteresis value is indicative of an intermediate display characteristics _{H (H = ΔV 0.5 Δ T} / d) Can be. The evaluation of the hysteresis characteristic H was as follows. Evaluation Code; evaluation content (hysteresis characteristic HΔV _0.5 Δ _T /
d number in the range) ○; 0.00~0.35 △; 0.36~0.40 × ; 0.41~

2. Film thickness measurement; by micrometer.
Measurement temperature; room temperature. The thickness of the polymer / liquid crystal composite film was determined by measuring the overall thickness of the completed liquid crystal composite display element and subtracting the thickness of the used film of ITO-deposited PET or the like.

3. Comprehensive evaluation; was an overall rating of the hysteresis characteristic value H of the low driving electric field (voltage) characteristic E _0.9 △ _T and the polymer / liquid crystal composite film of a liquid crystal composite display device. In the table,
A, B, C, D and E are displayed, and as a liquid crystal composite display element, A is extremely good, B is good, C is ordinary, D is bad, and E is bad. A and B
Those with a rating of can be used practically. Evaluation Code and hysteresis characteristics H of the comprehensive evaluation the external driving electric field E _0.9 delta _T
Are evaluated as follows. Overall rating symbol; content; evaluation Symbol of external driving electric field E _0.9 Δ _T
No.; Evaluation of hysteresis H symbol A; very good; ◎; ○ B; good; ○; ○ C; Average; ◎, ○; △, × D; bad; △, ×; ○, △ E; quite poor: ×; ×

Next, a synthesis example of a polymer of an asymmetric fumaric acid diester will be described. Synthesis Example 1 Isopropyl fumarate = ethyl (EtiP
F) 10 parts by weight of the mixture were placed in a glass ampule, and azobisisobutyronitrile (hereinafter A) was used as a radical polymerization initiator.
0.05 parts by weight, based on all monomers charged with IBN (abbreviated as Wako Pure Chemical Industries, Ltd.), and purified benzene 0.1%.
After taking 5 parts by weight into a glass ampule, the atmosphere was sufficiently replaced with nitrogen, the pressure reduction and degassing were repeated, and the ampule was sealed under vacuum. Next, this ampoule was placed in a shaking thermostat at 40 ° C., and radical polymerization was carried out for 72 hours. After the polymerization was completed, benzene was put into the ampoule, and then poured into a large amount of hexane to precipitate the polymer. The polymer of EtiPF was isolated, and reprecipitation was repeated with a benzene-hexane system. Let poly EtiPF (hereinafter H (EtiP
F))) (8.7 parts by weight). Table 1 shows the weight average molecular weight of the polymer, where a is the polymer obtained in Synthesis Example 1. It was determined by GPC (gel permeation chromatography) measurement using a column with an exclusion limit of 10 million and conversion from standard polystyrene. In addition, it identified by < ¹ > H-NMR and IR.

Synthesis Example 2 The monomer composition, the radical polymerization initiator and the type and amount of the polymer precipitation solvent (poor solvent) of Synthesis Example 1 were changed to 10 parts by weight of n-butyl fumarate isopropyl (hereinafter abbreviated as BuiPF), Parloyl IPP (diisopropyl peroxydicarbonate, purity 99%, manufactured by NOF Corporation) 0.0
Synthesis Example 1 below except that 2 parts by weight and methanol were used.
The BuiPF polymer (H (nBuiP
9.1 parts by weight (abbreviated as F)) (91% yield). The polymer obtained in this synthesis 2 was designated as "b", and the results of the subsequent analysis are shown in the table.

Synthesis Example 3 The monomer composition, the radical polymerization initiator and the type and amount of the polymer precipitating solvent (poor solvent) in Synthesis Example 1 were changed to 10 parts by weight of isopropyl fumarate = secbutyl (hereinafter abbreviated as sBiPF), Dimethyl butyrate ｛, abbreviated as MAIB,
The same procedure as in Synthesis Example 1 was followed, except that 0.01 parts by weight, methanol, manufactured by Wako Pure Chemical Industries, Ltd. were used.
As a result, 9.0 parts by weight (yield: 90%) of a polymer of BiPF (abbreviated as H (sBiPF)) was obtained. This polymer was designated as c, and the results of the same analysis are shown in the table below.

