JP2000290654A - Liquid crystal composite display device and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal composite display device excellent in electrooptical characteristics retainability with time and durability. SOLUTION: This liquid crystal composite display device having light modulation function and so designed as to have a water-insoluble polymer/liquid crystal composite membrane composed of a water-insoluble polymer and liquid crystal and disposing two sheets of electroconductive base materials with at least one of them having light transmissivity on both sides of the membrane respectively so that the electroconductive parts stand against each other. This device is obtained by curing with active energy rays a polymeric precursor/liquid crystal composition prepared by mixing a liquid crystal with a water-insoluble polymeric precursor containing at least one unsaturated fatty acid diester of the formula (R1 and R2 are each a 1-12C straight-chain alkyl, 3-12C branched alkyl, 3-12C cycloalkyl or 7-20C aryl, optionally having heteroatom(s) and/or substituent(s); n is an integer of 1-15).

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, the present invention relates to a liquid crystal composite display element having excellent retention and durability of electro-optical characteristics over time and a method of manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, various methods have been studied for realizing a liquid crystal composite display element which does not require a polarizing plate and has a high display luminance in order to utilize light scattering behavior. Here, with the liquid crystal composite display element, at least one of the two sheets is disposed such that the conductive portions face each other with a conductive base material having light transmittance,
It has a structure sandwiching a polymer / liquid crystal composite film composed of a polymer and a liquid crystal. The polymer / liquid crystal composite film can be roughly classified into 1) a method in which a composition in which a liquid crystal is emulsion-dispersed in an aqueous solution of a water-soluble polymer (phase separation occurs at this stage) is applied to a substrate and dried. . 2) A method in which a composition in which a water-insoluble polymer and liquid crystal are dissolved in a common solvent is applied to a substrate and dried (phase separation occurs in the drying process). 3) A composition in which a polymer precursor (which is polymerized by an active energy ray or the like) and liquid crystal are mixed and applied to a substrate, or injected into a cell composed of two substrates. Thereafter, it is prepared by a method of irradiating with ultraviolet rays or the like (phase separation is caused by irradiation with active rays). As an example of the above 1), a method of dispersing a liquid crystal capsule in PVA using polyvinyl alcohol (PVA) which is a water-soluble polymer is disclosed (Japanese Patent Publication No. 3-52843). However, since a water-soluble polymer is used, it is known that durability such as moisture resistance is poor. As an example of the above 2), a method using polyfumarate or polyitaconate having high hydrophobicity among water-insoluble polymers is disclosed (JP-A-4-136817, JP-A-5-136817).
No. 289062, JP-A-9-218398, etc.). However, as described above, the water-insoluble polymer having a high hydrophobicity and a low miscibility with the liquid crystal has excellent durability over time of the electro-optical properties of the composite film, but has a high compatibility with the substrate. It is not sufficient in terms of adhesion. As an example of the above 3),
A method using a photocurable acrylate compound as a polymer precursor is disclosed (JP-A-64-626).
No. 15). Although it is considered that the adhesiveness with the substrate which is a problem in the above is almost sufficient, the interaction with the liquid crystal of the polymer precursor is not taken into consideration, and the durability of the electro-optical properties over time is insufficient. The problem is that there are many things.

[0003]

SUMMARY OF THE INVENTION A first object of the present invention is to maintain the electro-optical characteristics over time, which is a problem when using a liquid crystal composite display element, and to adhere the composite film constituting the display element to a substrate. An object of the present invention is to provide a highly durable liquid crystal composite display device having excellent durability. A second object of the present invention is to provide a method for manufacturing the above liquid crystal composite display element.

[0004]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have found that a monomer having a specific structure is used as a polymer precursor and irradiated with energy rays or the like to cure the polymer. And obtained the knowledge that they exhibit excellent characteristics, and completed the present invention. The present invention provides the following [1] to [6]
It is.

