WO2016159672A1

WO2016159672A1 - Liquid crystal device

Info

Publication number: WO2016159672A1
Application number: PCT/KR2016/003306
Authority: WO
Inventors: 임은정; 민성준; 유정선; 김정운; 김진홍; 오동현
Original assignee: 주식회사 엘지화학
Priority date: 2015-03-31
Filing date: 2016-03-31
Publication date: 2016-10-06

Abstract

The present application relates to a liquid crystal device and the like. The liquid crystal device of the present application can implement a transparent white state, a transparent black state, and a scattering state according to the frequency and/or the amount of voltage to be applied. The liquid crystal device, for example, can be applied to uses of a vehicle window, a smart window, a window protection film, a display device, a display shielding plate, a 3D image display active retarder, or a viewing angle-adjusting film, or the like.

Description

Liquid crystal elements

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0045015, filed March 31, 2015 and Korean Patent Application No. 10-2016-0038645, filed March 30, 2016. All contents disclosed in the documents of the Korean patent application are included as part of the present specification.

The present application relates to a liquid crystal element and its use.

The liquid crystal device can control the transmittance of light by switching the alignment of the liquid crystal through an external signal such as application of a voltage, and thus can be used as a variable transmittance device. The liquid crystal device may be applied to display devices of various information devices as well as various light blocking products such as light blocking plates for organic light emitting diodes (OLEDs) or automotive and smart windows.

The light shielding or light-transmitting mechanism of the liquid crystal device may be classified into a transparent white, a transparent black or a scattering state, and the like, and a general liquid crystal device may switch between the transparent white and the transparent black states, or switch between the transparent white and the scattering states. It is a double state device. In the above, the transparent white state has a high linearity of light transmittance and a low haze, and the transparent black state has a low linearity of light transmittance and a low haze, and the scattering state has a low linearity light transmittance and a high haze. It can mean a state.

A liquid crystal element applied to a display device or the like is a device for switching between transparent white and transparent black states, and switching between transparent white and scattering states, for example, so-called PDLC (Polymer) as described in Patent Document 1 or the like. Dispersed Liquid Crystal).

Patent Document 1: Republic of Korea Patent Publication No. 2014-0077861

The present application provides a liquid crystal device and its use.

The present application relates to a triple state liquid crystal device. In the present application, the term triple phase liquid crystal device may implement a transparent white state, a transparent black state, and a scattering state, and may refer to a device capable of mutual switching between the three types of states.

In the present application, the term transparent white state means a state in which the linear light transmittance of the liquid crystal element or the liquid crystal layer is 25% or more and the haze is 5% or less, which may be referred to as a first state. In addition, the term transparent black state may mean a state in which the linear light transmittance is 15% or less and the haze is 5% or less, which may be referred to as a second state. The term scattering state may mean a state in which the linear light transmittance is 10% or less and the haze is 80% or more, which may be referred to as a third state.

In the first state, the linear light transmittance is 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more 90% or more, haze of 3% or less, 2.5% or less, 2% or less, 1.5% or less, or 1% or less, and the second state has a linear light transmittance of 20% or less, 15% or less, 10% or less, or 5 % Or less, haze of 3% or less, 2.5% or less, 2% or less, 1.5% or less, or 1% or less, and in the third state, linear light transmittance is 5% or less, and haze is 90% or more or 95% or more. Can be.

In the present application, the transmittance, the linear light transmittance, and the haze are numerical values measured according to the ASTM D1003 standard.

The liquid crystal device of the present application includes a liquid crystal layer. The term liquid crystal layer may mean a layer comprising at least a liquid crystal compound.

The liquid crystal layer of the present application may have a horizontal conductivity of 1.0 × 10 ⁻⁴ μS / cm or more. When the liquid crystal layer is adjusted to show the horizontal conductivity in this range, the liquid crystal layer implements all of the first to third states according to the magnitude and frequency of the applied voltage, and changes from one of the three states to another. It was confirmed that switching was possible. The horizontal conductivity of the liquid crystal layer is, in another example, 2.0 × 10 ^-4 μS / cm or more, 3.0 × 10 ^-4 μS / cm or more, 4.0 × 10 ^-4 μS / cm or more, 5.0 × 10 ^-4 μS / cm or more , 6.0 × 10 ^-4 μS / cm or more, 7.0 × 10 ^-4 μS / cm or more, 8.0 × 10 ^-4 μS / cm or more, 9.0 × 10 ^-4 μS / cm or more or 1.0 × 10 ^-3 μS / cm or more Can be. In another example, the horizontal conductivity is 5.0 × 10 ⁻² μS / cm or less, 3.0 × 10 ⁻² μS / cm or less, 1.0 × 10 ⁻² μS / cm or less, 9.0 × 10 ⁻³ μS / cm or less, 7.0 × 10 Or less than ⁻³ μS / cm, 5.0 × 10 ⁻³ μS / cm, 3.0 × 10 ⁻³ μS / cm or less, or 2.5 × 10 ⁻³ μS / cm or less.

In the present application, the term horizontal conductivity is conductivity measured while applying a voltage to the liquid crystal layer, and the direction of the electric field in a state where a voltage is applied so that the direction of the electric field due to the optical axis of the liquid crystal layer and the applied voltage is substantially horizontal. It may be measured according to. The measurement frequency of the voltage applied above is 60 Hz, the measurement voltage may be 0.5V.

Meanwhile, vertical conductivity, which will be described later, is a conductivity measured while applying a voltage to the liquid crystal layer, and the voltage of the electric field is applied in a state in which a voltage is applied so that the direction of the electric field due to the optical axis of the liquid crystal layer and the applied voltage is substantially perpendicular. It may be a value measured along the direction. The measurement frequency of the voltage applied above is 60 Hz, the measurement voltage may be 0.5V.

The optical axis of the liquid crystal layer may be determined according to the type of liquid crystal compound. For example, if the liquid crystal compound is in a rod shape, the optical axis of the liquid crystal layer may mean a long axis direction in a state in which the liquid crystal compounds included in the liquid crystal layer are aligned. For example, when the liquid crystal compounds in the liquid crystal layer are vertically aligned in parallel with the thickness direction of the liquid crystal layer, the horizontal conductivity may be determined by applying a voltage to form an electric field along the thickness direction of the liquid crystal layer. It may be the conductivity measured along the thickness direction. Further, when the liquid crystal compound in the liquid crystal layer has a rod shape and the liquid crystal compounds are horizontally aligned in the liquid crystal layer, the vertical conductivity may be applied while applying a voltage to form an electric field in the thickness direction of the liquid crystal layer. It may be the conductivity measured in the thickness direction.