Synthesis Example 4 The monomer composition, radical polymerization initiator and polymer precipitating solvent (poor solvent) of Synthesis Example 1 were determined using 1-phenyl-2-propyl = isopropyl fumarate (hereinafter referred to as 1Ph2P).
H (1Ph2PiP) was prepared in the same manner as in Synthesis Example 1 except that 10 parts by weight of iPF), 0.01 parts by weight of parloyl IPP (manufactured by NOF CORPORATION), and methanol were used.
8.5% by weight (F) of F) was obtained. This polymer was designated as d, and the results of the same analysis are shown in the table below.

Synthesis Example 5 8 parts by weight of 1Ph2PiPF and 2 parts by weight of iPiPF were placed in a glass ampoule,
After 0.03 parts by weight of perloyl IPP as a radical polymerization initiator and 1 part by weight of purified benzene were placed in a glass ampule, the atmosphere was sufficiently replaced with nitrogen, the pressure reduction and degassing were repeated, and the ampule was sealed under vacuum. Next, this ampoule was placed in a shaking thermostat at 40 ° C., and radical polymerization was carried out for 72 hours. After the polymerization, put benzene in the ampoule, then pour into a large amount of methanol to precipitate the polymer,
The polymer was isolated, and reprecipitation was repeated with a benzene-methanol system, and then dried under reduced pressure to obtain 1Ph2PiP.
F / iPiPF copolymer ｛C (1Ph2PiPF /
iPiPF) (= 8/2 weight / weight) and｝ of 8.7 parts by weight (yield 87%) were obtained. This polymer was designated e, and the results of the same analysis are shown in the table below.

Synthesis Example 6 The monomer composition and the type and amount of the radical polymerization initiator of Synthesis Example 5 were measured using isopropyl-t-butyl fumarate (hereinafter referred to as tBi).
6 parts by weight) and 4 parts by weight of iPiPF, and perloyl IPP, 0.04 parts by weight as a radical polymerization initiator.
Except that it was changed to 2 parts by weight, the same procedure as in Synthesis Example 5 was followed.
tBiPF / iPiPF copolymer (hereinafter C (tBiPF
/ IPiPF) (6/4 weight / weight) was obtained in an amount of 9.4 parts by weight (yield 94%). This polymer was designated as f, and the results of the same analysis are shown in the table below.

Synthesis Example 7 The monomer composition and the type and amount of the radical polymerization initiator of Synthesis Example 5 were 8 parts by weight of EtiPF and 2 parts by weight of sBsBF, and MAIB was 0.1% as a radical polymerization initiator.
An EtiPF / sBsBF copolymer (hereinafter referred to as C (Eti
PF / sBsBF) (8/2 weight / weight) (9.3 weight parts (93% yield)). This polymer was defined as g, and the results of the same analysis are shown in the table below.

Synthesis Example 8 The monomer composition, the radical polymerization initiator, and the type and amount of the polymer precipitation solvent (poor solvent) in Synthesis Example 5 were changed to 4 parts by weight of n-amyl-isopropyl fumarate (hereinafter abbreviated as nAiPF) and iPiPF4. Synthesis Example 5 was repeated except that the weight parts, vinyl acetate (VAc) 2 parts by weight, dimethyl azobisisobutyrate (hereinafter abbreviated as MAIB) as a radical polymerization initiator, and hexane as a polymer precipitating solvent were used. Similarly, nAiPF / iPiPF / V
Ac copolymer (hereinafter C (nAiPF / iPiPF / VA)
c)) (4/4/2 weight / weight / weight) to 9.4
Parts by weight (94% yield) were obtained. This polymer was designated as h, and the results of the same analysis are shown in the table below.

Synthesis Example 9 The monomer composition of Synthesis Example 8 and the type and amount of the radical polymerization initiator were changed to 7 parts by weight of 1Ph2PiPF and iPiPF
1Ph2P in the same manner as in Synthesis Example 8 except that 2 parts by weight and 1 part by weight of vinyl acetate (VAc) were changed to 0.03 parts by weight of AIBN as a radical polymerization initiator.
iPF / iPiPF / VAc copolymer (hereinafter C (1Ph)
2PiPF / iPiPF / VAc) (7/2/1
8.8 parts by weight (yield: 88%). This polymer was designated as i, and the results of the same analysis are shown in the table below.

