KR102401497B1 - Smart display device and optical film comprising the same - Google Patents

Abstract

[구조식 2]

The present invention relates to an optical cell; a polymer matrix formed inside the optical cell; and a liquid crystal mixture in which a liquid crystal compound represented by the following Structural Formula 1 dispersed in the polymer matrix and an additive for regulating a phase transition temperature represented by the following Structural Formula 2 are mixed; relates to a smart display device comprising a. Thereby, by dispersing a polymer matrix inside the optical cell, an additive that controls the phase transition temperature in the polymer matrix, a chiral dopant that can increase light scattering, and a gelator with the liquid crystal compound, various phase transition temperatures are realized in winter It can be used as an optical film for black ice display indicating the freezing section of a road, a smart window that controls light shielding at a predetermined temperature, and a sensor-type attachment film that controls light transmission and scattering according to temperature.
[Structural Formula 1]

[Structural Formula 2]

Description

Smart display device and optical film including the same

The present invention relates to a smart display device and an optical film including the same, and more particularly, to a smart display device in which transmission and scattering are controlled according to a phase transition of a material using a difference in refractive index of a phase that changes according to temperature, and an optical film including the same It's about film.

Smart window optical film is an optical film that can actively or passively control light scattering and reflection in response to changes in the surrounding environment or artificial environment. In particular, the liquid crystal-based smart window optical film can reversibly control transmission and scattering by applying an electric field to the optical cell, and based on this, can perform functions such as room temperature control and privacy protection. As a representative example, there is a PDLC (Polymer-Dispersed Liquid Crystal) mode in which liquid crystals are dispersed in micropores of a certain size in a polymer matrix, scattering, and arranged through application of an electric field to transmit light.

PDLC is manufactured by mixing and injecting a monomer matrix and liquid crystal between two transparent conductive polymer films or substrates. An optical film with a thickness of several tens of micrometers can be produced by exposing the injected mixture to ultraviolet light to polymerize the monomer, forming liquid crystal droplets with a size of hundreds of nanometers, and enclosing them in a polymer matrix and dispersing them irregularly. When electricity is applied, the liquid crystals are aligned in an electric field, and when the light is transmitted and the electric field is removed, strong scattering occurs due to the difference in refractive index between the liquid crystal and the matrix interface and the light can be blocked. However, if the polymer content exceeds 40% due to the strong anchoring energy between the liquid crystal and the polymer matrix interface, a high voltage of 100 V or more is required as a drivable threshold voltage, and the reproducibility is poor, and a large-area film is produced. it becomes difficult to do

As another representative liquid crystal optical film, PSCT (Polymer Stabilized Cholesteric Texture) uses selective reflection according to the helical pitch of the cholesteric liquid crystal phase and reflects only light in the desired wavelength band by adding various wavelength bands or specific dyes. ) exists. The cholesteric phase is an optical film that takes advantage of the fact that it can selectively reflect incident light according to the direction of the rotation axis of the phase. It is an optical film that can implement , transmission, and selective color reflection. However, in order to initially arrange the cholesteric phase, a process of coating and rubbing a horizontal alignment layer on the substrate is required, and a narrow viewing angle occurs due to a change in the length of the spiral structure according to the viewing angle. In addition, there are various problems in which the liquid crystal mixture escapes out of the cell during large-area expansion and additional processing.

Therefore, in order to solve this problem, in the past research, a gelator capable of inducing gelation of liquid crystal was added to the liquid crystal dispersion medium to reduce the anchoring energy between the interfaces. However, in this study, a problem arises in that many variables must be considered because a molecular model must be constructed that fully considers the molecular interaction between the liquid crystal, the gelator, and the monomer. In addition, the network formed through the gelator has a problem in that the stability of the network decreases according to the temperature change.

Korean Patent Publication No. 10-2019-0045889 Korean Patent Publication No. 10-2017-0065324

An object of the present invention is to build a polymer matrix inside an optical cell, an additive that controls the phase transition temperature in the polymer matrix, a chiral dopant that can increase light scattering, and a gelator together with a liquid crystal compound An optical film for black ice display that shows the freezing section of a road in winter by realizing various phase transition temperatures by dispersing it, a smart window that controls light shielding at a predetermined temperature, and a sensor-type attachment film that controls light transmission and scattering according to temperature An object of the present invention is to provide a smart display device capable of actively controlling light shielding rather than passive light shielding by applying a conventional electric or magnetic field, and an optical film including the same.