On the other hand, unless otherwise specified, the vertical or horizontal conductivity in the present application, as described above, the measurement frequency of the voltage applied to the liquid crystal layer is 60 Hz, the voltage is 0.5V in each of the above methods Accordingly, the conductivity measured at room temperature may be a value converted to a numerical value represented by an area of 1 cm ² (width: 1 cm, length: 1 cm) and having a thickness of 1 cm.

In the examples described later, the measured area of the liquid crystal layer having an area of 9 cm ² (width: 3 cm, length: 3 cm), the thickness of 15 μm is 1 cm ² (width: 1 cm, length: 1 cm), and the thickness is It converted into the numerical value which the liquid crystal layer which is 1 cm will display.

Formula applied to the conversion is the same as the following formula 1 to 3.

[Equation 1]

C = 1 / ρ

[Formula 2]

R = 1 / CR

[Equation 3]

R = ρ × D / A

In Equations 1 to 3, C is a horizontal or vertical conductivity, ρ is a specific resistance of the liquid crystal layer, CR is a measured value of horizontal or vertical conductivity, R is a resistance of the liquid crystal layer, D is the thickness of the liquid crystal layer, A Is the area of the liquid crystal layer.

For example, after calculating the resistance (R) by substituting the measured value (CR) of the conductivity measured for the liquid crystal layer having a predetermined thickness and area into Equation 2, the liquid crystal layer (R) and the Equation 3 are used. The specific resistance (ρ) of area: 1 cm ² (= width: 1 cm, length: 1 cm) and thickness: 1 cm) can be obtained, and the resistivity can be substituted into Equation 1 to obtain vertical or horizontal conductivity.

In the present specification, the horizontal alignment of the liquid crystal layer or the liquid crystal compound is a state in which the liquid crystal compounds of the liquid crystal layer are substantially horizontally aligned in the form of a rod, which is a liquid crystal compound. (Rin) is in the range of 150 nm to 3,000 nm, the thickness direction retardation (Rth) according to the following formula B may mean a case in the range of 0 nm to 100 nm or 0 nm to 50 nm, the term liquid crystal layer Alternatively, the vertical alignment of the liquid crystal compound is in the form of a rod, which is a liquid crystal compound, and the liquid crystal compounds of the liquid crystal layer are substantially vertically aligned, for example, the planar phase difference Rin is 0 nm to 100 nm or The thickness direction retardation (Rth) may be in the range of 0 nm to 50 nm, and in the range of 150 nm to 3000 nm.

[Formula A]

Rin = d (nx-ny)

[Formula B]

Rth = d (nz-ny)

In Equations A and B, d is the thickness of the liquid crystal layer, nx is the refractive index in the slow axis direction in the liquid crystal layer plane, ny is the refractive index in the direction perpendicular to the slow axis, nz is the thickness direction, that is, the slow axis and It is the refractive index of the direction perpendicular to all the perpendicular directions. As used herein, the term refractive index may be a refractive index for light having a wavelength of 550 nm, unless otherwise specified.

In addition, as described above, in the present application, the conductivity is 1 cm ² (width: 1 cm, length: 1 cm) and the thickness at room temperature measured under a measurement frequency of 60 Hz and a measurement voltage of 0.5 V, unless otherwise specified. Is a value converted into a numerical value represented by a 1 cm liquid crystal layer, and the conductivity may be measured according to a manufacturer's manual using a measuring instrument (LCR meter, manufactured by Aglient, Inc., E4980A). In the case where the measured temperature affects the numerical value among the physical properties described in the above, unless otherwise specified, the physical property is a numerical value measured at room temperature, where the term normal temperature is a natural temperature that is warmed or undecreased. It can mean any temperature in the range of about 10 ° C to 30 ° C, for example, about 23 ° C or about 25 ° C.

The method of adjusting the conductivity itself of the liquid crystal layer is well known, and for example, additives suitable for the liquid crystal layer, for example, ionic impurities, ionic liquids, salts, reactive monomers, The conductivity can be controlled by adding additives such as initiators or anisotropic dyes.

The ratio (PC / VC) of the vertical conductivity (VC) of the liquid crystal layer and the horizontal conductivity (PC) of the liquid crystal layer is about 0.2 or more, about 0.25 or more, about 0.3 or more, about 0.35 or more, about 0.4 or more, or about 0.45 or more. , At least about 0.5, at least about 0.55, at least about 0.6, at least about 0.65 or at least about 0.7. In addition, the ratio (PC / VC) may be about 2.5 or less, about 2.0 or less, about 1.5 or less, or about 1.0 or less. The ratio (VC / PC) of the horizontal conductivity (PC) of the liquid crystal layer and the vertical conductivity (VC) of the liquid crystal layer is about 2.0 or less, about 1.9 or less, about 1.8 or less, about 1.7 or less, about 1.6 or less, or about 1.5 or less. , About 1.4 or less, about 1.3 or less, about 1.2 or less, about 1.1 or less, or about 1.0 or less. In addition, the ratio (VC / PC) may be about 0.5 or more, about 0.3 or more, about 0.2 or more, or about 0.1 or more. Such conductivity (PC, VC) may also be adjustable by appropriate addition of the additives described above. When the ratio of the conductivity (VC / PC and / or PC / VC) is adjusted as described above, it may be advantageous in terms of driving efficiency of the liquid crystal device.

The liquid crystal device may be in the first or second state in an initial state. In the present application, the term initial state may refer to a state in which an external signal for driving a liquid crystal compound such as a voltage is not applied.

In the initial state as described above, it may be switched to another state (any one of the first to third states) by applying a voltage of a predetermined frequency, and may change the magnitude and / or frequency of the applied voltage, or change the applied voltage. By removing it can be switched to another state.

In the liquid crystal device, the application frequency F1 and the application voltage V1 for the implementation of the first or second state and the application frequency F2 and the application voltage V2 for the implementation of the third state are the following condition 1 and / or 2 can be satisfied.

[Condition 1]

F1> F2

[Condition 2]

V1 ≦ V2.

That is, the applied frequency F1 required to implement the second state when the initial state is the first state, or the applied frequency F1 required to implement the first state when the initial state is the second state, It is always larger than the applied frequency F2 required to implement the third state according to condition 1 above. In one example, the ratio of the applied frequency (F1 / F2) is greater than 1, for example, may be 1.5 or more, 2 or more, 2.5 or more or 3 or more. In another example, the ratio F1 / F2 may be 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4.5 or less.