Synthesis Example 10 The monomer composition of Synthesis Example 5, the types and amounts of the radical polymerization initiator and the polymer precipitant (poor solvent) were 7 parts by weight of sBiPF, 3 parts by weight of VAc, and 3 parts by weight of the radical polymerization initiator. The sBiPF / VAc copolymer (hereinafter C) was prepared in the same manner as in Synthesis Example 5 except that 0.04 parts by weight of MAIB and hexane as the polymer precipitant were used.
(Abbreviated as (sBiPF / VAc)) (7/3 weight / weight) was obtained in an amount of 9.1 parts by weight (yield 91%). This polymer is designated j, and the results of the same analysis are shown in the table below.

Synthesis Example 11 The monomer composition, the type and the amount of the radical polymerization initiator and the polymer precipitant (poor solvent) of Synthesis Example 5 were changed to 7 parts by weight of cyclohexyl-isopropyl fumarate (hereinafter abbreviated as cHiPF) and VAc 3. CHiPF / VAc copolymer (hereinafter referred to as C (cHi) in the same manner as in Synthesis Example 5 except that parts by weight were changed to AIBN as a radical polymerization initiator, 0.02 parts by weight and hexane as a polymer precipitant.
PF / VAc) (7/3 weight / weight) (9.5 weight parts (95% yield)). This polymer is represented by k, and the results of the same analysis are shown in the table below.

Synthesis Example 12 The monomer composition and the type and amount of the radical polymerization initiator of Synthesis Example 5 were measured using cyanoethyl-isopropyl fumarate (hereinafter referred to as CN).
2 parts by weight of iPiPF, 8 parts by weight of iPiPF,
Then, CNEtiPF / iPiPF was prepared in the same manner as in Synthesis Example 5 except that dimethyl azobisisobutyrate (MAIB) was changed to 0.05 part by weight as a radical polymerization initiator.
8.7 parts by weight of a copolymer (hereinafter abbreviated as C (CNEtiPF / iPiPF)) (2/8 weight / weight) (yield 87
%). This polymer was designated as 1 and the results of the same analysis are shown in the table below.

Synthesis Example 13 The monomer composition of Synthesis Example 8 and the type and amount of the radical polymerization initiator were determined by using 2 parts by weight of CNEtiPF, 7 parts by weight of iPiPF,
1 part by weight of VAc was placed in a glass ampoule, and dimethyl azobisisobutyrate (MAI) was used as a radical polymerization initiator.
B) A CNEtiPF / iPiPF / VAc copolymer (hereinafter C (CNEtiPF / iPiPF / VA) in the same manner as in Synthesis Example 8 except that the amount was changed to 0.02 parts by weight.
8.2) by weight (yield: 82%) was obtained (abbreviated as c)) (2/7/1 weight / weight / weight). The polymer was defined as m, and the results of the same analysis are shown in the table below.

Synthesis Example 14 The monomer composition of Synthesis Example 5, the types and amounts of the radical polymerization initiator and the polymer precipitant (poor solvent) were changed to 3 parts by weight of hydroxyethylisopropyl fumarate (hereinafter abbreviated as OHEtiPF) and 7 parts by weight of sBsBF. Take the part into a glass ampoule,
OHEtiPF / s was prepared in the same manner as in Synthesis Example 5 except that 0.04 parts by weight of perloyl IPP was used as the radical polymerization initiator and hexane was used as the polymer precipitant.
BsBF copolymer (hereinafter C (OHEtiPF / sBs)
BF) (abbreviated as BF) (3/7 weight / weight) was obtained in an amount of 9.3 parts by weight (yield: 93%). This polymer is represented by n, and the results of the same analysis are shown in the table below.

Synthesis Example 15 The monomer composition and the type and amount of the radical polymerization initiator and the type and amount of the polymer precipitant (poor solvent) in Synthesis Example 8 were changed to OH
OHEtiPF was prepared in the same manner as in Synthesis Example 8 except that 1 part by weight of EtiPF, 8 parts by weight of iPiPF, and 1 part by weight of VAc were placed in a glass ampule, and 0.01 parts by weight of MAIB was used as a radical polymerization initiator and hexane was used as a polymer precipitant. / SBsBF / VAc copolymer
(Hereinafter abbreviated as C (OHEtiPF / iPiPF / VAc)) (1/8/1 weight / weight) to 8.3 parts by weight (yield 8
3%). This polymer was designated as o, and the results of the same analysis are shown in the table below.