Another object of the present invention is to develop a method for manufacturing an optical film that is simplified in three steps of dispersing material mixing, injection, and photopolymerization, and a liquid crystal compound, an additive for controlling the phase transition temperature, a chiral dopant capable of increasing light scattering, and A method of manufacturing an optical film that can be applied to a device that displays black ice on a road surface in winter by setting the phase transition temperature to 0°C or slightly higher is to provide

According to one aspect of the present invention,

optical cell;

a polymer matrix formed inside the optical cell; and

A smart display device comprising a liquid crystal compound represented by the following Structural Formula 1 dispersed in the polymer matrix and a liquid crystal mixture in which an additive for regulating a phase transition temperature represented by the following Structural Formula 2 is mixed is provided.

[Structural Formula 1]

In Structural Formula 1,

M is the mesogenic core,

,

, 또는

이고, P and Q are each independently a C1 to C30 straight-chain alkyl group, a cyan group,

,

, or

ego,

j, k, and l are each independently the number of repeating units that are integers from 1 to 30,

m and n are each independently an integer from 1 to 30.

[Structural Formula 2]

In Structural Formula 2,

M is the mesogenic core,

R is a C1 to C30 straight-chain alkyl group.

Preferably, in Structural Formula 1,

M is a rod-shaped mesogen or a plate-shaped mesogen core,

,

, 또는

이고, P and Q are each independently a C1 to C10 straight-chain alkyl group, a cyan group,

,

, or

ego,

j, k, and l are each independently the number of repeating units that are integers from 1 to 10,

m and n may be integers from 1 to 10.

Preferably in Structural Formula 2

M is a rod-shaped mesogen or a plate-shaped mesogen core,

R may be a C1 to C10 straight-chain alkyl group.

The phase transition temperature of the liquid crystal mixture may be adjusted according to the content of the additive.

The liquid crystal mixture may further include a chiral dopant.

The chiral dopant may be any one selected from chiral dopants S811, CB15, A131, ZL1-457, DBH1281, and d-2.

The liquid crystal mixture may further include a gelator.

The gelator may be a compound represented by any one selected from the following Chemical Formulas 5 to 7.

[Formula 5]

[Formula 6]

[Formula 7]

The rod-shaped mesogen may be any one selected from the following compounds 1 to 35.

The plate-shaped mesogen may be any one selected from the following compounds 36 to 61.

Most preferably, the liquid crystal compound represented by Structural Formula 1 may be a compound represented by Formula 1 or Formula 2 below.

[Formula 1]

[Formula 2]

The additive represented by Formula 2 may be a compound represented by Formula 3 below.

[Formula 3]

The additive may be included in an amount of 10 to 30 wt% based on the total weight of the liquid crystal mixture.

The liquid crystal mixture may further include a chiral dopant, and the chiral dopant may be included in an amount of 35 to 45 wt% based on the total weight of the liquid crystal mixture and the chiral dopant.

The liquid crystal mixture further comprising the chiral dopant may further include a gelator, and the gelator may be included in an amount of 0.1 to 2 wt% based on the total weight of the liquid crystal mixture further comprising the chiral dopant and the gelator.

The phase transition temperature of the liquid crystal mixture may be controlled in the range of 0°C to 4°C.

The polymer matrix may be a polymer of a monomer including pentaerythritol tetraacrylate (PETTA), isobornyl methacrylate (IBMA), and tetrahydrofurfuryl acrylate (THFFA).

According to another aspect of the present invention,

Two film substrates facing each other at a predetermined interval;

a polymer matrix formed between opposite surfaces of the two film substrates; and

A smart optical film comprising a liquid crystal compound in which the liquid crystal compound represented by the following Structural Formula 1 dispersed in the polymer matrix and an additive for regulating the phase transition temperature represented by the following structural formula 2 is mixed; is provided.

[Structural Formula 1]

In Structural Formula 1,

M is the mesogenic core,

,

, 또는

이고, P and Q are each independently a C1 to C30 straight-chain alkyl group, a cyan group,

,

, or

ego,

j, k, and l are each independently the number of repeating units that are integers from 1 to 30,

m and n are each independently an integer from 1 to 30.

[Structural Formula 2]

In Structural Formula 2,

M is the mesogenic core,

R is a C1 to C30 straight-chain alkyl group.

All of the two transparent substrates may be transparent substrates, or one of the two substrates may be a transparent substrate and the other may be a substrate including a predetermined color or pattern.

The liquid crystal mixture may further include a chiral dopant.

The liquid crystal mixture may further include a gelator.

The smart optical film may be for displaying black ice on a road surface.