[1] A water-insoluble polymer / liquid crystal composite film composed of a water-insoluble polymer and a liquid crystal, and at least two sheets on both sides of which are provided with a conductive base material having a light-transmitting property, and a conductive portion facing each other In a liquid crystal composite display device having a light modulation function, which is arranged so as to satisfy the following general formula (1):

[0006]

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Wherein R ¹ and R ² may be the same or different, and R ¹ and R ²
Is a linear alkyl group having 1 to 12 carbon atoms, 3 to 12 carbon atoms
A cycloalkyl group having 3 to 12 carbon atoms or an aryl group having 7 to 20 carbon atoms, which may have a hetero atom or a substituent, and n is an integer of 1 to 15. A) a polymer precursor / liquid crystal composition obtained by mixing a liquid crystal with a water-insoluble polymer precursor containing at least one unsaturated fatty acid diester represented by A liquid crystal composite display element characterized by the above-mentioned.

[2] When the unsaturated fatty acid diester is n = 1
The following general formula (2)

[0009]

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Wherein R ¹ and R ² may be the same or different, and R ¹ and R ²
Is a linear alkyl group having 1 to 12 carbon atoms, 3 to 12 carbon atoms
A cycloalkyl group having 3 to 12 carbon atoms or an aryl group having 7 to 20 carbon atoms, which may have a hetero atom or a substituent. The above liquid crystal composite display element which is an itaconic acid diester represented by the following formula:

[3] The water-insoluble polymer precursor is a monomer (A) represented by the general formula (1) or (2) and a vinyl monomer copolymerizable with the monomer (A) B) The liquid crystal composite display element described above.

[4] The liquid crystal composite display device as described above, wherein the copolymerizable vinyl monomer is a hydroxy group-containing (meth) acrylic acid derivative.

[5] A polymer precursor / liquid crystal composition obtained by mixing a liquid crystal with a water-insoluble polymer precursor containing at least one monomer represented by the general formula (1) or (2). The product is applied to one conductive substrate, then cured by an active energy ray, and further obtained by laminating the other conductive substrate facing each other. Method.

[6] The method according to the above, wherein the compound of the polymer precursor / liquid crystal composition is injected into a cell composed of opposing conductive substrates and then cured by an active energy ray. A method for manufacturing a liquid crystal composite display element.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a "liquid crystal composite display element" means that the first layer is a conductive base material, the second layer is a composite film of a water-insoluble polymer / liquid crystal, and the third layer is a conductive layer. The base material is a main component. Among them, one of the first and third conductive base materials has light transmittance. That is, the present invention relates to a water-insoluble polymer comprising a water-insoluble polymer and a liquid crystal.
A liquid crystal composite display element having a light modulation function in which a liquid crystal composite film and a conductive base material on which at least one of the two is light-transmitting are disposed so that the conductive portions face each other,
The following general formula (1)

[0016]

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A polymer precursor / liquid crystal composition obtained by mixing a water-insoluble polymer precursor containing at least one or more unsaturated fatty acid diesters and a liquid crystal is obtained by curing with an active energy ray. A liquid crystal composite display device comprising Here, R ¹ and R ² in the formula may be the same or different groups, and R ¹ and R ² are a straight-chain alkyl group having 1 to 12 carbon atoms and 3 carbon atoms. Represents a branched alkyl group having up to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aryl group having 7 to 20 carbon atoms, and may have a hetero atom or a substituent, and n represents an integer of 1 to 15 .

Further, the present invention relates to the following general formula (2) wherein the unsaturated fatty acid diester is n = 1.

[0019]

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It is preferable to contain at least one or more itaconic acid diesters represented by Here, R ¹ and R ² in the formula may be the same or different groups, and R ¹ and R ² are a straight-chain alkyl group having 1 to 12 carbon atoms and 3 carbon atoms. To 12 branched alkyl groups, cycloalkyl groups having 3 to 12 carbon atoms or 7 to 20 carbon atoms
Represents an aryl group. Further, R ¹ and R ² may have a hetero atom in the above group. Further, R ¹ and R ² may have a substituent on the above group.

