JPH0283524A - Liquid crystal device and its production - Google Patents

Abstract

PURPOSE:To obtain the subject device capable of driving it at a low voltage, and making it a large-sized by composing a dimmer layer interposed between two sheets of substrates, of a transparent solid material of a liquid crystal material and a urethane-acrylate resin, and by constituting the transparent solid material so as to be in a particle state or a particle state or a three dimensional net-work state in the liquid crystal material. CONSTITUTION:The liquid crystal material and the transparent solid material are interposed between the two sheets of the substrates. The liquid crystal used, is composed of preferably a nematic, a smectic or a cholesteric liquid crystal. The liquid crystal material is composed of 4-substd. benzoic acid-4'- substd. phenyl ester, etc., and is necessary to form a continuous phase between the two sheets of the substrates. The transparent solid material contd. in the continuous phase of the liquid crystal material may be a particle-like dispersion and preferably the three dimensional net-work structure. The solid material is composed of preferably a UV ray curing type urethane-acrylate resin as an essential component. Thus, the liquid crystal is made it possible to drive at the low voltage.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a thin film containing a liquid crystal that can be formed over a large area. limit.

Blocking and transmitting can be controlled electrically, and it is used in the windows of buildings and show windows to block the field of view, as well as in curtains to control daylight, as well as to display characters and figures, and to provide high-speed response. By electrically switching the display, it can be used as a display device for advertising boards, guide boards, decorative display boards, etc.

(Prior art) Liquid crystal display elements have conventionally been TN using nematic liquid crystal.
type and STN type are in practical use.

A device using a ferroelectric liquid crystal has also been proposed.

These require polarizing plates and also require alignment treatment. On the other hand, as a method for producing large, inexpensive liquid crystal devices that are bright and have good contrast without requiring these, there is a method that involves encapsulating liquid crystals, dispersing liquid crystal droplets in a polymer, and making the polymer into a film. It has been known. Here, as the encapsulating substance, gelatin, arabic gum, polyvinyl alcohol, etc. have been proposed (% Table No. 58-501631, USP 44
No. 35047).

In the technology disclosed in the above specification, if the liquid crystal molecules encapsulated with polyvinyl alcohol have positive dielectric constant anisotropy in a thin layer, the liquid crystal molecules can be encapsulated in the presence of an electric field. are aligned in the direction of the electric field, and when the refractive index n0 of the liquid crystal and the refractive index np of the polymer are equal, transparency is exhibited. When the electric field is removed, the liquid crystal molecules return to their random alignment, and the refractive index of the liquid crystal droplet shifts by no. The liquid crystal droplet scatters light at its interface, blocking the transmission of light. becomes cloudy. In addition to the above-mentioned technology, there are several other known technologies in which thin films are made of polymers containing dispersed encapsulated liquid crystals. JP-A No. 62-2231 discloses a liquid crystal dispersed in a special ultraviolet curable polymer.

(Problems to be Solved by the Invention) The important characteristics required for the practical use of large liquid crystal devices such as those described above are (1) ability to be driven at low voltage, (11) sufficient contrast (ability to be driven in 110 time divisions) There is.

In particular, (1) and (11D) are extremely important characteristics in order to make the driving part of a device inexpensive. It has not been possible to create a liquid crystal device that does not.

As a result of intensive study on the preferred combination of the structure of a liquid crystal device and the transparent solid material used in the device, the present inventors found that it can be driven at a much lower voltage than conventional large liquid crystal devices, and that it can be driven with a polarizing plate. We have succeeded in creating a liquid crystal device that can be made larger without the need for the use of.

(Means for Solving the Problems) In order to solve the above problems, the present invention provides a liquid crystal device described below.

That is, the liquid crystal device according to the present invention has two substrates, at least one of which is transparent, which may have an electrode layer, and a light control layer supported between the substrates, and the light control layer is Consisting of a transparent solid substance consisting of a liquid crystal material and a urethane acrylate resin, the liquid crystal material forming a continuous phase, and the transparent solid substance existing in the liquid crystal material in the form of particles or a three-dimensional network. LCD display featuring
(hereinafter referred to as the liquid crystal device of the present invention).

