Patent Application
20160355733
The present invention relates to the field of display technology, and particularly relates to a liquid crystal composition, a patterned phase delay film prepared from the liquid crystal composition and preparation method thereof, and a display device comprising the phase delay film.
3D Technology comprises polarized 3D technology and Shutter Glass (SG) technology (also known as shutter 3D technology). Currently, glasses with polarization function in the polarized 3D technology need to be installed in a Liquid Crystal Display (LCD) module, which makes the cost relatively high and becomes the main factor that limits its application. However, Film-type Patterned Retarder (FPR) technology developed by LG Display utilizes films as substitutes of the glasses, which allows the costs to be reduced by three quarters and achieves a strong competitiveness in price.
Conventional FPR preparation processes are relatively complex. First of all, it requires coating with an alignment liquid. After drying, an alignment film having two different rotatory directions distributed at intervals from each other is prepared using polarizing ultraviolet light. Thereafter, a liquid crystal layer is coated on the alignment film, and the effect of the alignment film allows the liquid crystal layer to have different rotatory directions in adjacent lines. Then a FPR film is obtained by polymerization with ultraviolet light.
Embodiments of the present invention are directed to the problem that the preparation process of a patterned phase delay film in the prior art is complex, and provide a liquid crystal composition, a patterned phase delay film prepared from the liquid crystal composition and preparation method thereof, and a display device comprising the phase delay film.
According to one aspect of the present invention, there is provided a liquid crystal composition which comprises a photo-polymerizable liquid crystal mixture and a heat-polymerizable liquid crystal mixture. The photo-polymerizable liquid crystal mixture and the heat-polymerizable liquid crystal mixture have opposite rotatory directions.
In an embodiment, a mass ratio of the photo-polymerizable liquid crystal mixture to the heat-polymerizable liquid crystal mixture is 1:(0.4-3).
In an embodiment, the photo-polymerizable liquid crystal mixture comprises a small molecule nematic liquid crystal, a photo-polymerizable monomer, a UV-absorbing dye, a chiral additive and a photoinitiator.
In an embodiment, assume that total mass of the photo-polymerizable liquid crystal mixture is 100%, the photo-polymerizable liquid crystal mixture comprises 28-69.5% of small molecule nematic liquid crystal, 15-40% of photo-polymerizable monomer, 2-15% of UV-absorbing dye, 0-25% of chiral additive and 0.5-5% of photoinitiator.
The photo-polymerizable monomer may either be a photo-polymerizable liquid crystal monomer or a non-liquid crystal photo-polymerizable monomer. In an embodiment, the photo-polymerizable liquid crystal monomer may include any one of the following substances:
In an embodiment, the UV-absorbing dye includes:
In an embodiment, the photoinitiator includes:
In an embodiment, the heat-polymerizable liquid crystal mixture comprises a small molecule nematic liquid crystal, a heat-polymerizable monomer, a curing agent and a chiral additive.
In an embodiment, assume that total mass of the heat-polymerizable liquid crystal mixture is 100%, the heat-polymerizable liquid crystal mixture comprises 35-73% of small molecule nematic liquid crystal, 10-20% of heat-polymerizable monomer, 12-20% of curing agent and 5-25% of chiral additive.
In an embodiment, the heat-polymerizable monomer includes a bisphenol F epoxy resin having the following molecular formula:
or a polyethylene glycol bisglycidyl ether having the following molecular formula:
In an embodiment, the curing agent includes 1,8-diamino-3,6-dioxaoctane having the following molecular formula:
or 4,4′-diaminodicyclohexylmethane having the following molecular formula:
In an embodiment, the chiral additive includes any one of the following substances:
With the liquid crystal composition of the embodiments of the present invention, a patterned phase delay film with high reflectance and transmittance can be obtained by UV-polymerizing and photo-polymerizing the liquid crystal composition. The preparation process is simple and the costs are low.
According to another aspect of the present invention, there is provided a patterned phase delay film which is prepared from the above-mentioned liquid crystal composition.