Examples of the itaconic acid diester in which R ¹ and R ² are a linear alkyl group having 1 to 12 carbon atoms and a branched alkyl group having 3 to 12 carbon atoms include, for example, dimethyl itaconate and itaconic acid. Diethyl, itaconic acid di-n
-Propyl, diisopropyl itaconate, di-t-butyl itaconate, di-s-butyl itaconate, di-4-methyl-2-pentyl itaconate, di-n-nonyl itaconate, -n-octyl itaconate = t-butyl (hereinafter, referred to as t-butyl)
With = symbols in order to clearly distinguish the R ¹ and R ^2. The same shall apply hereinafter), isopropyl itaconate = t-butyl, isopropyl itaconate = isoamyl, isopropyl itaconate = 2-ethylhexyl, isopropyl itaconate =
Nonyl, t-butyl itaconate = s-butyl, t-butyl itaconate = isoamyl, t-butyl itaconate = 4
-Methyl-2-pentyl, t-butyl itaconate = 2-
Ethylhexyl and the like.

Examples of the cycloalkyl group having 3 to 12 carbon atoms for R ¹ or R ² include dicyclohexyl itaconate and dicyclooctyl itaconate. R ¹
Alternatively, examples of R ² being an aryl group having 7 to 20 carbon atoms include, specifically, dibenzyl itaconate, dibiphenyl itaconate, benzyl itaconate = isopropyl, biphenyl itaconate = t-butyl and the like. Can be

The hetero atoms of the itaconic diester containing a hetero atom in R ¹ or R ² include oxygen (O), nitrogen (N), sulfur (S) and silicon (Si). Examples of itaconic acid diesters containing heteroatoms of oxygen (O), nitrogen (N) and sulfur (S) include, for example, N, N-dimethylaminoethyl isopropyl itaconate, t-butyl itaconate = 1-butoxy-2 Dipropyl itaconate containing a hetero atom, such as -propyl, isopropyl itaconate = 2-cyanoethyl, glycidyl itaconate = isopropyl, and 2-methylthioethyl itaconate isopropyl;

Examples of itaconic acid diesters containing a silicon (Si) heteroatom in R ¹ or R ² include, for example, methyl itaconate = trimethylsilyl, ethyl itaconate = trimethylsilyl, isopropyl itaconate = trimethylsilyl, cyclohexyl itaconate = trimethylsilyl, T-butyl itaconate = trimethylsilyl;

Further, the substituent of the itaconic acid diester having a substituent at R ¹ or R ² includes a halogen atom, and specifically, chlorine (Cl) and fluorine (F). Examples of the itaconic acid diester containing a halogen atom include perfluorooctylethyl itaconate = isopropyl, t-butyl itaconate = trifluoromethyl,
Preferable examples thereof include itaconic acid diesters containing a halogen atom such as isopropyl itaconate = pentafluoroethyl, hexafluoroisopropyl itaconate = isopropyl, and bis (1-chloroisopropyl) itaconate. Examples of the itaconic acid diester containing an aryl group and a hetero atom in R ¹ or R ² include benzyl itaconate = trimethylsilyl.

The copolymerizable vinyl monomers other than the above-mentioned itaconic acid diester which can be blended with the polymer precursor include, for example, styrene, methylstyrene and their derivatives; (meth) acrylic acid and its lower Alkyl esters; crotonic acid and its lower alkyl esters; fumaric acid and its lower alkyl esters; maleic acid and its lower alkyl esters; vinyl ethers such as isobutyl vinyl ether; vinyl esters such as vinyl acetate and vinyl pivalate; Allyl esters such as allyl acetate and allyl benzoate; maleimides; vinyl chloride, vinylidene chloride and the like can be preferably exemplified. Upon use, these copolymerizable vinyl monomers can be used alone or in combination of two or more.

Furthermore, as a copolymerizable vinyl monomer used for the purpose of enhancing the adhesion between the formed composite film and the substrate, a hydroxy group-containing (meth) acrylic acid derivative is particularly preferably mentioned. Can be. In particular,
Monofunctional monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate , 2
And polyfunctional monomers such as -hydroxy-1,3 dimethacryloxypropane, 2-hydroxy-3-acryloyloxypropyl methacrylate, and tetramethylolmethane triacrylate. Furthermore, as a commercial product,
For example, an acrylic acid adduct to a polyfunctional epoxy compound sold by Kyoeisha Chemical Co., Ltd. (for example, trade name,
Epoxy ester 200PA, 3002M, 200E
A, 400EA, 70PA, etc.).