According to another aspect of the present invention,

(a) preparing a precursor mixture by mixing a polymer monomer for preparing a polymer matrix, a liquid crystal compound represented by the following Structural Formula 1, and an additive for controlling a phase transition temperature represented by the following Structural Formula 2;

(b) preparing two film substrates having opposite surfaces spaced apart from each other by a predetermined interval, and injecting the precursor mixture between the two film substrates; and

(c) irradiating ultraviolet light to the precursor mixture to photopolymerize the polymer monomer; is provided a method for producing a smart optical film comprising.

[Structural Formula 1]

In Structural Formula 1,

M is the mesogenic core,

,

, 또는

이고, P and Q are each independently a C1 to C30 straight-chain alkyl group, a cyan group,

,

, or

ego,

j, k, and l are each independently the number of repeating units that are integers from 1 to 30,

m and n are each independently an integer from 1 to 30.

[Structural Formula 2]

In Structural Formula 2,

M is the mesogenic core,

R is a C1 to C30 straight-chain alkyl group.

The precursor mixture may further include a chiral dopant.

The precursor mixture may further include a gelator.

The smart display device of the present invention and an optical film including the same are an additive that controls a phase transition temperature that builds a polymer matrix inside an optical cell and controls the phase transition temperature in the polymer matrix, a chiral dopant that can increase light scattering, and a gel By dispersing the detector together with the liquid crystal compound, various phase transition temperatures are realized, such as an optical film for black ice display that shows the freezing section of a road in winter, a smart window that controls light shielding at a predetermined temperature, and light transmission and scattering according to the temperature. It can be used as a sensor-type adhesive film that adjusts, and it is possible to actively control light shielding rather than passive light shielding by applying a conventional electric or magnetic field.

The manufacturing method of the smart optical film of the present invention is very advantageous for large area by developing a manufacturing method of an optical film that is simplified in three steps of dispersion material mixing, injection, and photopolymerization, liquid crystal compound, an additive to control the phase transition temperature, light By controlling the type and ratio of chiral dopant and gelator that can increase the scattering degree, it can respond actively in a variety of temperature ranges. Applicable to the device.

1 is a schematic diagram showing the driving principle of a smart display device of the present invention.
2 is a schematic diagram of the phase transition temperature control by adding an additive to the liquid crystal compound of the smart display device of the present invention.
3 is a schematic diagram of the improvement of the scattering degree by adding a gelator to the liquid crystal compound of the smart display device of the present invention.
4 is a schematic diagram of a smart display device capable of realizing color when light is transmitted.
5 is a schematic diagram showing a method of manufacturing a smart optical film of the present invention.
6 is an analysis result of a phase transition temperature change according to the chiral dopant content of Experimental Example 1. FIG.
7 is an analysis result of the phase transition temperature change according to the additive content of Experimental Example 2.
8 is an analysis result of a phase transition temperature change according to the additive and chiral dopant contents of Experimental Example 3. FIG.
9 is an analysis result of scattering degree change according to the addition of a gelator in Experimental Example 4.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art can easily carry out the present invention.

However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that detailed descriptions of related known technologies may obscure the gist of the present invention in describing the present invention, the detailed description thereof will be omitted. .

The terminology used herein is used only to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, element, or combination thereof described in the specification exists, and includes one or more other features or It should be understood that the possibility of the presence or addition of numbers, steps, acts, elements, or combinations thereof is not precluded in advance.

1 is a schematic diagram showing the driving principle of a smart display device of the present invention, FIG. 2 is a schematic diagram of phase transition temperature control by adding an additive to a liquid crystal compound of a smart display device of the present invention, and FIG. 3 is a smart display device of the present invention It is a schematic diagram of the scattering degree improvement by adding a gelator to the liquid crystal compound of

Hereinafter, a smart display device and a smart optical film of the present invention will be described with reference to FIGS. 1 to 4 .

First, the smart display device of the present invention includes an optical cell; a polymer matrix formed inside the optical cell; and a liquid crystal mixture in which a liquid crystal compound represented by the following Structural Formula 1 dispersed in the polymer matrix and an additive for regulating a phase transition temperature represented by the following Structural Formula 2 are mixed.

[Structural Formula 1]

In Structural Formula 1,

M is the mesogenic core,

,

, 또는

이고, P and Q are each independently a C1 to C30 straight-chain alkyl group, a cyan group,

,

, or

ego,

j, k, and l are each independently the number of repeating units that are integers from 1 to 30,

m and n are each independently an integer from 1 to 30.

Preferably, in Structural Formula 1,

M is a rod-shaped mesogen or a plate-shaped mesogen core,

,

, 또는

이고, P and Q are each independently a C1 to C10 straight-chain alkyl group, a cyan group,

,

, or

ego,

j, k, and l are each independently the number of repeating units that are integers from 1 to 10,

m and n may be integers from 1 to 10.