Synthesis Example 16 The following synthesis example was conducted except that the monomer composition and the type and amount of the radical polymerization initiator of Synthesis Example 1 were changed to 10 parts by weight of iPiPF and 0.02 parts by weight of perloyl IPP as a radical polymerization initiator. In the same manner as in 5, 9.3 parts by weight (93% yield) of an iPiPF copolymer iPiPF polymer (hereinafter abbreviated as H (iPiPF)) was obtained. This polymer was designated as A, and the results of the same analysis are shown in the table below.

Synthesis Example 17 The monomer composition and the type and amount of the radical polymerization initiator of Synthesis Example 1 were 10 parts by weight of dicyclohexyl fumarate (hereinafter abbreviated as CHcHF), and MAIB was 0.03% as a radical polymerization initiator. A cHcHF polymer (hereinafter referred to as H (cHc
HF)) was obtained in an amount of 9.3 parts by weight (yield: 93%).
This polymer was designated as B, and the results of similar analysis are shown in the table below.

Synthesis Example 18: Synthesis of PMMA The monomer composition and the amount of the radical polymerization initiator of Synthesis Example 1 were
8. Polymethyl methacrylate (hereinafter abbreviated as H (MMA)) was used in the same manner as in Synthesis Example 1 except that 10 parts by weight of methyl methacrylate was placed in a glass ampoule and changed to 0.08 part by weight of AIBN as a radical polymerization initiator. 0 parts by weight (yield 90%) were obtained. The results of the same analysis are shown in the table below. Synthesis Examples 2 to 15, (Comparative) Synthesis Examples 16 to 18
Tables 1, 2 and 3 show the compositions of
Shown in

[0087]

[Table 1]

[0088]

[Table 2]

[0089]

[Table 3]

The abbreviations used in the table are as follows. <Asymmetric fumaric acid ester>;EtiPF; ethyl fumarate = isopropyl, BuiPF; butyl fumarate = isopropyl, sBiPF; sec-butyl fumarate = 1Ph2PiPF; 1-phenyl-2-propyl = fumarate, tBiPF; T-butyl acid isopropyl, nAiPF; n-amyl isopropyl fumarate, cHiPF; cyclohexyl isopropyl, CNEtiPF; cyanoethyl fumarate = isopropyl, OHEtiPF; hydroxyethyl fumarate = isopropyl, <symmetric fumarate>;iPiPF; Isopropyl isopropyl = sBsBF; sec-butyl fumarate = sec-butyl, cHcHF; cyclohexyl fumarate = cyclohexyl Monomer>;VAc; vinyl acetate, MMA; methyl methacrylate,

Next, a to o obtained in Synthesis Examples 1 to 18 are used.
And a polymer of A to C, and a water-soluble polymer PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., KH-
17, polymerization degree 1700, saponification degree 81.51, this PV
Using A as a polymer D and a nematic liquid crystal, the following operation was performed to produce a liquid crystal composite display element.

Example 1-1 [Step 1]: 50 mm × 50 mm × 100 μm light-transmitting ITO-deposited PET film (manufactured by Teijin Limited, film thickness 1)
00 μm｝; 3 parts by weight of H (EtiPF) synthesized in Synthesis Example 1, which is a water-insoluble polymer, and 7 parts by weight of a nematic mixed liquid crystal: TL-202 (manufactured by BDH) on the layer [1]. The resulting mixture was mixed and dissolved in a water-insoluble solvent toluene using a wave rotor (WR40, manufactured by Thermonics Co., Ltd.) so as to obtain a 10% by weight toluene solution. A 10% by weight toluene solution of H (ETiPF) / liquid crystal (3/7% by weight) prepared by dissolution was applied on the ITO-deposited PET film by using a doctor blade, and dried by a vacuum dryer.
Vacuum drying was performed while gradually increasing the temperature at 0 ° C. for 2 hours, 80 ° C. for 1 hour, and 120 ° C. for 1 hour to sufficiently evaporate the water-insoluble solvent toluene to evaporate the polymer / liquid crystal composite film (; layer [2 ]) Was formed. [Step 2]: Then, another light-transmitting ITO vapor-deposited PET film (; layer [; layer [2]) so that the transparent conductive substrate faces the entire surface of the layer [2] on the prepared water-insoluble polymer / liquid crystal composite film. 3]) to produce a desired liquid crystal composite display element (1) -1. The thickness of the water-insoluble polymer / liquid crystal composite composite film at that time was measured by the above method using a micrometer. Its film thickness was 10 μm.