Meanwhile, when the initial state is the first state, the applied voltage V1 required to implement the second state or when the initial state is the second state, the applied voltage V1 required to implement the first state is: According to the condition 2, it is smaller than or equal to the applied voltage V2 required to implement the third state. In one example, the ratio of the applied voltage (V2 / V1) may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more or 5.5 or more. The ratio V2 / V1 may be 20 or less, 15 or less or 10 or less in another example.

The applied frequency F1 required to implement the second state when the initial state is the first state, or the applied frequency F1 required to implement the first state when the initial state is the second state, is for example. For example, it may be 90 Hz or more, 100 Hz or more, 150 Hz or more, 200 Hz or more, 250 Hz or more, or 300 Hz or more. In another example, the applied frequency F1 may be 600 Hz or less, 500 Hz or less, or 400 Hz or less.

In addition, the applied frequency F2 required to implement the third state may be 110 Hz or less, 100 Hz or less, 90 Hz or less, 80 Hz or less, 70 Hz or less, 60 Hz or less, 50 Hz or less, or 40 Hz or less. . In another example, the applied frequency F2 may be 10 Hz or more or 20 Hz or more.

The applied voltage V1 required to implement the second state when the initial state is the first state or the applied voltage V1 required to implement the first state when the initial state is the second state is, for example. For example, 50V or less, 45V or less, 40V or less, 35V or less, 30V or less, 25V or less, 20V or less, or 15V or less. The applied voltage V1 may be 5V or more in another example.

In addition, the applied voltage V2 required to implement the third state may be 50V or more or 65V or more. In another example, the applied voltage V2 may be 200 V or less, 150 V or less, 100 V or less, 80 V or less, or 70 V or less.

The applied frequency F1 and / or F2 and / or the applied voltage V1 and / or V2 are, for example, in accordance with a change in conductivity of the liquid crystal layer within a range satisfying the condition 1 and / or 2. Can be adjusted.

In one example, the triple phase liquid crystal device may satisfy Equation A below.

[Formula A]

20 ≤ H1 / H2

In Equation A, H1 is the haze of the triple-phase liquid crystal device at a frequency of 30 Hz and a voltage of 60 V, and H2 is a voltage unapplied state or at a frequency of 100 Hz and a voltage of 10 V. It is the haze of the said triple phase liquid crystal element.

In Formula A, H1 / H2 may be a ratio of haze (H1) of the liquid crystal device expressed in the third state and haze (H2) of the liquid crystal device expressed in the first or second state. In the present application, by adjusting the conductivity of the liquid crystal layer to the above range it is possible to implement a haze difference of the same range as the formula (A). In Formula A, H1 / H2 is, in another example, 25 or more, 30 or more, 35 or more, 40 or more, 45 or more, 50 or more, 55 or more, 60 or more, 65 or more, 70 or more, 75 or more, 80 or more, 85 or more Or 90 or more. In Formula A, H1 / H2 may be 100 or less or 98 or 96 or less in another example.

In one example, the liquid crystal device may satisfy Equation B below.

[Formula B]

5 ≤ T1 / T2

In Equation B, T1 is a linear light transmittance of the triple phase liquid crystal device in a state where no voltage is applied or a frequency of 100 Hz and a voltage of 10 V is applied, and T2 is a state where a frequency of 30 Hz and a voltage of 60 V are applied. The haze of the triple-phase liquid crystal device in.

In Formula B, T1 may be a straight light transmittance in the first state, and T2 may be a straight light transmittance in the second or third state. In the present application, by adjusting the conductivity of the liquid crystal layer in the above range, it is possible to implement a difference in the linear light transmittance in the same range as the formula (B). In Formula B, T1 / T2 is, in another example, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, 40 or more, 45 or more, 50 or more, 55 or more, 60 or more, 65 or more, 70 or more , 75 or more, 80 or more, 85 or more, or 90 or more. In another example, T1 / T2 may be 100 or less or 98 or 96 or less in another example.

The liquid crystal layer of the liquid crystal element may contain at least a liquid crystal compound. As a liquid crystal compound, a suitable kind can be selected according to a use without a restriction | limiting in particular. In one example, a nematic liquid crystal compound may be used as the liquid crystal compound. The liquid crystal compound may be a non-reactive liquid crystal compound. The term non-reactive liquid crystal compound may mean a liquid crystal compound having no polymerizable group. Examples of the polymerizable group include acryloyl group, acryloyloxy group, methacryloyl group, methacryloyloxy group, carboxyl group, hydroxy group, vinyl group, epoxy group, etc., but are not limited thereto. Known functional groups known as may be included.

The liquid crystal compound included in the liquid crystal layer may have positive dielectric anisotropy or negative dielectric anisotropy. In the present application, the term "dielectric anisotropy" may mean a difference between an abnormal dielectric constant (ε e, extraordinary dielectric anisotropy, dielectric constant in the major axis direction) and the normal dielectric constant (ε o, ordinary dielectric anisotropy, dielectric constant in the short axis direction) of the liquid crystal compound. The dielectric anisotropy of the liquid crystal compound may be, for example, within a range of within ± 40, within ± 30, within ± 10, within ± 7, within ± 5, or within ± 3. When the dielectric anisotropy of the liquid crystal compound is adjusted to the above range, it may be advantageous in terms of driving efficiency of the liquid crystal device.

The refractive index anisotropy of the liquid crystal compound present in the liquid crystal layer may be appropriately selected in consideration of target properties, for example, haze characteristics of the liquid crystal element. The term “refractive index anisotropy” may mean a difference between an extraordinary refractive index and a normal refractive index of a liquid crystal compound. The refractive index anisotropy of the liquid crystal compound may be in the range of, for example, 0.1 or more, 0.12 or more, or 0.15 or more to 0.23 or less, 0.25 or less, or 0.3 or less. When the refractive index anisotropy of the liquid crystal compound satisfies the above range, for example, a normal transmission mode device having excellent haze characteristics may be implemented.