In the above polymer precursor, the unsaturated fatty acid diester or itaconic acid diester represented by the general formula (1) or (2) is preferably 40% by weight.
To 100% by weight, more preferably 60% to 100% by weight.
% By weight. If the amount of the unsaturated fatty acid diester or itaconic acid diester is less than 40% by weight, the compatibility with the liquid crystal in the polymer / liquid crystal composite film formed is not preferred.

In the present invention, usable liquid crystals are not particularly limited, as long as they can be used as liquid crystals for liquid crystal display devices. Specifically, for example, p-alkoxy-p'-alkyl Azoxy compounds such as azobenzene and p-azoxyphenetole; p-alkoxy-
Nitrogen base compounds such as p'-alkylbenzylideneaniline; phenyl ester compounds such as p-alkoxy-p'-cyanophenylbenzoic acid and cholesteric benzoic acid; p-alkoxy-p'-cyanobiphenyl;
Biphenyl compounds such as alkoxy-p'-carboxylic acid biphenylalkyl esters; phenylcyclohexane compounds; dioxane compounds; pyrimidine compounds. These liquid crystals can be used alone or as a mixture when used. As other liquid crystals, those described in “Liquid Crystal Device Handbook”, edited by the 142nd Committee of the Japan Society for the Promotion of Science, published by Nikkan Kogyo Shimbun, Chapter 3, Liquid Crystal Materials can also be used.

In the present invention, the polymer precursor and a liquid crystal are blended, and a polymer precursor / liquid crystal composition is blended. The composition can be compounded by a commonly used mixing method.

If necessary, an organic solvent capable of dissolving the polymer precursor and the liquid crystal, an initiator corresponding to active energy rays, and the like may be added to the composition. Usable organic solvents are general-purpose organic solvents for the purpose of adjusting viscosity, etc.
For example, methanol, ethanol, chloroform, methyl ethyl ketone, methyl isobutyl ketone, benzene,
Preferable examples include toluene.

The active energy rays for curing include:
Radiation such as electron beams and ultraviolet rays can be preferably mentioned. Although the irradiation dose is not particularly limited, for example, a cured composite film that is preferably irradiated with ² to 50 Mrad in the case of an electron beam and 10 to 50 mW / cm ² in the case of an ultraviolet ray for ⁵ to 1000 seconds is obtained. It is formed.

As an initiator corresponding to an active energy ray, for example, a photopolymerization initiator used for ultraviolet curing may be any one having a polymerization initiating ability by ultraviolet irradiation. Specifically, for example, benzyldimethyl ketal, 2,2-dimethoxy-1,2-diphenylethane-1
-One, 2-benzyl-2-dimethylamino-1- (4
Acetophenone-based initiators such as -morpholinophenyl) -butane; benzophenone-based initiators such as benzophenone, bis4-dimethylaminophenylketone and phenylbenzoylketone; 2,4-diethylthioxanthone;
Thioxanthone-based initiators such as -chloro-4-propoxythioxanthone and isopropylthioxanthone; S-phenyl thiobenzoate-based initiator, oxime ketone-based initiator, acylphosphine oxide-based initiator, acylphosphonate-based initiator, titanocene-based initiator Initiators and the like can be mentioned. These can be used alone or as a mixture. Depending on the type of the polymerization initiator, a method may be used in which a reaction accelerator such as a tertiary amine such as p-dimethylaminobenzoate is added. The mixing ratio of the polymerization initiator is 0.1 to the polymer precursor / liquid crystal composition.
Desirably, the amount is 001 to 20 parts by weight. If the compounding ratio of the initiator is less than 0.001 part by weight, the curing becomes insufficient, and if it exceeds 20 parts by weight, the amount of the generated initiator fragments is too large when the composition is polymerized and cured, all of which are easily deteriorated. It is not preferable because durability is reduced.

The composition of the polymer precursor / liquid crystal composition is not particularly limited, but the ratio of the precursor / liquid crystal is preferably 60/40 to 2/98 by weight, more preferably. , 40/60 to 5/95 weight ratio.

Next, a method for manufacturing the liquid crystal composite display device of the present invention will be described. As a method for manufacturing the liquid crystal composite display element of the present invention, there are the following two methods. In the first production method, the polymer precursor / liquid crystal composition prepared as described above is applied to a conductive base material, cured using an active energy ray, and then the opposing conductive base material is provided. Is the way.
The second manufacturing method is a method of injecting the polymer precursor / liquid crystal composition prepared as described above into a cell composed of two conductive substrates, and then curing the cell with an active energy ray.

As the conductive substrate used in the present invention, a transparent glass substrate having an electrode layer of ITO (indium oxide), NESA (tin oxide) or the like can be preferably mentioned. Furthermore, a substrate obtained by providing an electrode layer on various transparent resins can also be used.

When the liquid crystal composite display element of the present invention is produced by the above-mentioned first production method, the method of applying to the base may be, for example, a batch method such as a brush coating method, a spray method, a dipping method, or a gravure method. Continuous coating machines such as a coating method and a doctor blade method can be used.

When the liquid crystal composite display element of the present invention is manufactured by the above-described second manufacturing method, it is usually used in a step of manufacturing a liquid crystal panel when a polymer precursor / liquid crystal composition is injected into a cell. The injection device used can be used.

The thickness of the composite film of the liquid crystal composite display device manufactured by the above-described first and second manufacturing methods is not particularly limited, but is usually 2 to 200 μm, and the characteristics as the display device are taken into consideration. If done, preferably 5-20 μm
It is.

[0040]

The liquid crystal composite display element of the present invention has excellent retention of electro-optical characteristics over time, which is a problem in long-term use of the liquid crystal composite display element, and excellent adhesion between the composite film constituting the display element and the substrate. A highly durable liquid crystal composite display device has become possible. Further, the method of manufacturing a liquid crystal composite display element of the present invention,
The highly durable liquid crystal composite display device described above can be easily manufactured.

[0041]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The cured composite film characteristics and display characteristics were evaluated as follows. 1. Cured composite film characteristics 1-1. Evaluation method of curability: After coating on a base material with a predetermined film thickness, the surface curability of the composite film cured by irradiation with ultraviolet rays (UV) or electron beams (EB) was classified as follows by a finger. In addition, the same determination was made in the case of the partial casting method. Evaluation symbol: Evaluation content ；: No tackiness on the surface of the composite film. Δ: The surface of the composite film is not sticky, but the elasticity when pressed with a finger is felt. ×: The composite film surface is sticky or does not recover when pressed with a finger.

1-2. Evaluation method of adhesion Two types of adhesive tapes (cellophane, mending tape)
It was determined as follows by a peel test. Evaluation symbol: Evaluation content ；: No clear peeling was observed on both tapes. Δ: Partial peeling was observed with the cellophane tape, and no peeling was observed with the mending tape. X: Peeling is observed with both tapes. ○; ○; ○ or △ ○; △; ○ △; △; △ ×; ○ or △; XX; ×; ○ or △

2. Evaluation of display characteristics of liquid crystal composite display element; After injecting various compositions such as water-insoluble polymer / liquid crystal into the constructed test cell, after UV irradiation, display element characteristics before and after heating test and adhesion before heating test The properties were evaluated and classified as follows. ΔT ₁ defines the change in transmittance of the test cell before and after the heating test as follows. ΔT ₁ = T _S1 −T ₀₁ , where T _S1 is the transmittance when a voltage of 50 V is applied to the test cell, and T ₀₁ is the transmittance when no voltage is applied to the test cell. ΔT _H is defined as the transmittance change after a heating test at 120 ° C. for 30 hours as follows. Here _{ΔT H = T S h-T} 0 h, T S h , the voltage 5 to a test cell after the heating test
The transmittance when 0 V is applied, T ₀ h, indicates the transmittance when no voltage is applied to the test cell after the heating test. Absolute value of the difference ABS (ΔT) = | ΔT ₁ −ΔT _H |
Was determined and classified according to the following criteria. Evaluation symbol: Evaluation content ；: ABS (ΔT) is less than 5%. Δ: ABS (ΔT) is 5% or more and less than 10%. ×: ABS (ΔT) is 10% or more.

2-2. Evaluation Method of Adhesion The center of the cured cell was broken using a metal punch, and the cells were classified as follows according to the degree of adhesion of the glass substrate to the composite film. Evaluation symbol: Evaluation content : Glass shards are stuck to the composite film and cannot be easily peeled. Δ: The glass fragments adhere to the composite film, but can be easily peeled. ×: Peeled at the time of destruction. ○; ○; ○ ○; ○; △ ×; ○; × ×; ×; ○ Table 2 shows the adhesion of the liquid crystal element and the retention of the display element characteristics before and after the heating test. The items of the comprehensive evaluation are summarized below.

Examples 1-1 to 1-10 As shown in Tables 1 and 2, polymer precursor blends using itaconic acid diesters having various substituents were prepared.

Comparative Examples 1-1 and 1-2 As shown in Table 3, a precursor blend was prepared using only the (meth) acrylic precursor except for the itaconic acid diester. The formulations are shown in Tables 1 and 2.

Examples 2-1 to 2-14 As shown in Tables 3, 4 and 5, the polymer precursor / liquid crystal blended with the polymer precursor blends of Tables 1 and 2, a nematic liquid crystal, and a photoinitiator were blended. A blend was prepared, applied on an aluminum substrate with a bar coater, and then cured with ultraviolet light or an electron beam to form a cured composite film on the aluminum substrate. The film thickness was about 10 μm. The ultraviolet irradiation conditions of Examples 2-1 to 10 were 25 mW / cm ² for 80 seconds. The electron beam irradiation conditions of Examples 2-11 to 14 were 5Mr at room temperature.
ad (acceleration voltage 150 KV). The curability and adhesion of the obtained cured composite film were evaluated by the above-described method for evaluating the characteristics of the cured composite film. The results are summarized in Tables 3, 4 and 5.

COMPARATIVE EXAMPLES 2-1 and 2-2 UV irradiation and cured composite film properties were evaluated in the same manner as in the above examples, except that the formulations of the comparative examples shown in Table 2 were used. Show.

Comparative Examples 2-3 to 5 In place of the polymer precursor used in Examples 2-1 to 2-14 and Comparative Examples 2-1 and 2-2, a polymer previously polymerized was used. Prepare a 15% toluene solution based on polymer and liquid crystal, apply it on an aluminum substrate with a bar coater, and evaporate toluene at 80 ° C for 5 hours to form a liquid crystal composite film on the aluminum substrate. Formed. Composite membrane properties were similarly evaluated in the manner described above. The results are summarized in Table 6.

Examples 3-1 to 3-11 The polymer precursor / liquid crystal compositions shown in Tables 7 and 8 were injected into a test cell having a 5 × 5 mm ² ITO pattern, and then irradiated with ultraviolet rays. A liquid crystal composite display device was prepared by curing the composition. The cell gap (corresponding to the composite film thickness) of 10 μm was used. The device characteristics and the adhesiveness of the prepared device characteristics were evaluated according to the evaluation method of the liquid crystal composite display device described above. The results are shown in 7 and 8.

Comparative Examples 3-1 and 3-2 The same procedures and evaluations as those in Examples 3-1 to 3-11 were conducted except that the comparative examples shown in Table 2 were used.
The results are summarized in Table 9.

Comparative Examples 3-3 to 3-5 The polymer / liquid crystal toluene solution described in Comparative Examples 2-3 to 2-5 was spin-coated on a glass substrate on which an ITO pattern before formation was drawn. After application, it was dried. While pressing the glass substrate on which the ITO pattern was drawn on the composite film on the substrate, the periphery was sealed with an adhesive to form an evaluation test cell. The evaluation was performed on the adhesion and the property retention before and after the heating test in the same manner as described above. The results are summarized in Table 9.

[0053]

[Table 1]

[0054]

[Table 2]

The abbreviations shown in Tables 1 and 2 are as follows. <Component 1>DiPITA; diisopropyl itaconate, DEtITA; diethyl itaconate, DHFMeITA; bis (trifluoromethyl) itaconate, DcHITA; dicyclohexyl itaconate, <component 2>DCPA; dimethylol tricyclodecane acrylate, CHDVE; cyclohexanedi Methanol divinyl ether, 70PA; Epolite 70P acrylic acid adduct, 80MFA; Epolite 80MF acrylic acid adduct, <Other components>MMA; Methyl methacrylate

[0056]

[Table 3]

[0057]

[Table 4]

[0058]

[Table 5]

[0059]

[Table 6]