Examples 1-2 to 1-15, Comparative Examples 2-1 to
2-6 Hereinafter, according to Example 1, as shown in Table 1, Example 1
In Examples 1-2 to 1-15, instead of the polymer a as the matrix polymer of the water-insoluble polymer / liquid crystal composite film of No. 1, the polymers bo were replaced with the comparative examples 2-1 to 2 In -6, ABC and D were used as the water-insoluble polymer or the water-soluble polymer, respectively, and the liquid crystal type and amount were as shown in Table 2 using the liquid crystal composite display elements (1) -2 to (1). -15) and (2) -1 to (2) -6. The thickness of the polymer / liquid crystal composite film at that time is shown in Tables 4 to 7 together with the results measured by the above-described method. Comparative Example 2-4
Is a polymer D of a water-soluble polymer, PVA, so that a liquid crystal composite display element was prepared using water as a solvent instead of a water-insoluble solvent.

The liquid crystal display devices (1) -1 to 1 obtained above were obtained.
Using (1) -15 and (2) -1 to (2) -6, the display characteristics of the liquid crystal composite display device were evaluated in accordance with the above-described display characteristics measuring method. The results are shown in Tables 4, 5, 6 and 7.

[0095]

[Table 4]

[0096]

[Table 5]

[0097]

[Table 6]

[0098]

[Table 7]

As a result, it can be seen that the example of the present invention has a lower driving electric field voltage and better hysteresis characteristics than the comparative example.

Reference Example 1 Examples 1-1, 1-2, 1-5 and 1-
The following adhesion tests were performed using the liquid crystal composite display elements of Examples 12, 1-15 and Comparative Examples 2-1 and 2-2. Table 8 shows the results.

[0101]

[Table 8]

The adhesion test is as follows. <Adhesion test method> A commercially available cellotape (registered trademark) was adhered to the prepared liquid crystal composite display element, and the ITO vapor-deposited PE was drawn when the cellotape was pulled in the direction of 180 degrees.
The peeling state of the T film was observed to evaluate the adhesion.
Perform cellophane tape removal test at 10 different locations,
The following evaluation criteria evaluated. Evaluation symbol: Evaluation content (number of peeled pieces): up to 2 ○: up to 3 △: 4 to 8 ×; 9 to 10

From the above results, it can be seen that in the examples using the asymmetric fumaric acid diester polymer used in the present invention, the adhesion can be improved as compared with the comparative example using the symmetric fumaric acid ester polymer. I understand.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a driving (voltage) AM (Ampl)
FIG. 3 is a diagram showing an example (waveform of an Iteration Modulation).

FIG. 2 is a diagram showing a temporal change in light transmittance of a composite film corresponding to application and removal of a voltage.

FIG. 3 is a diagram showing a hysteresis curve of light transmittance when the voltage used for measurement rises and falls.

[Explanation of symbols]

fm; fm indicates a triangular wave Fm modulated wave (Hs) fc; fc indicates an Fc carrier wave (Hz) to be vibrated ΔT; ΔT (%) indicates the transmittance of the liquid crystal composite display element during on-off. Shows the change in 0.5 △ T; 0.5 △ T has a transmittance change (△ T%) of 50
%. 0.9 △ T; 0.9 △ T has a transmittance change (△ T%) of 90
%. _{△ V 0.9 △ T; △ V} 0.9 △ T represents the value of the applied voltage at which the transmittance exhibits a 0.9 △ T. _{△ V 0.5 △ T; △ V} 0.5 △ T is the value of the hysteresis characteristic shown during lifting of the applied voltage, the value of the voltage difference when the transmittance showed 0.5 △ T.