The liquid crystal layer may include appropriate additives for controlling conductivity. Examples of the additives include ionic impurities, ionic liquids, salts, reactive monomers, initiators, or anisotropic dyes. The components that can control the conductivity of the liquid crystal layer are well known. For example, the ionic impurities include TEMPO (2,2,6,6-Tetramethylpiperidine-1-Oxyl Free radical), and the ionic liquid. BMIN-BF4 ([1-butyl-3-methylimideazolium] BF4) and the like, and salts include CTAB (Cetrimonium bromide), CTAI (Cetrimonium Iodide) or CTAI3 (Cetrimonium triiodide). Reactive mesogen, which has a good mesogenic functional group, can be used, and as an initiator, for example, TPO (2,4,6-Trimethylbenzoyl-diphenyl-phosphineoxide) can be used. As the anisotropic dye, for example, an azo-based dye, for example, BASF X12 and the like may be used, but is not limited thereto. The ratio of the compound in the liquid crystal layer may be appropriately selected in consideration of the desired conductivity and the orientation of the liquid crystal compound.

In one example, the liquid crystal layer is an additive for controlling the conductivity in order to form a liquid crystal layer having excellent physical properties while effectively securing the above-described conductivity while having excellent solubility with respect to the liquid crystal and reducing dispersion characteristics. Reactive mesogens. The term reactive mesogen may refer to a liquid crystal compound having at least one polymerizable functional group. For example, when the reactive mesogen is mixed with the non-reactive liquid crystal compound as a conductivity modifier, the physical properties of the liquid crystal layer can be stably maintained while effectively achieving the aforementioned conductivity. The reactive mesogen may exist in an unreacted state in the liquid crystal layer, that is, in a state in which polymerization is not performed, and at least a part may be polymerized if necessary.

Reactive mesogens that can be used in the present application include polymerization of 1 to 6, 1 to 5, 1 to 4 or 1 to 3 aromatic ring structures or mesogen cores containing aliphatic ring structures. Reactive mesogens to which functional groups are linked can be used. In the case where the aromatic or aliphatic ring structure is two or more, the two or more ring structures may be directly connected to each other or connected by a linker to form a mesogen core. As said linker, C1-C10, C1-C8 or C1-C6 alkylene group, ester group (-C (= O) -O- or -OC (= O)-), an ether group, carbon number Alkenylene group having 2 to 10, 2 to 8 carbon atoms or 2 to 6 carbon atoms, oxyalkyrene group having 1 to 10 carbon atoms, 1 to 8 carbon atoms or 1 to 6 carbon atoms (-O-alkylene group-, -alkylene group-O- Or alkylene group-O-alkylene group-) and the like can be exemplified. As the aromatic ring structure in the above, there may be exemplified an aromatic ring structure having 6 to 20 carbon atoms, 6 to 16 carbon atoms or 6 to 12 carbon atoms, for example, a benzene structure. In addition, as the aliphatic ring structure in the above, an aliphatic ring structure having 6 to 20 carbon atoms, 6 to 16 carbon atoms or 6 to 12 carbon atoms may be exemplified, for example, a cyclohexane structure. Meanwhile, the reactive mesogen may include 1 to 10, 1 to 8, 1 to 6, 1 to 4 or 1 or 2 polymerizable groups. Such a polymerizable group may be linked to the mesogen core. The polymerizable group may be directly connected to the mesogen core or connected by an appropriate spacer, and the same kind as the linker may be exemplified as the spacer. In addition, as the polymerizable functional group, acryloyl group, acryloyloxy group, methacryloyl group, methacryloyloxy group, carboxyl group, hydroxy group, vinyl group, epoxy group and the like can be exemplified, but is not limited thereto. .

In the present application, the ratio of the reactive mesogen in the liquid crystal layer may be adjusted within a range capable of achieving the conductivity. For example, the reactive mesogen may be included in a ratio of 1 to 30 parts by weight based on 100 parts by weight of the non-reactive liquid crystal compound. In another example, the ratio may be 5 parts by weight or more, and 25 parts by weight or less, 20 parts by weight or less, or 15 parts by weight or less.

The liquid crystal layer may not contain an ionic compound, for example, the ionic liquid or salt described above. Such ionic compounds are widely known as additives for controlling conductivity of the liquid crystal layer, but the present inventors have confirmed that such compounds have poor solubility in the liquid crystal compound and thus deteriorate the physical properties of the liquid crystal layer. Therefore, the ratio of the ionic compound in the liquid crystal layer may be 2 wt% or less, 1.5 wt% or less, 1 wt% or less, or about 0.7 wt% or less. Since the said ionic compound is an arbitrary component, the minimum of the said ratio is 0 weight%.

The liquid crystal layer may further include an anisotropic dye. The anisotropic dye can contribute to the transmittance variable by improving the light shielding rate of a liquid crystal element, for example. As used herein, the term “dye” may mean a material capable of intensively absorbing and / or modifying light in at least part or entire range within a visible light region, for example, in a wavelength range of 400 nm to 700 nm, The term "anisotropic dye" may refer to a material capable of anisotropic absorption of light in at least part or the entire range of the visible light region.

As the anisotropic dye, for example, a known dye known to have a property that can be aligned according to the alignment state of the liquid crystal compound by a so-called host guest effect can be selected and used. As the anisotropic dye, for example, a black dye can be used. Such dyes are known, for example, but not limited to azo dyes, anthraquinone dyes, and the like.

Anisotropic dyes are dyes having a dichroic ratio, that is, a value obtained by dividing the absorption of polarization parallel to the long axis direction of the anisotropic dye by the absorption of polarization parallel to the direction perpendicular to the long axis direction. Can be used. The dye may satisfy the dichroic ratio at at least some of the wavelengths or at any one within the wavelength range of the visible region, for example, in the wavelength range of about 380 nm to 700 nm or about 400 nm to 700 nm. The upper limit of the dichroic ratio may be, for example, about 20 or less, 18 or less, 16 or less, or about 14 or less.

The ratio in the liquid crystal layer of the anisotropic dye may be appropriately selected according to the desired physical properties, for example, the variable transmittance. For example, the anisotropic dye may be 0.01% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight. Or more, 0.9 wt% or more, or 1.0 wt% or more, and may be included in the liquid crystal layer. The upper limit of the ratio in the liquid crystal layer of the anisotropic dye is, for example, 2 wt% or less, 1.9 wt% or less, 1.8 wt% or less, 1.7 wt% or less, 1.6 wt% or less, 1.5 wt% or less, 1.4 wt% or less, 1.3 wt% or less, 1.2 wt% or less, or 1.1 wt% or less.