The abbreviations shown in Tables 3, 4, 5, and 6 are as follows. <Liquid crystal> TL-202: Nematic liquid crystal composition, manufactured by BDH, TL-204: Nematic liquid crystal composition, manufactured by BDH, TL-205: Nematic liquid crystal composition, manufactured by BDH, E7: Nematic liquid crystal, manufactured by Merck Composition, E8; Nematic liquid crystal composition, manufactured by Merck Co., Ltd. <UV curing initiator> a: Merck Co., Ltd., Darocure 1173, b: Ciba Geigy Co., Ltd., Irgacure 651, <Polymer>PDiPF; Polyisopropyl difumarate The polymer of
Polymer / liquid crystal 15% by weight toluene solution, PDiPITA; polymer of diisopropyl polyitaconate, polymer / liquid crystal 15% by weight toluene solution, PMMA: methyl methacrylate polymer, polymer / liquid crystal 15% by weight Toluene solution.

From the results in Tables 3, 4, 5, and 6,
Examples 2-1 to 2-14 of the present invention correspond to Comparative Examples 2-3 and 2
-4, the cured composite film characteristics are superior. Further, in Examples, since 2-1 to 2-14 can be produced in a shorter time than Curing Examples 2-3 to 2-5 due to curing by UV rays or curing by EB rays, It can be seen that the productivity is excellent even if they are equal.

[0062]

[Table 7]

[0063]

[Table 8]

[0064]

[Table 9]

From the results of Tables 7, 8 and 9, it can be seen from Examples 3-1 to 3-11 that the liquid crystal composite display element of the present invention was used.
Indicates that the display characteristics and the adhesion are excellent in a well-balanced manner as compared with Comparative Examples 3-1 to 3-5.

Claims (6)

[Claims] 1. A water-insoluble polymer / liquid crystal composite film comprising a water-insoluble polymer and a liquid crystal, and at least two sheets on both sides of which a conductive substrate opposing a light-transmitting material is opposed to a conductive portion. In the liquid crystal composite display device having a light modulation function arranged as described above, the following general formula (1) is used. (Wherein, R ¹ and R ² may be the same or different groups, and R ¹ and R ^{2 each} have 1 carbon atom)
Represents a linear alkyl group having from 12 to 12 carbon atoms, a branched alkyl group having from 3 to 12 carbon atoms, a cycloalkyl group having from 3 to 12 carbon atoms, or an aryl group having from 7 to 20 carbon atoms, and may have a hetero atom or a substituent. In many cases, n represents an integer of 1 to 15. A) a polymer precursor / liquid crystal composition obtained by mixing a liquid crystal with a water-insoluble polymer precursor containing at least one unsaturated fatty acid diester represented by A liquid crystal composite display element characterized by the above-mentioned. 2. An unsaturated fatty acid diester represented by the following general formula (2) wherein n = 1: (Wherein, R ¹ and R ² may be the same or different groups, and R ¹ and R ^{2 each} have 1 carbon atom)
Represents a straight-chain alkyl group having 12 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 7 to 20 carbon atoms, and may have a hetero atom or a substituent. Good. 2. The liquid crystal composite display element according to claim 1, which is an itaconic acid diester represented by the formula: 3. A water-insoluble polymer precursor comprising a monomer (A) represented by the general formula (1) or (2) and a vinyl monomer (B) copolymerizable with said monomer. 3. The liquid crystal composite display device according to claim 1, further comprising: 4. The copolymerizable vinyl monomer is a hydroxy group-containing (meth) acrylic acid derivative.
The liquid crystal composite display device according to any one of the above items. 5. The method for producing a liquid crystal composite display element according to claim 1, wherein said water-insoluble polymer contains at least one monomer represented by the general formula (1) or (2). A polymer precursor / liquid crystal composition obtained by mixing a precursor and a liquid crystal is applied to one conductive substrate, cured by active energy rays, and then bonded to the other conductive substrate. A method for producing a liquid crystal composite display element, characterized by being obtained by: 6. After injecting the compound of the polymer precursor / liquid crystal composition into a cell composed of opposing conductive substrates,
6. The method for manufacturing a liquid crystal composite display device according to claim 5, wherein the curing is performed by an active energy ray.