More preferably, in Structural Formula 1,

M is a rod-shaped mesogen,

P and Q are each independently a C1 to C10 straight-chain alkyl group, or a cyan group,

m and n may be 1 or 2.

[Structural Formula 2]

In Structural Formula 2,

M is the mesogenic core,

R is a C1 to C30 straight-chain alkyl group.

Preferably, in Structural Formula 2

M is a rod-shaped mesogen or a plate-shaped mesogen core,

R may be a C1 to C10 straight-chain alkyl group.

More preferably, in Structural Formula 2,

M is a rod-shaped mesogen,

R may be a C1 to C10 straight-chain alkyl group.

Based on 100 parts by weight of the liquid crystal mixture, 30 to 50 parts by weight of the polymer matrix may be included, and more preferably 35 to 45 parts by weight. When the polymer matrix is less than 30 parts by weight, it is difficult for the liquid crystal mixture to be uniformly and stably dispersed in the optical cell. have.

As the liquid crystal compound, one having various phase transition temperatures may be selected and used as needed. An additive may be mixed here to lower the phase transition temperature, a chiral dopant may be added to lower the phase transition temperature and light scattering may be increased, and a gelator may be added to maximize scattering.

As the liquid crystal compound, if necessary, a single liquid crystal compound may be used, or a eutectic mixture of two or more types may be used. At this time, when a single liquid crystal compound is used, it is easier to lower the phase transition temperature when mixed with the additive, but since the temperature section of the section representing the liquid crystal phase is too short, when the temperature is lowered to 0 ° C or lower, the light scattering effect may not appear. have. Therefore, when used for black ice display on the road surface, the light scattering effect should be exhibited even in a wide temperature range from a little higher than 0°C to a temperature lower than 0°C. do.

On the other hand, the liquid crystal mixture may lower the phase transition temperature according to the mixing of the additive, but since the domain of the liquid crystal is formed very large and the light scattering effect may be insignificant, it is preferable to add a chiral dopant. When a chiral dopant is added, a strong light scattering effect can be exhibited compared to the nematic phase due to the small domains because the liquid crystal mixture forms a pochalconic phase. In addition, although the chiral dopant serves to lower the phase transition temperature like the additive, it is preferable to use it together with the additive because the phase transition temperature drop alone is not sufficient. In addition, when the additive and the dopant are used together, the amount of the expensive chiral dopant can be reduced, which is effective in terms of cost.

For example, when a smart display device is used to display black ice on a road surface, the phase transition temperature is set slightly higher than 0 ° C. It can be recognized that black ice is formed on the road surface.

The chiral dopant may be any one selected from chiral dopants S811, CB15, A131, ZL1-457, DBH1281, and d-2, but the scope of the present invention is not limited thereto.

Chemical formulas of chiral dopants are as follows.

[Formula_S811]

[Formula_CB15]

[Formula_A131]

[Formula_ZLl-457]

[Formula_d-2]

The rod-shaped mesogen may be any one selected from the following compounds 1 to 35.

Preferably, the compounds 1 to 35 may have a bonding position represented by A below.

The plate-shaped mesogen may be any one selected from the following compounds 36 to 61.

Preferably, the compounds 36 to 61 may have a bonding site represented by A below.

In order to utilize the smart display device of the present invention for displaying black ice on a road surface in winter, it is necessary to set the phase transition temperature slightly higher than 0°C.

The phase transition temperature of the liquid crystal mixture is preferably controlled in the range of 0 °C to 4 °C. In this case, since the phase transition temperature is at or slightly higher than the temperature at which black ice is formed on the road surface, the state immediately before or when the black ice is formed may be displayed.

Even more preferably, the liquid crystal compound represented by Structural Formula 1 may be a compound represented by Formula 1 or Formula 2 below.

[Formula 1]

[Formula 2]

Preferably, the additive represented by the structural formula (2) may be a compound represented by the following formula (3).

[Formula 3]

The additive is preferably included in an amount of 10 to 30 wt% based on the total weight of the liquid crystal mixture, more preferably 15 to 25 wt%, and even more preferably 17 to 22 wt%.

Preferably, the liquid crystal mixture further includes a chiral dopant, and the chiral dopant is preferably included in an amount of 35 to 45 wt%, more preferably 38 to 42 wt%, based on the total weight of the liquid crystal mixture and the chiral dopant. content may be included.

The chiral dopant may produce a distorted structure in the liquid crystal, thereby lowering the phase transition temperature of the liquid crystal and increasing light scattering.

More preferably, the liquid crystal mixture may further include a gelator together with a chiral dopant. The light scattering effect can be further improved by further including the gelether.

The gelator is preferably included in an amount of 0.1 to 2 wt%, more preferably 0.5 to 1.5 wt%, even more preferably 0.8 to 1.2, based on the total weight of the liquid crystal mixture and the gelator further comprising the chiral dopant. It is preferable to include wt%. When less than 0.1wt% is added, the effect of improving the scattering degree hardly appears, and when it exceeds 2wt%, the network formed by the gelator may be unstable to temperature change.

As the polymer matrix, any polymer of a transparent material that can be polymerized by a photopolymerizable monomer can be applied, and a mixed monomer of PETTA (pentaerythritol tetraacrylate), IBMA (isobornyl methacrylate) and THFFA (tetrahydrofurfuryl acrylate) can be used, but the present invention The scope is not limited here.

It may be one or more selected, but the scope of the present invention is not limited thereto.

Hereinafter, the smart optical film of the present invention will be described.

The present invention is a smart optical film, two film substrates facing each other at a predetermined interval; a polymer matrix formed between opposite surfaces of the two film substrates; and a liquid crystal mixture in which a liquid crystal compound represented by the following Structural Formula 1 dispersed in the polymer matrix and an additive represented by the following Structural Formula 2 for controlling a phase transition temperature are mixed.

[Structural Formula 1]

In Structural Formula 1,

M is the mesogenic core,

,

, 또는

이고, P and Q are each independently a C1 to C30 straight-chain alkyl group, a cyan group,

,

, or

ego,

j, k, and l are each independently the number of repeating units that are integers from 1 to 30,

m and n are each independently an integer from 1 to 30.

[Structural Formula 2]

In Structural Formula 2,

M is the mesogenic core,

R is a C1 to C30 straight-chain alkyl group.

Both of the two transparent substrates may be transparent substrates. In this case, when the phase transition temperature of the liquid crystal mixture is exceeded, light transmits and appears transparent, and when the phase transition temperature is below the phase transition temperature, the light is scattered and appears white.

Alternatively, as shown in FIG. 4 , one of the two substrates may be a transparent substrate, and the other may be a substrate including a predetermined color or pattern. In this case, when light is irradiated toward the transparent substrate and the light is transmitted through the smart display device, the predetermined color or pattern is visible, and when the light is scattered, it may appear white. By forming various colors or patterns on the lower plate of the film substrate, it can be applied as an optical device in which the background is not visible during scattering.

Since the description related to the polymer matrix, the liquid crystal compound, and the additive is the same as in the smart display device described above, specific details will be referred to.

5 is a schematic diagram showing a method of manufacturing a smart optical film of the present invention.

Hereinafter, a method of manufacturing a smart optical film of the present invention will be described with reference to FIG. 5 .

First, a precursor mixture is prepared by mixing a polymer monomer for preparing a polymer matrix, a liquid crystal compound represented by Structural Formula 1, and an additive for controlling a phase transition temperature represented by Structural Formula 2 (step a).

Preferably, the precursor mixture may further include a chiral dopant to implement a cholesteric liquid crystal optical film.

More preferably, the precursor mixture may further include a gelator together with a chiral dopant to improve the scattering degree of the liquid crystal.

Since the components included in the precursor mixture are the same as those described above, a detailed description thereof will be referred to.

The polymer monomer means a polymer monomer for synthesizing the polymer constituting the above-mentioned polymer matrix, and the monomer may be a monomer corresponding to a desired polymer compound. The polymer compound is the same as exemplified in the description of the smart display device above.

If necessary, a crosslinking agent, a physical property enhancing agent, a phase separation accelerator, etc. may be additionally included.

Next, two film substrates having opposite surfaces spaced apart by a predetermined interval are prepared, and the precursor mixture is injected between the two film substrates (step b).

Since the film substrate is the same as the description of the smart optical film of the present invention above, specific details will be referred to that part.

Thereafter, the precursor mixture is irradiated with ultraviolet light to photopolymerize the polymer monomer (step c).

Accordingly, a polymer matrix is formed between the substrates, and the liquid crystal mixture in which the liquid crystal compound, the additive, the chiral dopant, and the gelator are mixed can be uniformly and stably dispersed in the polymer matrix.

Hereinafter, examples according to the present invention will be described in detail.

[Example]

Example 1: Liquid crystal compound + chiral dopant

A liquid crystal mixture was prepared by mixing the liquid crystal compound represented by the following Chemical Formula 1 and the chiral dopant represented by the following Chemical Formula 4 in a weight ratio of 8:2. In addition, a monomer mixture was prepared in a weight ratio of pentaerythritol tetraacrylate (PETTA):isobornyl methacrylate (IBMA):tetrahydrofurfuryl acrylate (THFFA)=8:46:46 to prepare a polymer matrix. After mixing the prepared liquid crystal mixture and the monomer mixture in a weight ratio of 8:2, it was injected into an optical cell formed with a cell gap of 20 μm, and photopolymerized by irradiating ultraviolet rays with an intensity of 50 mW/cm ² for about 30 minutes. Accordingly, a polymer matrix was formed, and a smart display device in which the liquid crystal mixture was uniformly and stably dispersed in the polymer matrix was manufactured.

[Formula 1]

[Formula 4]

Example 2: Liquid crystal compound + chiral dopant

A smart display device was manufactured in the same manner as in Example 1, except that a liquid crystal mixture in which a liquid crystal compound and a chiral dopant were mixed in a weight ratio of 8:2 was used instead of a liquid crystal mixture in which a liquid crystal mixture was mixed in a weight ratio of 7:3.

Example 3: Liquid crystal compound + chiral dopant

A smart display device was manufactured in the same manner as in Example 1, except that a liquid crystal mixture in which a liquid crystal compound and a chiral dopant were mixed in a weight ratio of 8:2 was used instead of a liquid crystal mixture in which a liquid crystal mixture was mixed in a weight ratio of 6:4.

Example 4: Liquid crystal compound + additive

A eutectic mixture in which the liquid crystal compound represented by the following formula (1) and the liquid crystal compound represented by the following formula (2) are mixed in a weight ratio of 1:1 is prepared, and the eutectic mixture and the additive represented by the following formula (3) are mixed with 90: A smart display device was manufactured in the same manner as in Example 1, except that a liquid crystal mixture mixed in a weight ratio of 10 was used.

[Formula 1]

[Formula 2]

[Formula 3]

Example 5: Liquid crystal compound + additive

A smart display device was manufactured in the same manner as in Example 4, except that a liquid crystal mixture in which the eutectic mixture and the additive were mixed in a weight ratio of 85:15 instead of a weight ratio of 90:10 was used.

Example 6: Liquid crystal compound + additive

A smart display device was manufactured in the same manner as in Example 4, except that a liquid crystal mixture in which the eutectic mixture and additives were mixed in a weight ratio of 80:20 instead of a weight ratio of 90:10 was used.

Example 7: Liquid crystal compound + additive

A smart display device was manufactured in the same manner as in Example 4, except that a liquid crystal mixture in which the eutectic mixture and additives were mixed in a weight ratio of 75:25 instead of a weight ratio of 90:10 was used.

Example 8: Liquid crystal compound + additive

A smart display device was manufactured in the same manner as in Example 4, except that a liquid crystal mixture in which the eutectic mixture and additives were mixed in a weight ratio of 70:30 instead of a weight ratio of 90:10 was used.

Example 9: Liquid crystal compound + additive + chiral dopant

A smart display device was manufactured in the same manner as in Example 6, except that the chiral dopant represented by Chemical Formula 4 was added to the liquid crystal mixture in a weight ratio of 8:2.

Example 10: Liquid crystal compound + additive + chiral dopant

A smart display device was prepared in the same manner as in Example 6, except that the chiral dopant represented by Chemical Formula 4 was added to the liquid crystal mixture in a weight ratio of 7:3.

Example 11: Liquid crystal compound + additive + chiral dopant

A smart display device was manufactured in the same manner as in Example 6, except that a liquid crystal mixture in which the chiral dopant represented by Chemical Formula 4 was added to the liquid crystal mixture in a weight ratio of 6:4 was used.

Example 12: Liquid crystal compound + additive + chiral dopant

A smart display device was manufactured in the same manner as in Example 11, except that an optical cell having a cell gap of 10 μm was used instead of 20 μm.

Example 13: Liquid crystal compound + additive + chiral dopant + gelator

A smart display device was manufactured in the same manner as in Example 12, except that a gelator represented by the following Chemical Formula 5 was added to the liquid crystal mixture in a weight ratio of 99:1.

[Formula 5]

Comparative Example 1: Liquid crystal compound

A smart display device was manufactured in the same manner as in Example 1, except that only a liquid crystal compound was used without using a chiral dopant.

Comparative Example 2: Liquid crystal compound

A smart display device was manufactured in the same manner as in Example 4, except that only a eutectic mixture of liquid crystal compounds was used without using an additive.