The liquid crystal layer may further comprise a polymer network. The polymer network may serve as a spacer, for example, to maintain a gap in the liquid crystal layer. The polymer network may exist in phase separation from the liquid crystal compound. The polymer network in the liquid crystal layer may be included in the liquid crystal layer, for example, in a structure in which the polymer network is distributed in a continuous liquid crystal compound, a so-called polymer network liquid crystal (PNLC) structure, or include a liquid crystal compound in the polymer network. The liquid crystal region may be included in the liquid crystal layer in a structure in which the liquid crystal region is dispersed, a so-called Polymer Dispersed Liquid Crystal (PDLC) structure.

The polymer network may be, for example, a network of precursors comprising a polymerizable compound. Thus, the polymer network may comprise a polymerizable compound in a polymerized state. As the polymerizable compound, a non-liquid crystalline compound which does not exhibit liquid crystallinity may be used. As the polymerizable compound, a compound having at least one polymerizable functional group known to be able to form a polymer network of so-called PDLC or PNLC devices, or a non-polymerizable compound having no polymerizable functional group if necessary can be used. Examples of the polymerizable compound which may be included in the precursor may include an acrylate compound, but are not limited thereto.

The ratio in the liquid crystal layer of the polymer network may be appropriately selected in consideration of target properties, for example, haze or transmittance characteristics of the liquid crystal element. The polymer network may be included in the liquid crystal layer at a ratio of, for example, 40 wt% or less, 38 wt% or less, 36 wt% or less, 34 wt% or less, 32 wt% or less, or 30 wt% or less. The lower limit of the ratio in the liquid crystal layer of the polymer network is not particularly limited, but for example, at least 0.1% by weight, 1% by weight, at least 2% by weight, at least 3% by weight, at least 4% by weight, at least 5% by weight, and 6% by weight. Or at least 7 wt%, at least 8 wt%, at least 9 wt% or at least 10 wt%.

The liquid crystal device of the present application may further include, for example, two substrates, and a liquid crystal layer may be present between the substrates. As illustrated in FIG. 1, in the liquid crystal device, the two

substrates

1011 and 1012 are disposed to face each other, and the liquid crystal layer 102 exists between the two

substrates

1011 and 1012 disposed to face each other. Can be.

As the substrate, known materials can be used without particular limitation. For example, inorganic films, plastic films, etc., such as a glass film, a crystalline or amorphous silicon film, a quartz, or an Indium Tin Oxide (ITO) film, can be used. As the substrate, an optically isotropic substrate, an optically anisotropic substrate such as a retardation layer, a polarizing plate, a color filter substrate, or the like can be used.

Examples of the plastic substrate include triacetyl cellulose (TAC); COP (cyclo olefin copolymer) such as norbornene derivatives; Poly (methyl methacrylate); PC (polycarbonate); PE (polyethylene); PP (polypropylene); PVA (polyvinyl alcohol); DAC (diacetyl cellulose); Pac (Polyacrylate); PES (poly ether sulfone); PEEK (polyetheretherketon Substrates including polyphenylsulfone (PPS), polyetherimide (PEI); polyethylenemaphthatlate (PEN); polyethyleneterephtalate (PET); polyimide (PI); polysulfone (PSF); polyarylate (PAR) or amorphous fluorine resin The substrate may have a coating layer of a silicon compound such as gold, silver, silicon dioxide or silicon monoxide, or a coating layer such as an antireflection layer, if necessary.

The substrate may be a substrate having liquid crystal alignment. In the present application, the term “substrate having liquid crystal alignment” may refer to a substrate provided with an alignment capability that may affect, for example, alignment of adjacent liquid crystal compounds in a predetermined direction. . The liquid crystal layer can be maintained between the two substrates having the liquid crystal alignment property, so that the proper alignment state can be maintained in the initial state. The two substrates arranged opposite in the liquid crystal element may be, for example, substrates having vertical alignment or horizontal alignment. In the present application, the term "substrate having vertical alignment or horizontal alignment" may mean a substrate having an alignment capable of orienting adjacent liquid crystal compounds in a vertical direction or a horizontal direction.

As a board | substrate which has liquid crystal alignability, the board | substrate with which the alignment film was formed can be used, for example. Accordingly, the liquid crystal device may further include an alignment layer adjacent to the liquid crystal layer. For example, the alignment layers 201 and 202 may be present on the side of the liquid crystal layer 102 of the two opposing

substrates

1011 and 1012, as shown in FIG. 2. As the alignment film, for example, an alignment film known to be capable of exhibiting orientation characteristics by a non-contact method such as irradiation of linearly polarized light including a contact alignment film or a photoalignment film compound, such as a rubbing alignment film, can be used.

As another example of the board | substrate with which the orientation was guide | induced, the board | substrate which directly provided liquid crystal alignability can be used. For example, a substrate having a hydrophilic surface can be used as the substrate imparted with the vertical alignment capability. Substrates with hydrophilic surfaces, for example, have a wetting angle of water of 0 degrees to 50 degrees, 0 degrees to 40 degrees, 0 degrees to 30 degrees, 0 degrees to 20 degrees, or 0 degrees to 10 degrees. Or, it may be about 10 to 50 degrees, 20 to 50 degrees, 30 to 50 degrees. The method of measuring the wet angle with respect to the water of the substrate in the above is not particularly limited, it is possible to use a known wet angle measuring method in this field, for example, using a DSA100 device manufactured by KRUSS, Can be measured according to the manual. In order to have a hydrophilic surface in a board | substrate, the surface of a board | substrate may be hydrophilized, for example, or the board | substrate containing a hydrophilic functional group can be used. As the hydrophilization treatment, corona treatment, plasma treatment or alkali treatment can be exemplified.

The liquid crystal element may further include an electrode layer, for example, an electrode layer adjacent to the liquid crystal layer. For example, electrode layers 301 and 302 may be present on the side of liquid crystal layer 102 of two opposing

substrates

1011 and 1012, as shown in FIG. When the alignment film is present on the side of the liquid crystal layer of the substrate, the substrate, the electrode layer and the alignment film may be present in sequence. The electrode layer may be applied to the liquid crystal layer so as to switch the alignment state of the liquid crystal compound in the liquid crystal layer. For example, the electrode layer may be formed by depositing a conductive polymer, a conductive metal, a conductive nanowire, or a metal oxide such as indium tin oxide (ITO). The electrode layer may be formed to have transparency. In this field, various materials and forming methods capable of forming a transparent electrode layer are known, and all of these methods can be applied. If necessary, the electrode layer formed on the surface of the substrate may be appropriately patterned.