According to another aspect of the present invention, there is provided a preparation method for a patterned phase delay film, which comprises the following steps: injecting the above mentioned liquid crystal mixture into a liquid crystal cell; irradiating the liquid crystal cell covered with a photo mask with UV light to complete UV-polymerization; and heating the liquid crystal cell to complete heat-polymerization.
A person skilled in the art will appreciate that appropriate conditions for UV-polymerization and heat-polymerization may be selected in accordance with specific components of the liquid crystal composition and performance requirements on the obtained phase delay film.
In an embodiment, the condition for the UV-polymerization is wavelength of the UV light being 365 nm, intensity being 0.001-100 mW/cm2, and irradiation time being 5-240 min
In an embodiment, the condition for the heat-polymerization is temperature ranging from 30 to 120° C. and heating time ranging from 20 to 60 min.
According to another aspect of the present invention, there is provided a display device which comprises the above mentioned patterned phase delay film.
Since the display device comprises the above mentioned patterned phase delay film, it can be used in 3D display with the advantages of simple preparation, low costs, and the like.
To facilitate those skilled in the art to well understand the concept of the present invention, several embodiments of the present invention will be described in detail in conjunction with the drawings.
In one embodiment of the present invention, a liquid crystal composition is provided which comprises a laevorotatory photo-polymerizable liquid crystal mixture and a dextrorotatory heat-polymerizable liquid crystal mixture.
In another embodiment of the present invention, a liquid crystal composition is provided which comprises a dextrorotatory photo-polymerizable liquid crystal mixture and a laevorotatory heat-polymerizable liquid crystal mixture.
The photo-polymerizable liquid crystal mixture and heat-polymerizable liquid crystal mixture may comprise the previously mentioned various specific components. It should be understood that it is also possible to mix any other heat-polymerizable liquid crystal mixture and photo-polymerizable liquid crystal mixture in the prior art, as long as the optically rotatory directions of the two mixtures are opposite.
The photo-polymerizable liquid crystal mixture or heat-polymerizable liquid crystal mixture may comprise a small molecule nematic liquid crystal. In some embodiments, a liquid crystal temperature of the small molecule nematic liquid crystal ranges from −20° C. to 120° C., and an optical anisotropy Δn ranges from 0.19 to 0.21 (589 nm, 293K), e.g., SLC1717 (Shijiazhuang Yongshenghuaqing Liquid Crystal LTD.), MAT 10-1614 (Merck Corporation), ZBE-5371XX (JNC Corporation), and the like.
In one embodiment of the present invention, a patterned phase delay film is provided which is prepared from the above-mentioned liquid crystal composition. The preparation method comprises the following steps: injecting the above mentioned liquid crystal composition into a liquid crystal cell; irradiating the liquid crystal cell covered partially with a photo mask with UV light to complete the UV-polymerization; and heating the liquid crystal cell to complete the heat-polymerization so as to form the patterned phase delay film.
Specifically, the liquid crystal composition can be obtained by uniformly mixing the photo-polymerizable liquid crystal mixture and heat-polymerizable liquid crystal mixture by means of solvent evaporation or heat melting. The solvent evaporation and heat melting are conventional approaches. For the solvent evaporation, the solvent is usually selected from organic solvents, such as tetrahydrofuran, acetone, dichloromethane, or the like. For the heat melting, the liquid crystal composition can be heated to its clearing point temperature to carry out the melt mixing. The specific operation conditions will not be repeated here.
Then referring to
The concentration gradient of the photo-polymerizable monomer may be represented by a polymerization rate difference in the photo-polymerizable monomer polymerization. In the direction vertical to the polymer network (i.e. the direction vertical to the glass substrate 1 in the liquid crystal cell), the polymerization rate is faster at the side near the UV light, which causes the photo-polymerizable monomers away from the UV light and those at the place covered by the photo mask 3 to migrate to the side near the UV light. Most of the photo-polymerizable monomers may migrate to the light permeable region of the photo mask 3. The polymer network formed near the UV light is more intensive than that formed away from the UV light. That is, in the direction vertical to the polymer network (i.e. the direction vertical to the glass substrate 1 in the liquid crystal cell), the concentration gradient of the polymer network of photo-polymerizable monomers is formed. Moreover the photo-polymerizable monomers at the place covered by the photo mask 3 may migrate to the side near the UV light, so the concentration gradient of the polymer network of photo-polymerizable monomers is also formed in the horizontal direction of the liquid crystal cell.
Thus the photo-polymerizable liquid crystal monomers at the place of the liquid crystal cell 2 irradiated with the UV light are polymerized during the migration, and after the polymerization, a concentration gradient polymer network of photo-polymerizable monomers is formed at the place of the liquid crystal cell 2 irradiated with the UV light. The rotatory direction of the concentration gradient polymer network may be determined by the contents and optical rotation of the chiral substances in the system. So the system exhibits levorotation if the content of the laevorotatory substance is higher, and the network after polymerization is a laevorotatory network. If the content of the dextrorotatory substance is higher in the system, the system exhibits dextrorotation, and the network after polymerization is a dextrorotatory network.
Then the UV-polymerized liquid crystal cell is placed on a heating platform for heating, so that the heat-polymerizable monomers in the liquid crystal composition are polymerized. The temperature of the heating platform may be 30° C.-120° C., and the heat curing time may be 20-60 min. In some embodiments, the temperature of the heating platform may be 80° C.-100° C., and the heat curing time may be 40-50 min.
The polymerization of heat-polymerizable monomers takes place when the temperature reaches the heat initiation temperature. Pure UV light irradiation would not lead to the heat-polymerization. In addition, in the step of UV light irradiation, since the difference of the polymerization rates of the photo-polymerizable monomers may cause the photo-polymerizable monomers to move to the direction with the stronger UV light, a majority of the heat-polymerizable monomers will be passively migrated (in the opposite direction), and the concentration gradient of heat-polymerizable monomers may be also formed. The content of heat-polymerizable monomers is lower near the place where the UV light is stronger, while the content of heat-polymerizable monomers is higher at the place where the UV light is weaker and the place covered by the photo mask 3, so the most of the heat-polymerizable monomers are migrated to the place covered by the photo mask, and thus the concentration gradient of heat-polymerizable monomers is formed opposite to the concentration gradient of photo-polymerizable monomers. That is, the concentration gradient of heat-polymerizable monomers is also formed in both the horizontal direction and vertical direction of the liquid crystal cell. During the heating, the concentration gradient of the polymer network of heat-polymerizable monomers is also formed in both the horizontal direction and vertical direction of the liquid crystal cell. Similarly, as the rotatory direction of the concentration gradient polymer network is determined by the contents and optical rotation of the chiral substances in the system, the system exhibits levorotation if the content of the laevorotatory substance is higher and the network after polymerization is a laevorotatory network, and if the content of the dextrorotatory substance is higher, the system exhibits dextrorotation, and the network after polymerization is a dextrorotatory network.
In addition, the heat-polymerizable monomers remained at the exposed place of the photo mask (i.e. the irradiated place of the photo mask) are polymerized upon heating. But the heat-polymerizable monomers remained at the exposed place of the photo mask (with lower contents) are not sufficient to change the optical rotation of the polymer network of photo-polymerizable monomers which has higher contents. After the polymerization, the heat-polymerizable monomers function to further stabilize the laevorotatory polymer network which is formed previously from the photo-polymerizable monomers. As shown in
Moreover the concentration gradients of polymer networks may be formed in the different regions (i.e. the covered region and the exposed region of the mask), i.e., helical pitch gradients of a cholesteric liquid crystal composite system.
The helical pitch gradients of the cholesteric liquid crystal composite system correspond to the selective reflection bandwidth range. The corresponding relation may comply with the Bragg reflection formula: Δλ=Δn×Δp, wherein Δλ is the selective reflection bandwidth, Δn is the liquid crystal birefringence, and Δp is the helical pitch gradient of the liquid crystal composite system. Thus the different regions may reflect the lights of the corresponding bandwidth ranges.
In one embodiment of the present invention, a patterned phase delay film is provided which may be prepared from the liquid crystal composition according to the embodiments of the present invention by the above-mentioned preparation method. The patterned phase delay film may have the advantages of simple preparation process and low cost.