Table 1 below summarizes the configurations of the smart display devices of Examples 1 to 12.

division liquid crystal compound
(A) additive
(B) chiral dopant
(C) gelator
(D) A:B:C:D weight ratio Cell gap (㎛) Example 1 single compound not used use not used 80:0:20:0 20 Example 2 single compound not used use not used 70:0:30:0 20 Example 3 single compound not used use not used 60:0:40:0 20 Example 4 eutectic mixture use not used not used 90:10:0:0 20 Example 5 eutectic mixture use not used not used 85:15:0:0 20 Example 6 eutectic mixture use not used not used 80:20:0:0 20 Example 7 eutectic mixture use not used not used 75:25:0:0 20 Example 8 eutectic mixture use not used not used 70:30:0:0 20 Example 9 eutectic mixture use use not used A+B:C:D=80:20:0
A:B=80:20 20 Example 10 eutectic mixture use use not used A+B:C:D=70:30:0
A:B=80:20 20 Example 11 eutectic mixture use use not used A+B:C:D=60:40:0A:B=80:20 20 Example 12 eutectic mixture use use not used A+B:C=60:40A+B+C:D=99:1
A:B=80:20 10 Example 13 eutectic mixture use use use A+B:C=60:40A+B+C:D=99:1
A:B=80:20 10 Comparative Example 1 eutectic mixture not used not used not used 100:0:0:0 20 Comparative Example 2 single compound not used not used not used 100:0:0:0 20

[Experimental example]

Experimental Example 1: Analysis of phase transition temperature change according to chiral dopant content

In order to analyze the phase transition temperature change according to the chiral dopant content, by measuring the change in the enthalpy value according to the temperature change using Differential Scanning Calorimetry (DSC) for the smart display devices of Examples 1 to 3 and Comparative Example 1 The phase transition temperature was observed and the results are shown in FIG. 6 . 6 (a) is a graph of the measurement of the phase transition temperature, (b) is a photograph according to the temperature of the smart display device of Example 3.

According to this, it was confirmed that when the liquid crystal compound represented by Formula 1 having a phase transition temperature of 36° C. was mixed with a chiral dopant represented by Formula 3, the phase transition temperature could be sequentially lowered to 10° C. However, it is difficult to lower the phase transition temperature close to 0°C with only the chiral dopant.

Experimental Example 2: Analysis of Changes in Phase Transition Temperature According to the Content of Additives

In order to analyze the phase transition temperature change according to the additive content, the phase transition temperature was observed in the same manner as in Experimental Example 1 for the smart display devices of Examples 4 to 8 and Comparative Example 2, and the results are shown in FIG. 7 . 7 (a) is a phase transition temperature measurement graph, (b) is a photograph according to the temperature change of the smart display device of Example 11.

According to this, the phase transition temperature of the smart display device of Comparative Example 2 including the eutectic mixture of the liquid crystal compound of Formula 1 and the liquid crystal compound of Compound 2 and not including the additive is about 40° C., and the additive content is gradually increased to achieve the phase transition temperature. It was confirmed that it can be gradually lowered.

However, in Examples 7 and 8, in which 25 wt% or more of the additive was added, the change due to the phase transition tends to become unclear, so the smart display device of Example 6 containing 20 wt% of the additive was selected, and a chiral dopant was added thereto. It is preferable to use a method that further lowers the phase transition change by adding.

When 25 wt% or more of the additive is added, the section showing the nematic liquid crystal phase is very short, so that even a slight deviation from the desired phase transition temperature may cause a problem of light scattering or a large phase change.

Experimental Example 3: Analysis of Changes in Phase Transition Temperature According to the Content of Additives and Chiral Dopants

In order to analyze the phase transition temperature change according to the additive and chiral dopant content of the liquid crystal mixture, the phase transition temperature change was measured in the same manner as in Experimental Example 1 for the smart display devices of Examples 6 and 9 to 11. The results are shown in FIG. 8 .

According to this, the smart display device of Example 6 was able to lower the phase transition temperature of about 40°C by 20°C by adding an additive to the eutectic mixture of two liquid crystal compounds in a weight ratio of 8:2, and additionally a chiral dopant In the case of Example 11 by adding , it can be seen that the phase transition temperature was lowered to 2 to 4 °C.

Therefore, in order to manufacture a display device with high discrimination power by controlling the phase transition temperature close to 0° C. and effectively achieving light scattering so that it can be used for black ice display on the road surface in winter, an additive and a chiral dopant are mixed in an appropriate content ratio. was found to be effective.

Experimental Example 4: Analysis of scattering degree change according to the addition of a gelator

In order to compare the liquid crystal scattering degree of the smart display device when a gelator is added to the liquid crystal mixture, a photograph observing the degree of opacity at room temperature and 0° C. for the smart display devices of Examples 12 and 13 is shown in FIG. 9 shown in 9 (a) is a picture of the smart display device of Example 12, (b) is a picture of the smart display device of Example 13. According to this, it was confirmed that the smart display device of Example 13 in which the gelator was added had a high scattering degree at 0° C., so that the opacity was clearly increased even with the naked eye. That is, it was confirmed that by adding a gelator to a small amount of liquid crystal mixture for use as a black ice display device, the scattering degree of liquid crystal was increased to significantly improve visual identification.