The liquid crystal layer may further include a polarization layer disposed on one side or both sides of the liquid crystal layer if necessary. The polarizing layer may play a role of adjusting the light transmittance of the liquid crystal element according to the alignment state of the liquid crystal compound. As the polarizing layer, a known material may be used without particular limitation, and for example, an alignment layer of a poly (vinyl alcohol) based polarizing layer, a lyotropic liquid crystal (LLC) or a reactive mesogen (RM), and an anisotropic dye may be used. The same liquid crystal layer can also be applied. When the polarizing layers are disposed on both sides of the liquid crystal layer, the relationship between the light transmission axes of the polarizing layers is not particularly limited and may be adjusted according to the desired mode.

The liquid crystal device may further include any of the known structures, if necessary, in addition to the above configurations.

The liquid crystal device as described above may implement any one of the above-described first to third states according to an applied frequency and / or an applied voltage, and may be switched to another state by changing or removing the frequency and / or voltage. Can be.

The orientation state of the liquid crystal compound in each state is not particularly limited, and an appropriate orientation may be selected depending on, for example, the presence or absence of an anisotropic dye in the polarizing layer or the liquid crystal layer.

In one example, the liquid crystal layer may be in a vertical alignment state in the first state. The vertical alignment state may be a state in which the liquid crystal compounds therein are substantially vertically aligned and have the aforementioned planar and thickness direction retardations Rin and Rth.

In the second state, the liquid crystal layer may be in a horizontal alignment, vertical alignment, twist alignment, or hybrid alignment state. The horizontal alignment state may be a state in which the liquid crystal compounds therein are substantially horizontally aligned, and may have the aforementioned planar and thickness direction retardations (Rin and Rth), and the twisted alignment state may include the horizontally aligned liquid crystal compounds. It may mean a state that is rotated at a predetermined angle along the imaginary spiral axis, the hybrid alignment state may mean a case where two or more kinds of orientations are mixed among the horizontal, vertical and twist alignment state and the splay alignment state.

The liquid crystal layer may be in an electrohydrodynamic instability (EHDI) state in the third state. In this state, the liquid crystal compound may be randomly oriented without constant regularity, and thus high haze may be induced.

As a state of the liquid crystal device which can be implemented, an element which is the first state in the initial state and which is switched to the second state and / or the third state according to the magnitude and / or frequency of the applied voltage may be exemplified.

In such a device, the liquid crystal layer may be in a vertical alignment state in a first state, in a horizontal alignment state in a second state, and in the EHDI state in a third state. Such a device may be implemented using, for example, a liquid crystal compound having negative dielectric anisotropy as the liquid crystal compound while imparting liquid crystal alignment force using a vertical alignment layer. In this state, polarization layers may exist on both sides of the liquid crystal layer if necessary.

As another state of the liquid crystal device that can be implemented, an element which is the second state in the initial state and which is switched to the first state and / or the third state according to the magnitude and / or frequency of the applied voltage may be exemplified.

In such an element, the liquid crystal layer in the initial state may be in a horizontal alignment or twisted alignment state, or may be in a hybrid alignment state such as a splay alignment, in a first state, in a vertical alignment state, and in a third state, in an EHDI state. Such an element may be implemented using, for example, a horizontal alignment layer and a liquid crystal of positive dielectric anisotropy, or may be implemented using two kinds of alignment layers and positive dielectric anisotropy liquid crystals having different alignment directions on both sides of the liquid crystal layer, or horizontally. And a vertical alignment layer may be applied to both sides of the liquid crystal layer, and a positive dielectric anisotropy liquid crystal compound may be used as the liquid crystal compound. In this state, polarization layers may exist on both sides of the liquid crystal layer if necessary.

The implementation method of the liquid crystal elements of the above structures is not particularly limited, and if the process of controlling the conductivity of the liquid crystal layer is controlled, it may be implemented by applying a general method of manufacturing a liquid crystal element.

The present application may also be directed to a method of manufacturing a liquid crystal device comprising a liquid crystal layer. The method of manufacturing the liquid crystal device may be the method of manufacturing the liquid crystal device described above.

Therefore, the manufacturing method may include adjusting the horizontal conductivity of the liquid crystal layer to be 1.0 × 10 ⁻⁴ μS / cm or more. By the above process, the liquid crystal device may be configured to be switched between the first to third states described above.

The method of controlling the conductivity of the liquid crystal layer is not particularly limited. For example, a method of appropriately selecting the kind of the liquid crystal compound and / or the anisotropic dye used as the material to be used or adding the above-described salt component may be applied. Can be.

Other details in the manufacturing method of the liquid crystal device, for example, the conditions of the applied frequency (F1, F2) and / or the voltage (V1, V2) for the definition or driving of the first to third state is as described above. The same may apply.

The present application may also be directed to a method of driving a liquid crystal device comprising a liquid crystal layer. The driving method of the liquid crystal device may be the driving method of the liquid crystal device described above.

Therefore, the manufacturing method may include applying a voltage to the liquid crystal layer having a horizontal conductivity of 1.0 × 10 ⁻⁴ μS / cm or more, and controlling the frequency or magnitude of the applied voltage so that the liquid crystal device includes the first to the first to the same. And implementing any one of the third states. In addition, the method may further comprise controlling the frequency or magnitude of the applied voltage to switch from one of the first to third states to another.

The method of controlling the magnitude of the frequency and / or voltage applied for driving the liquid crystal element in the above method is not particularly limited and may be performed according to the above-mentioned conditions.

The present application also relates to the use of the liquid crystal element, for example, to an optical modulation device including the liquid crystal element. Such an optical modulation device can be applied to various applications, for example, such as a vehicle window, a smart window, a window shield, a display device, a light shielding plate for a display, an active retarder for displaying a 3D image, or a viewing angle adjusting film. Can be applied to

The present application relates to a liquid crystal device and the like. The liquid crystal device of the present application may implement a transparent white state, a transparent black state and a scattering state according to the frequency and / or magnitude of the applied voltage. The liquid crystal device may be applied to applications such as, for example, a vehicle window, a smart window, a window protective film, a display device, a display light shielding plate, an active retarder for displaying 3D images, a viewing angle adjusting film, and the like.

1 to 3 exemplarily illustrate liquid crystal elements.

4 to 31 is a view showing the results of measuring the total transmittance and haze in the test example.

1011 and 1012 two substrates arranged oppositely

102: liquid crystal layer

201 and 202: alignment film

301 and 302: electrode layer

Hereinafter, the above contents will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present application is not limited by the contents given below.

1. Conductivity evaluation

For the liquid crystal devices prepared in Examples and Comparative Examples, the conductivity was measured at room temperature under the condition that the measurement frequency is 60 Hz and the measurement voltage magnitude is 0.5V using an LCR meter (E4980A, Agilent). The horizontal conductivity was measured by applying a vertical voltage to the vertically aligned liquid crystal layer, that is, a voltage in the thickness direction, and when necessary, the vertical conductivity was measured by applying the vertical voltage to the horizontally aligned liquid crystal layer. The liquid crystal layer of each liquid crystal element was produced and measured so that area might be 9 cm <^2> (width: 3 cm, length: 3 cm), and thickness might be 15 micrometers.

2. Haze and transmittance evaluation

The haze and transmittance were measured according to ASTM D1003 standard using the haze meter and NDH-5000SP about the liquid crystal element manufactured by the Example and the comparative example. That is, the light is transmitted through the object to be measured and is incident into the integrating sphere. In this process, the light is diffused (DT, which means the sum of all the light emitted and diffused) and the straight light (PT, front of the diffuse light). Direction of the light emitted from the light beam, which is focused on the light receiving element in the integrating sphere, and the haze can be measured through the light. That is, the total transmitted light TT by the above process is the sum of the diffused light DT and the straight light PT (DT + PT), and the haze is the percentage of diffused light with respect to the total transmitted light (Haze (%) = 100XDT). / TT). In addition, in the following test example, the total transmittance means the total transmitted light (TT), and the straight transmittance means the straight light (PT).

Preparation Example 1.

After the spaces are arranged so that the vertical alignment layers face each other and have a cell gap of about 15 μm, two PC (polycarbonate) films in which an indium tin oxide (ITO) transparent electrode layer and a vertical alignment layer are sequentially formed are spaced apart from each other. The liquid crystal composition was inject | poured between the two PC films arrange | positioned, the edge was sealed, and the liquid crystal element of area 9cm <^2> and Cell gap 15micrometer was produced. The liquid crystal composition is a liquid crystal compound having a refractive index anisotropy of 0.25 and a dielectric anisotropy of -4.0 (manufacturer: HCCH, trade name: HNG726200-100), anisotropic dye (manufacturer: BASF, trade name: X12) and for controlling conductivity An additive (manufacturer: HCCH, trade name: HCM-021) was used in a weight ratio of 87: 10: 3 (HNG726200-100: X12: HCM-021). The measured value of the horizontal conductivity of the liquid crystal layer manufactured as described above was about 7.9 × 10 ⁻⁶ S, which was converted into a numerical value to be represented by a liquid crystal layer having an area of 1 cm ² and a thickness of 1 cm using Equations 1 to 3. The result was 1.3 × 10 ⁻³ μS / cm.

Test Example 1.

The total transmittance and the haze were evaluated while changing the driving frequency of the liquid crystal device manufactured in Production Example 1, and the results are summarized in FIGS. 4 to 17. 4 to 10 are sequentially the total transmittance measured at 30Hz, 60Hz, 100Hz, 300Hz, 500Hz, 700Hz and 1000Hz, respectively, Figures 11 to 17 are sequentially at 30Hz, 60Hz, 100Hz, 300Hz, 500Hz, 700Hz and 1000Hz Measured haze. As shown in the drawing, in the case of the liquid crystal device of Preparation Example 1, the first and second states can be implemented under conditions of about 300 Hz or more and less than 40 V, and conditions of an applied voltage of 60 V or more and less than 300 Hz or less than 300 Hz. It can be seen that the transmittance and haze by the EHDI drive are saturated.

In such a device, the conditions showing the appropriate first state (the state in which the liquid crystal compound is vertically oriented), the second state (the state in which the liquid crystal compound is horizontally aligned), and the third state (the EHDI state) are summarized in Table 1 below. .

	전압(V)Voltage (V)	주파수(Hz)Frequency (Hz)	전체투과율(%)Total transmittance (%)	직진광투과율(%)Straight light transmittance (%)	헤이즈(%)Haze (%)
제1상태 First state	00	00	29.529.5	29.029.0	0.90.9
제2상태Second state	1010	300300	14.714.7	14.514.5	1.21.2
제3상태 Third state	6060	100100	1.61.6	0.20.2	92.092.0

Preparation Example 2.

As a liquid crystal composition, a liquid crystal compound having a refractive index anisotropy of 0.25 and a dielectric anisotropy of -4.0 as a liquid crystal compound (manufacturer: HCCH, trade name: HNG726200-100), an anisotropic dye (manufacturer: BASF, trade name: X12), and an additive for controlling conductivity A device was manufactured in the same manner as in Preparation Example 1, except that (Manufacturer: HCCH, Trade Name: HCM-021) was used in a weight ratio of 89: 10: 1 (HNG726200-100: X12: HCM-021). . The measured value of the horizontal conductivity of the liquid crystal layer of the device was about 1.0 × 10 ^-5 S, which was converted into a numerical value that would be represented by a liquid crystal layer having an area of 1 cm ² and a thickness of 1 cm using Equations 1 to 3 above. 1.7 × 10 ⁻³ μS / cm.

Test Example 2.

The total transmittance and the haze were evaluated while changing the driving frequency of the liquid crystal device manufactured in Production Example 1, and the results are summarized in FIGS. 18 to 31. 18 to 24 are the total transmittance measured sequentially at 30 Hz, 60 Hz, 100 Hz, 300 Hz, 500 Hz, 700 Hz and 1000 Hz, respectively, and FIGS. 25 to 31 are sequentially at 30 Hz, 60 Hz, 100 Hz, 300 Hz, 500 Hz, 700 Hz and 1000 Hz, respectively. Measured haze. As shown in the drawing, in the liquid crystal device of Preparation Example 2, the first and second states can be implemented under conditions of about 100 Hz or more and less than 20 V, and an applied voltage of 60 V or less of 30 Hz or more and 100 Hz or less It can be seen that the transmittance and haze due to the EHDI drive are saturated under the conditions.

The conditions showing the appropriate first state (the state in which the liquid crystal compound is vertically aligned), the second state (the state in which the liquid crystal compound is horizontally aligned), and the third state (the EHDI state) in such a device are summarized in Table 2 below. .

	전압(V)Voltage (V)	주파수(Hz)Frequency (Hz)	전체투과율(%)Total transmittance (%)	직진광투과율(%)Straight light transmittance (%)	헤이즈(%)Haze (%)
제1상태 First state	00	00	58.558.5	57.557.5	1One
제2상태Second state	1010	100100	29.929.9	29.829.8	1.81.8
제3상태 Third state	6060	3030	15.015.0	0.70.7	95.695.6

Claims

A liquid crystal layer having a horizontal conductivity of at least 1.0 × 10 −4 μS / cm,

Triple phase liquid crystal element switched between the following first to third states (the horizontal conductivity is a value measured along the direction of the electric field in a state where a voltage is applied so that the direction of the optical axis and the electric field of the liquid crystal layer is horizontal) In this case, the measurement frequency is 60 Hz, the measurement voltage is 0.5V, and the conductivity is converted into a liquid crystal layer having an area of 1 cm 2 and a thickness of 1 cm.

First state: a state in which the linear light transmittance is 25% or more and the haze is 5% or less;

Second state: a state in which the linear light transmittance is 15% or less and the haze is 5% or less;

Third state: a state in which the linear light transmittance is 10% or less and the haze is 80% or more.
The triple phase liquid crystal device according to claim 1, wherein the horizontal conductivity of the liquid crystal layer is 5.0 × 10 −2 μS / cm or less.
The triple phase liquid crystal device according to claim 1, wherein the horizontal conductivity of the liquid crystal layer is 3.0 × 10 −2 μS / cm or less.
The triple phase liquid crystal device according to claim 1, wherein a ratio (PC / VC) of the vertical conductivity (VC) of the liquid crystal layer and the horizontal conductivity (PC) of the liquid crystal layer is 0.2 or more.
The triple phase liquid crystal device according to claim 1, wherein the ratio (VC / PC) of the horizontal conductivity (PC) of the liquid crystal layer and the vertical conductivity (VC) of the liquid crystal layer is 2.0 or less.
The triple phase liquid crystal device of claim 1, wherein the triple phase liquid crystal device satisfies the following formula A:

[Formula A]

20 ≤ H1 / H2

In Equation A, H1 is the haze of the triple-phase liquid crystal device at a frequency of 30 Hz and a voltage of 60 V, and H2 is a voltage unapplied state or at a frequency of 100 Hz and a voltage of 10 V. It is the haze of the said triple phase liquid crystal element.
The triple phase liquid crystal device of claim 1, wherein the triple phase liquid crystal device satisfies the following formula B:

[Formula B]

5 ≤ T1 / T2

In Equation B, T1 is a linear light transmittance of the triple phase liquid crystal device in a state where no voltage is applied or a frequency of 100 Hz and a voltage of 10 V is applied, and T2 is a state where a frequency of 30 Hz and a voltage of 60 V are applied. The haze of the triple-phase liquid crystal device in.
The triple phase liquid crystal device of claim 1, wherein the liquid crystal layer comprises a non-reactive liquid crystal compound and a reactive mesogen.
The triple phase liquid crystal device of claim 8, wherein the liquid crystal layer comprises 1 to 30 parts by weight of a reactive liquid crystal compound relative to 100 parts by weight of the non-reactive liquid crystal compound.
9. The triple phase liquid crystal device according to claim 8, wherein the liquid crystal layer further comprises an ionic compound in a ratio of 2% by weight or less.
The triple phase liquid crystal device according to claim 1, wherein the liquid crystal layer in the first state is in a vertical alignment state.
The triple phase liquid crystal device according to claim 1, wherein the liquid crystal layer in the second state is in a horizontal alignment, a vertical alignment, a twist alignment, or a hybrid alignment state.
The triple phase liquid crystal device according to claim 1, wherein the liquid crystal layer in the third state is in an electrohydraulic instability state.
It is a manufacturing method of the triple phase liquid crystal element containing a liquid crystal layer,

Adjusting the horizontal conductivity of the liquid crystal layer to 1.0 × 10 −4 μS / cm or more so that the triple phase liquid crystal device can be switched between the following first to third states; Manufacturing method (The said horizontal conductivity is the value measured along the direction of the said electric field in the state which applied the voltage so that the direction of the optical axis and the electric field of the said liquid crystal layer may be horizontal, where a measurement frequency is 60 Hz and a measurement voltage is 0.5. V, and the conductivity is converted into a liquid crystal layer having an area of 1 cm 2 and a thickness of 1 cm.

First state: a state in which the linear light transmittance is 25% or more and the haze is 5% or less;

Second state: a state in which the linear light transmittance is 15% or more and the haze is 5% or less;

Third state: a state in which the linear light transmittance is 10% or less and the haze is 80% or more.
15. The method according to claim 14, wherein the applied frequency F1 and the applied voltage V1 for the implementation of the second state and the applied frequency F2 and the applied voltage V2 for the implementation of the third state are equal to the following conditions 1 and 2. Method for producing a triple-phase liquid crystal device for forming a liquid crystal layer to satisfy:

[Condition 1]

F1> F2

[Condition 2]

V1 ≦ V2.
It is a drive method of a triple phase liquid crystal element containing a liquid crystal layer whose horizontal conductivity is 1.0x10 <-4> S / cm or more,

A method of driving a liquid crystal device comprising the step of adjusting the frequency or magnitude of the applied voltage to the liquid crystal device to implement any one of the following first to third states (the horizontal conductivity is the optical axis and the electric field of the liquid crystal layer Measured along the direction of the electric field with a voltage applied so that the direction of is horizontal, wherein the measured frequency is 60 Hz, the measured voltage is 0.5V, and the conductivity is 1 cm 2 in area, It is the conversion value into the liquid crystal layer which is 1 cm.):

First state: a state in which the linear light transmittance is 25% or more and the haze is 5% or less;

Second state: a state in which the linear light transmittance is 15% or more and the haze is 5% or less;

Third state: a state in which the linear light transmittance is 10% or less and the haze is 80% or more.
17. The method of claim 16, further comprising controlling the frequency or magnitude of the applied voltage to switch from one of the first to third states to another of the first to third states.
17. The method of claim 16, wherein the applied frequency F1 and the applied voltage V1 for the implementation of the second state and the applied frequency F2 and the applied voltage V2 for the implementation of the third state are equal to A method of driving a liquid crystal element for controlling the frequency or magnitude of an applied voltage to satisfy:

[Condition 1]

F1> F2

[Condition 2]

V1 ≦ V2.
An optical modulation device comprising the triple phase liquid crystal device of claim 1.