In the device of the present invention, the substrate may be made of a rigid material, such as glass, metal, etc., or may be a flexible material, such as a plastic film. Two substrates can be placed facing each other with an appropriate distance between them.

In addition, at least one of the layers must be transparent so that the light control layer supported between the two layers can be seen from the outside world. However, complete transparency is not required. If this liquid crystal device is used to operate on sources passing from one side of the device to the other, both substrates are provided with suitable transparency. Appropriate transparent or opaque electrodes may be disposed on the entire surface or part of the substrate depending on the purpose.

A liquid crystal material and a transparent solid component are interposed between the two substrates. Incidentally, it is desirable to interpose a spacer for maintaining the distance between the two substrates according to a conventional method, as in well-known liquid crystal devices.

Of course, the liquid crystal material does not need to be a single liquid crystal compound, and may be a mixture containing two or more types of liquid crystal compounds or substances other than liquid crystal compounds. Any material that is recognized as having positive dielectric anisotropy may be used. The liquid crystal used is preferably nematic liquid crystal, smectic liquid crystal, or cholesteric liquid crystal.

As a liquid crystal material, for example, 4-substituted benzoate number 4'-f
tm phenyl ester, 4-[substituted cyclohexanecarboxylic acid 4'-tA phenyl ester, 4-substituted cyclohexanecarboxylic acid 4'-[substituted biphenyl ester,
4-(4-1-substituted cyclohexanecarbonyloxy)benzoic acid 4'-substituted phenyl ester, 4-(4-substituted cyclohexyl)benzoic acid 4'-substituted phenyl ester,
4-(4-f&[Lcyclohexyl)benzoic R4'-substituted cyclohexyl ester, 4-substituted 4'-substituted biphenyl, 4-substituted phenyl-4'-[6cyclohexane,
4-substituted 4"-substituted terphenyl, 4-substituted piphenyl 4'-substituted cyclohexane, 2-(4-substituted phenyl/l
/)-5-substituted biriminone and the like.

Liquid crystal materials require the formation of a continuous phase between two substrates. If the ratio of liquid crystal material components is low, it is difficult to form a continuous phase. The proportion of the liquid crystal material in the components of the light control layer is preferably 60% by weight or more, and the proportion of the liquid crystal material in the light control layer is preferably 70% by weight or more.
The transparent solid component present in the continuous phase of this liquid crystal material is
It may be dispersed in the form of particles, but preferably has a three-dimensional network structure. In any case, it is essential to form an optical interface with the liquid crystal material and to cause light to scatter. Its transparency can be determined appropriately depending on the purpose of use of the device, and its solidity and properties are not limited to solidity, but can be flexible, pliable, and elastic depending on the purpose. It's okay. If the particles are in the form of particles, the particles are either too large compared to the wavelength of the light, or if they are too small, light scattering properties cannot be expected, or particles of an appropriate size and shape can be selected depending on the purpose.

As these transparent solid components, those having an ultraviolet curable urethane acrylate resin as an essential component are preferable.

These liquid crystal devices can preferably be manufactured as follows.

That is, (1) between two substrates, at least one of which is transparent, which may have an electrode layer, (a) a liquid crystal material, (b) an ultraviolet curable urethane acrylate composition, and (C) polymerization initiation. (2)
The method for manufacturing a liquid crystal device of the present invention comprises polymerizing the ultraviolet curable urethane acrylate composition by irradiating ultraviolet rays through a transparent substrate.

The ultraviolet curable urethane acrylate composition used in the present invention is composed of an ultraviolet curable oligomer and, if necessary, an ultraviolet curable monomer.

Examples of the above-mentioned ultraviolet curable oligomers include 1.

A terminal incyanate compound obtained by reacting a diisocyanate compound and a polyether polyol or a polyester polyol in advance is further reacted with a hydroxyl group-containing acrylic monomer and/or a hydroxyl group-containing methacrylic monomer. Examples include addition polymerizable compounds having an acryloyloxy group and/or a methacryloyloxy group.

Examples of diisocyanate compounds include 2.4-tolylene diisocyanate, 2.6-)lylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and bis(isocyanatomethyl)cyclohexane. These diisocyanate compounds can be used alone or in combination.

Examples of polyether polyols include (1) (
a) Ethylene glycol, 1,2-propylene glycol, 1,3-gutylene glycol, trimethylene glycol, 1,4-butanediol, entamethylene glycol, 1,6-hexanediol, diethylene glycol, cyclopylene glycol, polyethylene Glycol, polyzolobile/glycol, neopentyl glycol, 2,2.4-trimethyl-1,3-bentanediol, cyclohexanediol, tumethylolcyclohexane, hydrogenated bisphenols, alkylene oxide adducts of hydrogenated bisphenols, bisphenols Glycols such as alkylene oxide adducts, alkylene oxide adducts of halodanated bisphenols, trimethylolethane, trimethylolethane 4'/
, glycerin, pentaerythritol, and other trihydric or higher polyhydric alcohols; (b) polyether preols obtained by the reaction with alkylene oxides such as ethylene oxide and propylene oxide; (2) polytetra obtained by cationic polymerization of tetrahydrofuran; Methylene glycol; (3) Examples include polyether polyols obtained by copolymerization of tetrahydrofuran and fullylene oxide.

Examples of polyether preols include (1) those produced by a combination reaction of polybasic acids and polyhydric alcohols, (2)
Examples include addition reaction between a polybasic acid and an epoxy group-containing compound, and (3) ring-opening polymerization between a polyhydric alcohol and a lactone compound.

Examples of polybasic acids include isophthalic acid, orthophthalic acid, naphthalene dicardic acid, succinic acid, adipic acid, azelaic acid, cepacic acid, dodecanedioic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and halogenated phthalic acid. 3,6-endomethylene-1.2,3.6
- Saturated nocargonic acids such as titrahydroheptallic acid; saturated polycargonic acids such as pyromellitic acid and trimellitic acid; unsaturated radicals such as fumaric acid, maleic acid, citraconic acid, and itaconic acid? Examples include phosphoric acid and the like.

Examples of polyhydric alcohols include ethylene glycol, ]s2-:y°ropylene glycol, 1.3-butylene glycol, trimethylene glycol, 1.4-
2tanediol, (tantamethylene glycol, 1.6-
Hexanediol, diethylene glycol, cyclopylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 2.2.4-
Trimethyl-1,3-penta/diol, cyclohexanediol, dimethylolcyclohexane, hydrogenated bisphenols, alkylene oxide adducts of hydrogenated bisphenols, alkylene oxide adducts of bisphenols, alkylene oxide adducts of halodanated bisphenols Glycols, such as)! J,i
'-F-Rolethane, trimethylolpropane, glycerin, and trihydric or higher polyhydric alcohols such as pentaerythritol.

Examples of the epoxy group-containing compound include ethylene oxide, propylene oxide, and glycidyl ester of carboxylic acid.

Lactone compounds include β-gropiolactone, β-
Butyrolactone, δ-valerolactone, α, β, r-)
! J methoxy δ-valerolactone, β-methyl-δ-
Valerolactone, ε-cabroctone, β-methyl-e
-isoglopyru-g-caprolactone and the like.

Hydroxyl group-containing acrylic monomers and hydroxyl group-containing methacrylic monomers are obtained by the reaction of a compound having an epoxy group with acrylic acid, methacrylic acid, drying oil fatty acid or semi-drying oil fatty acid, or acrylic acid Alternatively, it can be obtained by reacting methacrylic acid or a functional derivative thereof with a polyhydric alcohol. In the latter case, the reaction molar ratio of acrylic acid or methacrylic acid to polyhydric alcohol is 1 or less when the polyhydric alcohol is a dihydric alcohol, 2 or less when the polyhydric alcohol is a trihydric alcohol, or 4 or less.
In the case of alcohol, it is 3 or less.

Specific examples of such compounds include the following compounds. Ethylene glycol monoacrylate, ethylene glycol monomethacrylate, 192-
f Robylene glycol monoacrylate), 1.2-propylene glycol monomethacrylate, 1.3-propylene glycol monoacrylate), 1.3-propylene glycol monomethacrylate, 1.4-butanool monoacrylate, L3 -butanediol methacrylate, 2-butene-1,4-diol monoacrylate, 2-butene-1,4-diol monomethacrylate,
1.6-hexanethiol monoacrylate? , 1.6-
2 such as hexanethiol monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, dipropylene glycol monoacrylate, diethylene glycol monoacrylate, etc.
Monoacrylate or monomethacrylate of alcohol; trimethylolethane monoacrylate, trimethylolethane bis(acryle)), l-methylolethane monomethacrylate, trimethylolethane bis(
methacrylate), trimethylolpropane monoacrylate, trimethylolpropane bis(acrylate), trimethylolpropane monomethacrylate, trimethylolpropane bis(methacrylate), glycerin monoacrylate, glycerin bis(acrylate), glycerin monomethacrylate , glycerin bis(
monoacrylates or bisacrylates of trihydric alcohols, such as (methacrylate); or monomethacrylates or bismethacrylates;
methacrylate), pentaerythritol tris(acrylate), bis-acrylate or tris-acrylate of a polyhydric alcohol of 4 or more valences, such as pentaerythritol tris(methacrylate), or bis-methacrylate or tris-methacrylate.

Examples of ultraviolet curable oligomers that can be used in the present invention include Aroex M-1100j, R70 Nix M-120 manufactured by Toagosei Chemical Industry Co., Ltd. (2)
0J, r C-9503J, l manufactured by Sartomer
-C-9504J, “Higashi Ester U-108-A J,” “Goku Ester U-4HA” manufactured by Shin Nakamura Chemical Industry ((trans))
”, “Viscoat 812” manufactured by Osaka Organic Chemical Industry (a)
”, “Viscoat 813”, etc.

Examples of the UV-curable monomer include styrene, chlorostyrene, α-methylstyrene, and divinylbenzene; substituents include methyl, ethyl, clovyl, butyl, amyl, 2-ethylhexyl, octyl, nonyl, dodecyl, and hexadecyl. , octadecyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, allyl, methallyl, glycidyl, 2
- Acrylates, methacrylates or 7-malates with groups such as hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl, etc.; ethylene glycol, polyethylene glycol, propylene glycol, borripropylene glycol , 1. Mono(meth)acrylates or poly(meth)acrylates such as 3-butylene glycol, tetramethylene glycol, hexamethylene glycol, trimethylolpronochloride, glycerin and pentaerythritol; vinyl acetate, vinyl butyrate or vinyl benzoate, Acrylonitrile, cetyl vinyl ether, limonene, cyclohexene, diallyl phthalate, diallyl isophthalate, 2-3- or 4-vinylpyridine, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-hydroxymethylacrylamide or N-hydroxyethylmethacrylamide and These alkyl ether compounds, di(meth)acrylates of diols obtained by adding 2 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol, trimethylol glono, 3 to 471 moles
Triol di- or tri(meth) obtained by adding mol or more of ethylene oxide or propylene oxide
Acrylate, di(meth)acrylate of diol obtained by adding 2 moles or more of ethylene oxide or propylene oxide to 1 mole of bisphenol A, 1 mole of 2-hydroxyethyl (meth)acrylate and phenyl isocyanate (L < Han-2 methyl isocyanate) Examples include reaction products with 1 mole of dipentaerythritol, poly(meth)acrylate of dipentaerythritol, trimethylolpropane triacrylate, tricyclodecane dimethylol diacrylate, polyethylene glycol noacrylate, polypropylene glycol. Particularly preferred are cyacrylate, hexanediol noacrylate, neointhyl glycol diacrylate, tris(acryloxyethyl)isocyanurate, and nonylphenoxypolyglopylene glycol mo/7 acrylate in terms of compatibility with the liquid crystal material.

The size of the three-dimensional network can be controlled by the combined use of the ultraviolet curable upper layer, thereby improving the performance of the liquid crystal device to a desired level.

As a photopolymerization initiator, for example, 2-hyproxy2-
Methyl-1-pheergulonyan-1-one (Merck & Co., Ltd. “Darocur 1173J”), 1-hydroxycyclohexylphenylct/(Chipa Geigy “Irgacure 184J”), 1-(4-isoglobylphenyl) −
2-Hydroxy-2-methylpropan-1-one (Merck & Co., Ltd. “Darocur 1116J”), benzyl dimethyl ketal (Chipa Geigy Co., Ltd. “Irgacure 651J”)
, 2-methyl-1-(4-(methylthio)phenyl]-
2-morpholinogloronone-1 (Irgacure 907J manufactured by Chipa Geigy), 2,4-noacylthioxanthone (Kayacure DETXJ manufactured by Nippon Kayaku Co., Ltd.) and P
- Mixture with ethyl trimethylaminobenzoate (Kayacure EPAJ manufactured by Honkayaku Co., Ltd.), inglobilteoxanthone (Kantacure I manufactured by Ward Prekin Sodde Co., Ltd.)
TXJ) and ethyl P-trimethylaminobenzoate, etc., and liquid 2-hydroxy-2-methyl-1-7enylglono and 7-1-one are combined with liquid crystal and UV-curable urethane acrylate compositions. This is particularly preferred in terms of compatibility.

Optional components include photosensitizers, chain transfer agents, antioxidants, thermal polymerization inhibitors, dyes, crosslinking agents, etc., and the types of the UV-curable prepolymers, UV-curable monomers, etc. It can be selected as appropriate depending on the desired performance of the liquid crystal device.

In particular, when using a chain transfer agent, UV-curable prepolymers,
UV curing is extremely effective depending on the type of monomer, preventing the resin from becoming too cross-linked, thereby making the liquid crystal material more responsive to electric fields and exhibiting low voltage drive performance. .

Good examples of chain transfer agents are butanediol dithioglopionate, pentaerythritol tetrakis (β-thioglopionate), triethylene glycol dimercaptan, and the like. The amount of chain transfer agent added varies depending on the type of UV-curable prepolymer or UV-curable monomer used, but if it is too small, the effect will be weak, and if it is too large, the opacity of the liquid crystal device will decrease, and the liquid crystal device will be damaged. This is not preferable because the contrast tends to deteriorate.

The effective amount thereof is preferably 0.05 to 30% by weight, and 0.1% by weight based on the ultraviolet curable urethane acrylate composition.
-20% by weight is particularly preferred.

In order to support a solution containing each of these components between two substrates, this solution may be injected between the substrates, but it may be applied onto one substrate using a coater such as a spinner.
Then, the other substrate may be placed on top of the other substrate.

Curing of the uncured solution can be accomplished by irradiating a suitable dose of ultraviolet light through the transparent substrate. Depending on the type of UV-curable polymer, UV-curable monomer, or optional components, heat or electron beams can be used instead.

The thickness of the light control layer is usually adjusted to a range of 5 microns to 30 microns.

The liquid crystal device configured in this manner is capable of time-division driving, which was not possible with conventional droplet dispersion type liquid crystal devices, and also has a lower driving voltage than conventional droplet dispersion type liquid crystal devices. For example, conventional droplet dispersion type liquid crystal devices require a driving voltage of 60 V or more in effective value, and in many cases 100 V or more. This liquid crystal device achieves a startup response time of 3 to 4 milliseconds and a fall response time of 5 to 8 milliseconds at a driving voltage of approximately 10 to 50V.

In addition, the liquid crystal device configured in this manner is ideal for manufacturing flexible liquid crystal devices using transparent plastic films such as polyethylene terephthalate as substrates, and is suitable for manufacturing flexible liquid crystal devices using rigid materials such as glass as substrates. In particular, a robust liquid crystal device can be produced. When a plastic film is used as a substrate,
It has the great industrial advantage of being able to easily mass-produce large-area liquid crystal devices using commonly known coating and laminating methods. According to the present invention, it is possible to easily manufacture a liquid crystal device that is sandwiched between such glass film substrates, has adhesive properties to the extent that there is no practical problem, and has a large area and flexibility.

In addition, in the present invention, when selecting each of the liquid crystal material and the transparent solid component, the proportion of the liquid crystal material is large, so that light scattering can be prevented without paying special attention to the refractive index of each material. An optical boundary surface having a shape and size sufficient to cause a droplet dispersion is effectively formed, and a high contrast of 1:2 to 14 is achieved, which is comparable to that of a conventional droplet dispersion type liquid crystal device.

Furthermore, the liquid crystal device of the present invention changes to a transparent state when the temperature reaches a temperature above which the liquid crystal material undergoes a phase transition to an isotropic liquid phase without applying a voltage, so a liquid crystal material having an appropriate phase transition temperature is selected. Therefore, it can also be used as a temperature-sensitive (temperature-responsive) optical modulation device in a desired temperature range.

(Examples) Hereinafter, the present invention will be described in more detail by showing examples of the present invention, but the present invention is not limited to these examples.

Synthesis Example 1 (Preparation of polyether urethane acrylate)
1 set with stirring device, thermometer, and condenser! In a four-bottle flask, add "Efsenol 4020J (polyether polyol manufactured by Asahi Ohlin (Ten)) 86.6i2,4
-tolylene diisocyaner) (TDI-100) 7.6
g and 0.004 g of dibutyltin silaurylate were charged, the temperature was raised to 60° C., and the mixture was reacted for 1 hour. Then, 5.8 g of hydroxyglobil acrylate, t-butyl bidroquinone o, o s , y, dibutyl tin dilauryl) 0. O15,9 was charged and reacted at 70°C for 8 hours to produce a 4-liether with an incyanato group content of 0.04% by weight and a viscosity of xylene:reaction product=3nia (weight ratio) of O as measured by a Gardner bubble viscometer. Urethane acrylate was obtained quantitatively.

Synthesis example 2 (preparation of polyether urethane acrylate)
- As a riether polyol, “PTG-850j (
Hodogaya Chemical Industry (Tosei polytetramethylene ether glycol 6&7g with number average molecular weight 850, TDI-1
0020,8,! ir, hydroxyglobil acrylate) 10. The reaction was carried out in the same manner as in Synthesis Example 1 except that S Il was used.

A polyether urethane acrylate having an isocyanate group content of 0.04% by weight and a viscosity of xylene:reaction product-4=6 (weight ratio) u2-V measured by an f-donor bubble viscometer was quantitatively obtained.

Synthesis Example 3 (Preparation of polyester urethane acrylate) Ethylene glycol: ], 6-hexanediol = 1
: 3 (molar ratio) and phthalic anhydride rR: adipic acid-1
: Number average molecular weight obtained by reaction with 1 (molar ratio) 100
0 polyester polyol 62412.4-tolylene diisocyanate: 2,5-tolylene diisocyanate) - 80:20 (weight ratio) mixture 21.7F, hydroxyethyl acrylate 15.9 gt, t-butylhide"cI quinone The reaction was carried out in the same manner as in Synthesis Example 1, except that hydroquinone was used instead.

Isocyanate group content 0.06% by weight, dimethylformamide measured by Gardner bubble viscometer: Reaction product-1
Polyester urethane acrylate having a viscosity of GI: 2 (weight ratio) was quantitatively obtained.

Synthesis Example 4 (Preparation of /reester urethane acrylate)
As a polyester polyol, “Kurapol L-101”
The reaction was carried out in the same manner as in Synthesis Example 1, except that 0'' (manufactured by Kuraray) 6LOg, TDI-10021,6ta, and hydroxypropyl acrylate 1a41I were used.

A polyester urethane acrylate having an isocyanate group content of 0807 by weight and a xylene:reaction product-3 viscosity (weight ratio) of R-8 as measured by a donor bubble viscometer was quantitatively obtained.

Synthesis Example 5 (Preparation of polyester urethane acrylate)
Number average molecule obtained from the reaction product of dodecanionic acid and Cardura E-10J (glycisol ester manufactured by Shell Chemical Co., Ltd.), 1xooo polyester polyol 70.69, trimethylhexamethylene diinocyanate 21, 2.9
The reaction was carried out in the same manner as in Synthesis Example 1, except that hydroxypropyl acrylate 8.2I was used.

A polyester urethane acrylate having an incyanato group content of 0.07 g and a xylene:reaction product-3 (weight ratio viscosity of u2-V) measured by a Gardner bubble viscometer was quantitatively obtained.

Example 1 Polyether urethane acrylate obtained in Synthesis Example 1) 10
0! Quantity parts, liquid crystal materials Dainippon Ink & Chemicals (Dogmade Nemati, liquid crystal composition rDOX-4062J 40
0yJL and 30 parts by weight of 2-hydroxy-2-methyl-1-phenyl fa pan-]-one as a photopolymerization initiator were mixed, and a small amount of glass fiber with an average particle size of 11 μm was added as a spacer. cm x 5
cm transparent conductive film with scissors shifted 2 m above and below, and the bottom of metal halide lung (80W/cm) is a5 m.
A liquid crystal device was obtained by passing the liquid crystal at a speed of /min. The applied energy corresponds to 500 rnJ/cm''.

The obtained nine liquid crystal devices were cut into 1 cm width pieces, and both ends were pulled using a tensile tester to evaluate adhesion.
6 kti/cm”.

In addition, the obtained liquid crystal device is 20V (50Hz AC)
It became completely transparent at the driving voltage. The light transmittance ratio (contrast) between the opaque state and the transparent state was 1:2.

When the cross section of the light control layer was observed using a scanning electron microscope, a three-dimensional polymer network was observed.

The characteristics of the liquid crystal material "DOX-40624" used are as follows.

Clearing point 60.3℃ Melting point -31℃ Threshold voltage Vth O,99 Birefringence
Δn O, 140 ordinary refractive index no
1.4970 dielectric constant anisotropy
227 Example 2 Preether urethane acrylate 10 obtained in Synthesis Example 2
A liquid crystal device was obtained in the same manner as in Example 1 except that 0f dobe was used.

Adhesion was evaluated in the same manner as in Example 1 and was found to be 1.0 kll/cm''.

Furthermore, the obtained liquid crystal device became completely transparent at a driving voltage of 30 V (50 Hz AC). Contrast is 1:
It was 3.

Example 3 Polyether urethane acrylate 67 obtained in Synthesis Example 1
A liquid crystal device was obtained in the same manner as in Example 1, except that a mixture of parts by weight and 33" parts of nonylphenoxy polypropylene glycol monoacrylate was used as the ultraviolet curable urethane acrylate composition.

Adhesion was evaluated in the same manner as in Example 1.
21 kg/2 vices.

Furthermore, the obtained liquid crystal device became completely transparent at a driving voltage of 20 V (50 Hz AC). Contrast is 1:
It was 4.

Example 4 Polyester urethane acrylate obtained in Synthesis Example 3) 1
A liquid crystal device was obtained in the same manner as in Example 1 except that a 00 TJ section was used.

Adhesion was evaluated in the same manner as in Example 1 and was found to be 1.7 kg 7 cm''.

Furthermore, the obtained liquid crystal device became completely transparent at a driving voltage of 20 V (50 Hz AC). Contrast is 1:
It was 2.

Example 5 Polyester urethane acrylate 10 obtained in Synthesis Example 4
A liquid crystal device was obtained in the same manner as in Example 1 except that 0 parts by weight was used.

Adhesion was evaluated in the same manner as in Example 1 and was found to be 1.5 kll/cm''.

Furthermore, the obtained liquid crystal device became completely transparent at a driving voltage of 30 V (50 Hz AC). Contrast is 1:
It was 2.

Example 6 Polyester urethane acrylate obtained in Synthesis Example 5) 10
A liquid crystal device was obtained in the same manner as in Example 1 except that 0 parts by weight was used.

Adhesion was evaluated in the same manner as in Example 1 and was found to be 1.4 kg/2.

Furthermore, the obtained liquid crystal device became completely transparent at a driving voltage of 20 V (50 Hz AC). Contrast is 1:
It was 4.

Comparative Example 1 100 parts by weight of rHX-620J (Nippon Kayaku (Kyusei Kaglolactone modified hydroxypiparic acid ester neopentyl glycol diacrylate) was used as an ultraviolet curable composition, and 2-hydroxy-2- as a photopolymerization initiator)
A liquid crystal device was obtained in the same manner as in Example 1 except that 2 parts by weight of methyl-1-phenylglo/#7-1-one was used.

Adhesion was evaluated in the same manner as in Example 1, and the result was 0.4 kg/c! r1” and k.

(Effects of the Invention) As described above, the present invention is a large-area, thin-film liquid crystal device that can be driven at a low voltage of 10 to 50 V, and has a short start-up response time even at such a low voltage. 3~
It has a high response speed of 4 milliseconds, a high contrast between transparent and opaque, and has a threshold value, so multiplex driving is possible.

Therefore, it is extremely easy to adjust lighting, adjust visibility, and display large-sized characters and graphics, and furthermore, it is extremely easy to manufacture such a liquid crystal device.

Further, since the liquid crystal device of the present invention has excellent adhesiveness to the substrate, a liquid crystal device having a large area and flexibility can be easily manufactured.

Agent Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. Two substrates, at least one of which is transparent, which may have an electrode layer, and a light control layer supported between the substrates, wherein the light control layer is made of a liquid crystal material. and a urethane acrylate resin, the liquid crystal material forms a continuous phase, and the transparent solid material is present in the liquid crystal material in the form of particles or a three-dimensional network. LCD device. 2. The liquid crystal device according to claim 1, wherein the urethane acrylate resin is polyether urethane acrylate or polyester urethane acrylate. 3. The liquid crystal device according to claim 1 or 2, wherein the liquid crystal material accounts for 60% by weight or more of the components of the light control layer. 4. The liquid crystal device according to claim 1, 2 or 3, wherein the transparent solid substance forms a three-dimensional network in the liquid crystal material. 5. Claim 1, wherein the light control layer has a thickness of 5 to 30 microns.
4. The liquid crystal device according to 2, 3 or 4. 6. The liquid crystal device according to claim 1, 2, 3, 4 or 5, wherein the liquid crystal material is a mixture of one or more selected from the group consisting of nematic liquid crystal, smectic liquid crystal and cholesteric liquid crystal. 7. (1) Between two substrates, at least one of which is transparent, which may have an electrode layer, (a) a liquid crystal material, (b) an ultraviolet curable urethane acrylate composition, and (c) polymerization initiation. 2. The method according to claim 1, comprising: interposing a light control layer forming material containing a light control layer agent, and then (2) irradiating the ultraviolet rays through a transparent substrate to polymerize the ultraviolet curable urethane acrylate composition. A method for manufacturing liquid crystal devices. 8. The ultraviolet curable urethane acrylate composition contains a terminal isocyanate compound obtained by reacting a diisocyanate compound and a polyether polyol or a polyester polyol in advance, and a hydroxyl group-containing acrylic monomer and/or a hydroxyl group-containing methacrylate monomer. 8. The method for producing a liquid crystal device according to claim 7, which contains an addition-polymerizable compound having two or more acryloyloxy groups and/or methacryloyloxy groups in the molecule obtained by reacting. 9. The method for manufacturing a liquid crystal device according to claim 7 or 8, wherein the liquid crystal material accounts for 60% by weight or more of the material constituting the light control layer. 10. The method for manufacturing a liquid crystal device according to claim 7, 8 or 9, wherein the liquid crystal material is a mixture of one or more selected from the group consisting of nematic liquid crystal, smectic liquid crystal and cholesteric liquid crystal.