In one embodiment of the present invention, a display device is provided which comprises the above-mentioned patterned phase delay film. Since the display device is configured with the above-mentioned patterned phase delay film, it can be used in 3D display.
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 (Shijiazhuang Yongshenghuaqing Liquid Crystal LTD.) as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomer having the molecular formula of:
the UV-absorbing dye having the molecular formula of:
the chiral additive having the molecular formula of:
and the photoinitiator having the molecular formula of:
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, a bisphenol F epoxy resin as the heat-polymerizable monomers having the following molecular formula:
4,4′-diaminodicyclohexylmethane as the curing agent having the following molecular formula:
and the chiral additive having the following molecular formula:
The laevorotatory photo-polymerizable liquid crystal mixture and dextrorotatory heat-polymerizable liquid crystal mixture may be mixed into a uniform mixture according to the mixing mass ratio of Table 1 by means of solvent evaporation, thereby obtaining a liquid crystal composition, wherein the total mass of the photo-polymerizable liquid crystal mixture is 1 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1 gram. The mass of each component in the photo-polymerizable liquid crystal mixture may be calculated according to the mass percentage in Table 1, and the corresponding mass of each component is weighed. The respective components may be placed into a 5 ml glass bottle. Acetone may be added slowly, dropwise into the glass bottle until the components are completely dissolved. Subsequently, the glass bottle may be placed on a heating platform of 40° C. for 5-6 hours until the solvent evaporates completely, and the formulation of the photo-polymerizable liquid crystal mixture is finished. Then, the heat-polymerizable liquid crystal mixture may be formulated according to the same process.
As shown in
The liquid crystal cell 2 may be irradiated with UV light at a wavelength of 365 nm, under an irradiation intensity of 1.4 mW/cm2, for 25 minutes.
As shown in
The UV-polymerized liquid crystal cell is placed on a heating platform (for heating), so that the heat-polymerizable monomers in the liquid crystal mixtures are polymerized. The temperature of the heating platform may be 80° C., and the heat curing time may be 45 minutes. The polymerization network obtained by curing the heat-polymerizable monomers may form a region which may reflect dextrorotatory visible light bands.
As shown in
Moreover, the concentration gradients of the polymer networks are formed at different regions (the covered region and exposed region of the mask), i.e., helical pitch gradients of a cholesteric liquid crystal composite system.
The film obtained by the two-step polymerization process is subjected to a spectrum test, and the result is as shown in
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 1.43 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 0.57 gram.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
the UV-absorbing dye having the molecular formula of:
the chiral additive having the molecular formula of:
and the photoinitiator having the molecular formula of:
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 (Shijiazhuang Yongshenghuaqing Liquid Crystal LTD.) as the small molecule nematic liquid crystal, a bisphenol F epoxy resin as the heat-polymerizable monomer having the following molecular formula:
4,4′-diaminodicyclohexylmethane as the curing agent having the following molecular formula:
and a chiral additive having the following molecular formula:
From such the liquid crystal composition, the patterned phase-delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 100 mW/cm2, the duration of UV irradiation is 5 minutes, the temperature of the heating platform is 40° C., and the heat curing time is 50 minutes.
The spectrogram of the patterned phase-delay film obtained after the two-step polymerization is similar to
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 0.67 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1.33 gram.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
the UV-absorbing dye having the molecular formula of:
the chiral additive having the molecular formula of:
and the photoinitiator having the molecular formula of:
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, a bisphenol F epoxy resin as the heat-polymerizable monomer having the following molecular formula:
4,4′-diaminodicyclohexylmethane as the curing agent having the following molecular formula:
and the chiral additive having the following molecular formula:
From such the liquid crystal composition, the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 30 mW/cm2, the duration of UV irradiation is 90 minutes, the temperature of the heating platform is 50° C., and the heat curing time is 40 minutes.
The spectrogram of the patterned phase-delay film obtained after the two-step polymerization is similar to
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 0.5 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1.5 gram.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
the UV-absorbing dye having the molecular formula of:
the chiral additive having the molecular formula of:
and the photoinitiator having the molecular formula of:
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystals, the polyethylene glycol bisglycidyl ether as the heat-polymerizable monomer having the following molecular formula:
1,8-diamino-3,6-dioxaoctane as the curing agent having the following molecular formula:
and the chiral additive having the following molecular formula:
From such the liquid crystal composition, the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 60 mW/cm2, the duration of UV irradiation is 60 minutes, the temperature of the heating platform is 70° C., and the heat curing time is 35 minutes.
The spectrogram of the patterned phase-delay film obtained after the two-step polymerization is similar to
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 1.11 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 0.89 gram.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystals, the photo-polymerizable liquid crystal monomers having the molecular formula of:
the UV-absorbing dye having the molecular formula of:
the chiral additive having the molecular formula of:
and the photoinitiator having the molecular formula of:
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the polyethylene glycol bisglycidyl ether as the heat-polymerizable monomer having the following molecular formula:
1,8-diamino-3,6-dioxaoctane as the curing agent having the following molecular formula:
and the chiral additive having the following molecular formula:
From such the liquid crystal composition, the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 0.001 mW/cm2, the duration of UV irradiation is 240 minutes, the temperature of the heating platform is 30° C., and the heat curing time is 60 minutes.
The spectrogram of the patterned phase-delay film obtained after the the two-step polymerization is similar to
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 0.57 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1.43 gram.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
the UV-absorbing dye having the molecular formula of:
the chiral additive having the molecular formula of:
and the photoinitiator having the molecular formula of:
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the polyethylene glycol bisglycidyl ether as the heat-polymerizable monomers having the following molecular formula:
1,8-diamino-3,6-dioxaoctane as the curing agent having the following molecular formula:
and the chiral additive having the following molecular formula:
From such the liquid crystal composition, the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 80 mW/cm2, the duration of UV irradiation is 30 minutes, the temperature of the heating platform is 100° C., and the heat curing time is 25 minutes.
The spectrogram of the patterned phase-delay film obtained after the two-step polymerization is similar to
The present embodiment provides the liquid crystal composition which comprises the laevorotatory photo-polymerizable liquid crystal mixture and the dextrorotatory heat-polymerizable liquid crystal mixture. The amounts of the components contained in the two mixtures as well as their mixing mass ratio are shown in Table 1, wherein the total mass of the photo-polymerizable liquid crystal mixture is 0.8 gram, and the total mass of the heat-polymerizable liquid crystal mixture is 1.2 gram.
The laevorotatory photo-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the photo-polymerizable liquid crystal monomers having the molecular formula of:
the UV-absorbing dye having the molecular formula of:
the chiral additive having the molecular formula of:
and the photoinitiator having the molecular formula of:
The dextrorotatory heat-polymerizable liquid crystal mixture may comprise SLC1717 as the small molecule nematic liquid crystal, the polyethylene glycol bisglycidyl ether as the heat-polymerizable monomer having the following molecular formula:
1,8-diamino-3,6-dioxaoctane as the curing agent having the following molecular formula:
and the chiral additive having the following molecular formula:
From such the liquid crystal composition, the patterned phase delay film may be prepared according to the same preparation process as in the first embodiment with the differences that the wavelength of the UV irradiation is 365 nm, the UV light intensity is 10 mW/cm2, the duration of UV irradiation is 150 minutes, the temperature of the heating platform is 120° C., and the heat curing time is 20 minutes.
The spectrogram of the patterned phase delay film obtained after the two-step polymerization is similar to
Table 1 shows the mass ratios of the photo-polymerizable mix liquid crystals and heat-polymerizable mix liquid crystals as well as the mixing ratios in the above embodiments.
It should be understood that the above embodiments disclosed herein are exemplary only and not limiting the scope of this disclosure. Without departing from the spirit and scope of this invention, other modifications, equivalents, or improvements to the disclosed embodiments are obvious to those skilled in the art and are intended to be encompassed within the scope of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201410779593.6 | Dec 2014 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2015/081730 | 6/18/2015 | WO | 00 |