Above, although embodiments of the present invention have been described, those of ordinary skill in the art can add, change, delete or add components within the scope that does not depart from the spirit of the present invention described in the claims. The present invention may be variously modified and changed by, etc., and this will also be included within the scope of the present invention.

Claims (17)

optical cell;
a polymer matrix formed inside the optical cell; and
A liquid crystal mixture in which a liquid crystal compound represented by the following Structural Formula 1 dispersed in the polymer matrix and an additive for regulating a phase transition temperature represented by the following Structural Formula 2 are mixed;
The polymer matrix is a polymer in which a mixed monomer of PETTA (pentaerythritol tetraacrylate), IBMA (isobornyl methacrylate) and THFFA (tetrahydrofurfuryl acrylate) is photopolymerized,
The liquid crystal mixture further comprises a chiral dopant,
The chiral dopant is any one selected from compounds represented by the following Chemical Formulas S811, CB15, A131, ZL1-457 and d-2,
The chiral dopant is included in an amount of 20 to 40 wt% based on the total weight of the liquid crystal mixture,
Smart display device, characterized in that it is for controlling active light shielding according to temperature change;
[Structural Formula 1]

In Structural Formula 1,
M is a biphenylene group,
Any one of P and Q is a C1 to C30 straight-chain alkyl group, and the other one is a cyan group,
m and n are 1.
[Structural Formula 2]

In Structural Formula 2,
M is a biphenylene group,
R is a C1 to C30 straight-chain alkyl group.
[Formula_S811]

[Formula_CB15]

[Formula_A131]

[Formula_ZLl-457]

[Formula_d-2]

delete delete According to claim 1,
A smart display device, characterized in that the phase transition temperature of the liquid crystal mixture is controlled according to the content of the additive. delete According to claim 1,
The liquid crystal mixture is a smart display device, characterized in that it further comprises a gelator (gelator). 7. The method of claim 6,
The gelator is a smart display device, characterized in that the compound represented by any one selected from the following formulas 5 to 7.
[Formula 5]

[Formula 6]

[Formula 7]

delete delete According to claim 1,
The liquid crystal compound represented by Structural Formula 1 is a smart display device, characterized in that it is a compound represented by the following Chemical Formula 1 or Formula 2.
[Formula 1]

[Formula 2]

The method of claim 1,
The additive represented by the structural formula (2) is a smart display device, characterized in that the compound represented by the following formula (3).
[Formula 3]

delete According to claim 1,
The liquid crystal mixture further comprising a chiral dopant further comprises a gelator,
The gelator is a smart display device, characterized in that contained in 0.1 to 2 wt% of the total weight of the liquid crystal mixture and the gelator further comprising the chiral dopant. According to claim 1,
A smart display device, characterized in that the phase transition temperature of the liquid crystal mixture is controlled in the range of 0 °C to 4 °C. delete Two film substrates facing each other at a predetermined interval;
a polymer matrix formed between opposite surfaces of the two film substrates; and
A liquid crystal mixture in which a liquid crystal compound represented by the following Structural Formula 1 dispersed in the polymer matrix and an additive for regulating a phase transition temperature represented by the following Structural Formula 2 are mixed;
The polymer matrix is a polymer in which a mixed monomer of PETTA (pentaerythritol tetraacrylate), IBMA (isobornyl methacrylate) and THFFA (tetrahydrofurfuryl acrylate) is photopolymerized,
The liquid crystal mixture further comprises a chiral dopant,
The chiral dopant is a compound represented by any one selected from the following formulas S811, CB15, A131, ZL1-457 and d-2,
The chiral dopant is included in an amount of 20 to 40 wt% based on the total weight of the liquid crystal mixture,
Smart optical film, characterized in that it is for active light shielding control according to temperature change.
[Structural Formula 1]

In Structural Formula 1,
M is a biphenylene group,
Any one of P and Q is a C1 to C30 straight-chain alkyl group, and the other one is a cyan group,
m and n are 1.
[Structural Formula 2]

In Structural Formula 2,
M is a biphenylene group,
R is a C1 to C30 straight-chain alkyl group.
[Formula_S811]

[Formula_CB15]

[Formula_A131]

[Formula_ZLl-457]

[Formula_d-2]

17. The method of claim 16,
The smart optical film is a smart optical film, characterized in that for displaying black ice on the road surface.

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