Continued on the front page F-term (reference) 2H089 QA16 RA03 SA17 4H027 BA01 BB11 BD04 BD08 BD20 BD22 BE02 BE03 4J100 AB00Q AB02Q AB03Q AB07Q AB08Q AC03Q AC23Q AE03Q AE06Q AE09Q AF10Q AG02Q AG04Q BA03 AS03 AL03 BA03 AS03 AL04 BA16Q BA31P BA31Q BA40P BA51P BA53P BA65P BB01P BB07P BB18P BC03P BC04P BC04Q BC09P BC43P BC54P CA01 CA04 DA01 JA39

Claims (9)

[Claims] 1. A water-insoluble polymer / liquid crystal composite film composed of a water-insoluble polymer and a nematic liquid crystal, and at least one of two sheets having conductive portions opposed to each other with both sides sandwiching the film. a liquid crystal composite display device having an optical modulation function consisting of a conductive substrate having sex, of its liquid crystal display characteristics, the external driving electric field E _0.9 delta _T (external driving voltage V _0.9 delta _T /
d) is 0.15 to 4.5 AC (V / μm), and the hysteresis characteristic value H is 0.0 to 0.35 AC (V / μm).
A liquid crystal composite display element characterized by the following. 2. The liquid crystal composite display device according to claim 1, wherein the water-insoluble polymer is a polymer containing at least 10% by weight to 100% by weight of an asymmetric fumaric acid diester as a constituent. 3. A polymer comprising an asymmetric fumaric acid diester as a water-insoluble polymer as a component is represented by the following general formula (1): ## STR1 ## (Wherein, R ¹ is a branched alkyl group having 3 to 12 carbon atoms,
Or a cycloalkyl group having 3 to 14 carbon atoms;
² is an alkyl group having 1 to 14 carbon atoms, and 3 to 1 carbon atoms.
Although it may have a cycloalkyl group of 4, an aryl group having 7 to 20 carbon atoms, and a hetero atom and / or a substituent, R ¹ ≠ R ² and represents a different hydrocarbon group. A) a polymer having a repeating unit of an asymmetric fumaric acid diester represented by the formula (1), having a weight average molecular weight of 20,000 to 1,50:
3. The liquid crystal composite display device according to claim 2, wherein the value is 000. 4. A polymer comprising an asymmetric fumaric acid diester as a component is a copolymer obtained by polymerizing an asymmetric fumaric acid diester and diisopropyl fumarate or disec-butyl fumarate, and having a weight average molecular weight of 20,0
4. The liquid crystal composite display device according to claim 2, wherein the number is from 00 to 1,500,000. 5. A copolymer comprising an asymmetric fumaric acid diester as a constituent component is obtained by polymerizing an asymmetric fumaric acid diester having a hydroxyalkyl group or a cyanoalkyl group with diisopropyl fumarate or disec-butyl fumarate. A polymer having a weight average molecular weight of 20,
The liquid crystal composite display device according to claim 4, wherein the number is from 000 to 500,000. 6. A polymer comprising an asymmetric fumaric diester as a constituent component is a copolymer obtained by polymerizing an asymmetric fumaric diester and a vinyl monomer, and has a weight average molecular weight of 20,000 to 1, The liquid crystal composite display device according to claim 3 or 4, wherein the number is 500,000. 7. The liquid crystal composite display device according to claim 1, wherein the weight ratio of the water-insoluble polymer to the nematic liquid crystal in the composite film is 40/60 to 5/95. 8. The liquid crystal composite display device according to claim 1, comprising a nematic liquid crystal containing a halogen atom. 9. The production method according to claim 1, wherein the nematic liquid crystal and the water-insoluble polymer are:
Using a coating solution dissolved in a water-insoluble solvent of a good solvent common to the nematic liquid crystal and the water-insoluble polymer, applied to one surface of a conductive substrate, and the water-insoluble solvent is evaporated by evaporation. Solidifying the water-insoluble polymer to form a matrix polymer, phase-separating the liquid crystal and the water-insoluble polymer in the matrix polymer, and further sandwiching one conductive substrate. A method for manufacturing a liquid crystal composite display element, comprising: