CN109705882A - A kind of liquid crystal media, polarization separating film and preparation method thereof - Google Patents
A kind of liquid crystal media, polarization separating film and preparation method thereof Download PDFInfo
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- CN109705882A CN109705882A CN201711014910.5A CN201711014910A CN109705882A CN 109705882 A CN109705882 A CN 109705882A CN 201711014910 A CN201711014910 A CN 201711014910A CN 109705882 A CN109705882 A CN 109705882A
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- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 4
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- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The present invention provides a kind of liquid crystal medias that can be applied to polarization separating film, and the liquid crystal media includes: the first component, and described first group is selected from by least one group formed selected from compounds of formula I；And optional second component, described second group is selected from the group being made of at least one polymerization initiator.The present invention also provides the polarization separating films and preparation method thereof comprising the liquid crystal media.The liquid crystal media transition temperature range of the invention is big, and optical anisotropy is good, and the polarization separating film thermal adaptability being made from it is good, and polarization separation effect is good, while its manufacture craft is simple, and yields is high, is applicable to be mass produced.P1‑R1‑MG‑R2‑P2 I。
Description
Technical Field
The present invention relates to a liquid crystal medium, and more particularly, to a liquid crystal medium suitable for a polarization separation film. The invention also relates to a polarization separation film containing the liquid crystal medium and a preparation method thereof.
Background
As a passive light emitting device, a liquid crystal display needs to rely on a backlight source at the back of the display screen to illuminate the screen. Due to the special structure and requirements of the liquid crystal display, the effectively utilized light is only light in a specific polarization direction, so that the utilization rate of the final light intensity of the traditional backlight source is only 5% of the original light intensity, the light utilization rate is low, the energy consumption is high, and adverse effects such as heating and black screen generation of the display are easily caused.
One solution to these problems is to directly use a backlight source capable of emitting light with specific polarization to achieve the effect of improving the light utilization rate. In this method, it is necessary to use a film having a polarization separation function for emitting light of a specific polarization by utilizing polarization-dependent total reflection, scattering, and interaction with a layer having an optically anisotropic property. Where the choice of the material for the optically anisotropic layer is of critical importance, birefringent materials having both ordinary and extraordinary refractive indices are generally chosen. In the prior art, polymers can be made birefringent by stretching the polymers, and thus can be applied to polarization separation membranes, such as polyethylene terephthalate (PET) and polyethylene Phthalate (PEN) as mentioned in "Polarized back light based on selective total internal reflection at microorganisms", and stretching polymerization and its manufacturing method are also described in US 5825543. However, in this technique, the control difficulty of the stretching process is high, the overall uniformity is not good, and the requirement on the manufacturing equipment is high, so that the manufacturing cost is increased. Meanwhile, the birefringent material made of PEN or PET has a narrow temperature adaptation range, and the birefringence is unstable along with the temperature change, so that the application field of the device made of the birefringent material is limited.
In another prior art, a liquid crystal polymer is used as a birefringent material, and the liquid crystal polymer is formed by polymerizing a liquid crystal monomer and then aligning the liquid crystal polymer, thereby forming a birefringent layer having optical anisotropy. However, this technique has disadvantages such as difficulty in aligning the liquid crystal polymer, non-uniformity in optical properties of the formed birefringent film, and poor polarization separation effect.
Therefore, it is desirable to provide a liquid crystal medium for a polarization separation film, which is made of a birefringent material with good temperature adaptability and good polarization separation effect, and has a simple manufacturing process, and is suitable for the purpose of mass production.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention aims to provide a liquid crystal medium which is applicable to a polarization separation film, has a large phase-change temperature range and good optical anisotropy, and a birefringent material prepared from the liquid crystal medium has good temperature adaptability, a good polarization separation effect, a simple manufacturing process and is applicable to large-scale production. Another object of the present invention is to provide a polarization separation film comprising the liquid crystal medium and a method for preparing the same.
The technical scheme of the invention is as follows:
one aspect of the present invention provides a liquid crystal medium applicable to a polarization separation film, the liquid crystal medium comprising:
a first component selected from the group consisting of at least one compound selected from formula I,
P1-R1-MG-R2-P2i; and
optionally a second component selected from the group consisting of at least one polymerization initiator,
wherein,
P1and P2Each independently represents a polymerizable group or-CH3And P is1And P2At least one of which is a polymerizable group;
R1and R2Each independently represents an alkyl group having 1 to 18 carbon atoms, wherein one or more H in the alkyl group may be substituted by F or Cl, and one or more non-adjacent-CH in the alkyl group2-may each be independently replaced by-O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COs-, -CH ═ CH-, -CH ═ CF-, -CF ═ CF-, -C ≡ C-, or-CH (cn) -in a manner that does not comprise two-O-groups adjacent to each other, or two groups selected from the group consisting of-OCO-, -SCO-, -OCOO-, -COs-, -COO-, and-CH ═ CH-adjacent to each other;
MG denotes a mesogen.
In some embodiments, R1And R2Each independently represents an alkyl group having 1 to 18 carbon atoms, wherein one or more of the alkyl groups are not adjacent to-CH2-may each be independently replaced by-O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COs-, -CH ═ CH-, -CH ═ CF-, -CF ═ CF-, -C ≡ C-, or-CH- (cn) -in a manner not comprising two-O-groups adjacent to each other, or two groups selected from the group consisting of-OCO-, -SCO-, -OCOO-, -COs-, -COO-, and-CH ═ CH-adjacent to each other.
In a preferred embodiment, the liquid-crystalline medium further comprises a third component selected from the group consisting of at least one polymerization inhibitor.
In a preferred embodiment, the mesogen is selected from the group consisting of a mesogen of formula II and/or a mesogen of formula III:
-H1-B1-H2-B2-H3- II；
wherein,
H1、H2、H3、H4and H6Each independently represents a ringA cyclic structure selected from the group consisting of A group of (a); wherein one or more H of the cyclic structures may each independently be replaced by F, Cl, CH3Or CH2CH3Substitution;
H5represents an unsaturated cyclic structure selected fromA group of (a);
B1and B2Each independently represents-COO-, -OCO-, -OCOO-, -OCH2-、-CH2O-、-CF2O-、-(CH2)2-、-C≡C-、-CH＝CH-、-CF2CF2-or-CF ═ CF —;
m is 0, 1 or 2.
In a preferred embodiment, the polymerizable group is CH2＝C(R3) -COO-, wherein R3Is CH3、CH2CH3Or H.
In some embodiments, the compound of formula I is preferably selected from the group consisting of:
in some embodiments, the compound of formula I is further preferably selected from the group consisting of formula I-1, formula I-2, formula I-4, and formula I-23.
In some preferred embodiments, the polymerization initiator is a free radical initiator, such as photoinitiator 184Photoinitiator 907TPO (2,4, 6-trimethylbenzoyl-diphenylphosphine oxide), and the like.
In some preferred embodiments, the mass percentage of the second component is no greater than 5%.
In some preferred embodiments, the third component may be And the like.
In some preferred embodiments, the mass percentage of the third component is no greater than 5%. Preferably, the mass percentage of the third component is not more than 2%.
In some preferred embodiments, the optical anisotropy Δ n of the liquid-crystalline medium is greater than 0.1. Preferably, the optical anisotropy Δ n of the liquid-crystalline medium is greater than 0.15.
In another aspect, the present invention provides a polarization separation film comprising the liquid crystal medium, the polarization separation film comprising: the light source comprises a base layer, a light source and a light source, wherein the base layer is provided with a light inlet surface and a light outlet surface, and the light outlet surface is provided with microstructures which are arranged in parallel; and the surface of the birefringent layer is seamlessly and tightly combined with the light-emitting surface of the base layer, the birefringent layer is formed by polymerizing the liquid crystal medium, and the optical axis direction of the birefringent layer is basically parallel to the long axis direction of the microstructure, wherein the natural light entering the polarization separation film from the light-in surface can realize polarization separation and emit polarized light with a required polarization direction.
In some preferred embodiments, the polarization separation film has a polarization contrast ratio of greater than 3.
Another aspect of the present invention provides a method of preparing the polarization separation film, the method comprising: forming an alignment layer on a substrate; coating the liquid crystal medium provided by the invention on the alignment layer to form a liquid crystal state birefringent layer; attaching the liquid crystal state birefringent layer to the base layer; aligning the liquid crystal medium in the liquid crystal state birefringent layer; polymerizing and curing the liquid crystal state birefringent layer; and removing the substrate and the alignment layer.
Has the advantages that:
the invention provides a polymerizable liquid crystal medium, which has the advantages of large phase-change temperature range, good optical anisotropy, good temperature adaptability of a birefringent material prepared from the liquid crystal medium, good polarization separation effect, simple manufacturing process, high yield and suitability for large-scale production, and can be applied to a polarization separation membrane.
Drawings
The invention may be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic view showing the mechanism and operation of a polarization separation film according to an embodiment of the present invention;
fig. 2 is a schematic flow diagram of a manufacturing process according to an embodiment of the invention.
Detailed Description
In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, it will be apparent to those skilled in the art that the present invention may be practiced without these specific details. The illustrated example embodiments have been set forth only for the purposes of example and that it is not intended to be limiting. Therefore, the scope of the present invention is not limited by the above-described embodiments, but is defined only by the scope of the appended claims.
In the embodiment, the three components are mixed uniformly in different proportions under heating to form a liquid crystal medium for preparing the polarization separation film. As shown in fig. 1, the polarization separation film includes a base layer 10 and a birefringent layer 20, and has microstructures arranged in parallel on a surface where the base layer 10 and the birefringent layer 20 are closely combined. The cross section of the microstructure can be an isosceles triangle as shown in fig. 1, or can be an asymmetric triangle, or can be a triangle with an arc-shaped top, a polygonal line, an arc-shaped or other concave-convex structure. The birefringent layer 20 is formed by polymerizing a liquid crystal medium having a refractive index n for ordinary raysoAnd refractive index n of extraordinary rayseAnd n iseGreater than no. The optical axis direction of the birefringent layer 20 is substantially parallel to the long axis direction of the microstructures of the surface of the base layer 20, so that the refractive index difference Δ n (i.e., optical anisotropy) of the birefringent layer 20 is maximized in the direction orthogonal to the extension direction, thereby improving the efficiency of polarization separation. In a preferred embodiment, the extraordinary refractive index n of the liquid crystal medium in the birefringent layer 20eAnd ordinary ray refractive index noThe difference Δ n (i.e., optical anisotropy) is greater than 0.1. The base layer 10 consists of an isotropic homogeneous medium having a refractive index which is equal to the ordinary refractive index n of the birefringent layer 20oSubstantially identical. Due to the presence of the birefringent layer 20, the s-polarized light and the p-polarized light have different optical paths inside the birefringent layer 20. For example, for s-polarized light 11, there is total reflection at the interface between the microstructure and the birefringent layer 20, and the totally reflected light enters the outgoing angle range and exits from the surface of the polarization separation film. For a p-polarized light ray 12, since the refractive indices in the base layer 10 and the birefringent layer 20 are substantially the same, there is no total reflection at the interface, and the original direction can be maintained to continue propagating in the form of a waveguide in the birefringent layer20, and the total reflection occurs at the interface with the air so as not to be emitted from the surface of the polarization separation film, thereby realizing the characteristic of polarization separation, and selectively emitting s-polarized light. The p-polarized light propagating in the form of a waveguide is partially converted into s-polarized light by scattering or optical rotation during propagation, and thus can be redirected to exit from the upper surface.
As shown in fig. 2, the method for preparing the polarization separation film includes the following steps: the alignment layer 30 is formed on the substrate 40 by rubbing, photo-alignment, oblique evaporation, LB film, or the like. The substrate 40 may comprise a hard material (e.g., optical glass), may also comprise a flexible substrate (e.g., PET), and the like. The material of the alignment layer 30 may be polyimide. Next, a liquid crystal medium in a liquid crystal state is coated on the alignment layer 30 to form the birefringent layer 20 in a liquid crystal state. Then, the base layer 10 is bonded to the birefringent layer 20 in the liquid crystal state by means of a device having a pressure bonding function. When the substrate 10 is attached to the liquid crystal display panel, the substrate 10 is positioned above the birefringent layer 20, and pressure is gradually applied to the upper surface of the substrate 10, so that the surface of the substrate 10 having the microstructure is in seamless contact with the birefringent layer 20 in the liquid crystal state, and the microstructure on the surface of the substrate 10 is completely embedded in the birefringent layer 20 in the liquid crystal state. After the lamination is completed, the entire structure is left at a certain temperature for a certain period of time, so that the molecules of the liquid crystal medium in the liquid crystal state birefringent layer 20 are aligned in the preset direction of the alignment layer 30, that is, in the long axis direction of the microstructure. In the alignment process, the substrate 40 needs to be positioned at the lowermost side, thereby improving the efficiency of liquid crystal alignment using gravity. After alignment, the birefringent layer 20 in the liquid crystal state is polymerized and cured by photopolymerization, thermal polymerization, and radiation polymerization, so as to be integrated with the base layer 10. Finally, the substrate 40 and the alignment layer 30 are removed, and a polarization separation film composed of the base layer 10 and the birefringent layer 20 is obtained.
In the following examples, the general procedure was to first mix the corresponding first, second or third components in proportions to form a specific liquid-crystalline medium, wherein some of the examples were each used to determine the ordinary refractive index n of the liquid-crystalline medium by conventional methods (Abbe refractometer, 589nm, 25 ℃ C.)oAnd refractive index n of extraordinary rayseCalculating delta n and measuring the phase change temperature (namely clearing point) of the sample; then, a polarization separation film was manufactured according to the above steps, in which the thickness of the base layer 10 was 50 mm, the thickness of the birefringent layer 20 was 20 mm, the microstructure of the surface of the base layer 10 was a prism structure as shown in fig. 1, the prism pitch was 25 mm, and the prism height was 8 mm; after the manufacture is finished, the polarization contrast of the polarization separation film is tested, and the specific operation is that a light source is arranged on the light inlet surface of the polarization separation film, a polaroid is arranged on the light outlet surface of the polarization separation film, then the light intensity of different polarized light rays passing through the polaroid is measured by a light flux meter, so that the ratio of the light intensity of s-polarization to the light intensity of p-polarization (polarization contrast) is calculated, and the optical performance of the liquid crystal medium is measured.
The components used in the following examples can be synthesized by a known method or obtained commercially. These synthesis techniques are conventional, and the resulting liquid crystal compounds were tested to meet the standards for electronic compounds.
Example 1
Wherein Δ n of the liquid-crystalline medium is 0.191, where no1.51, n of a common light guide plate material (e.g., PMMA)pAnd (4) matching. The clearing point temperature of the liquid crystal medium is 131 ℃, and the working temperature range of the liquid crystal medium serving as a birefringent layer medium is greater than the glass transition temperature of PET (polyethylene terephthalate) of 70 ℃ and the glass transition temperature of PEN of 120 ℃. The polarization contrast ratio of the polarization separation film was 6.5: 1.
Example 2
Wherein Δ n of the liquid-crystalline medium is 0.191. The polarization contrast ratio of the polarization separation film was 6: 1.
Example 3
Wherein the delta n of the liquid crystal medium is 0.151, and the clearing point temperature is 130 ℃. The polarization contrast ratio of the polarization separation film was 6.5: 1.
Example 4
Wherein Δ n of the liquid-crystalline medium is 0.189. The polarization contrast ratio of the polarization separation film was 5: 1.
Example 5
Wherein the polarization contrast ratio of the polarization separation film is 5: 1.
Example 6
Wherein the polarization contrast ratio of the polarization separation film is 4.5: 1.
Example 7
Wherein the polarization contrast ratio of the polarization separation film is 6: 1.
Example 8
Wherein the polarization contrast ratio of the polarization separation film is 7: 1.
Through the embodiments, the liquid crystal medium has a large phase-change temperature range and good optical anisotropy, so that the double-folded polarization separation film prepared from the liquid crystal medium has good temperature adaptability and good polarization separation effect, and meanwhile, the double-folded polarization separation film is simple in manufacturing process and high in yield and is suitable for large-scale production.
Although several exemplary embodiments have been described above in detail, the disclosed embodiments are merely exemplary and not limiting, and those skilled in the art will readily appreciate that many other modifications, adaptations, and/or alternatives are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of the present disclosure. Accordingly, all such modifications, adaptations, and/or alternatives are intended to be included within the scope of the present disclosure as defined by the following claims.
Claims (10)
1. A liquid crystal medium applicable to a polarization separation film, comprising:
a first component selected from the group consisting of at least one compound selected from formula I
P1-R1-MG-R2-P2I; and
optionally a second component selected from the group consisting of at least one polymerization initiator,
wherein,
P1and P2Each independently represents a polymerizable group or-CH3And P is1And P2At least one of which is a polymerizable group;
R1and R2Each independently represents an alkyl group having 1 to 18 carbon atoms, wherein one or more H in the alkyl group may be substituted by F or Cl, and one or more non-adjacent-CH in the alkyl group2-may each be independently replaced by-O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COs-, -CH ═ CH-, -CH ═ CF-, -CF ═ CF-, -C ≡ C-, or-CH (cn) -in a manner that does not comprise two-O-groups adjacent to each other, or two groups selected from the group consisting of-OCO-, -SCO-, -OCOO-, -COs-, -COO-, and-CH ═ CH-adjacent to each other;
MG denotes a mesogen.
2. The liquid-crystalline medium of claim 1, further comprising a third component selected from the group consisting of at least one polymerization inhibitor.
3. The liquid-crystalline medium according to claim 1, characterized in that the mesogen is selected from the group consisting of mesogens of formula II and/or III:
-H1-B1-H2-B2-H3- II；
wherein,
H1、H2、H3、H4and H6Each independently represents a cyclic structure selected from the group consisting of A group of (a); wherein one or more H of the cyclic structures may each independently be replaced by F, Cl, CH3Or CH2CH3Substitution;
H5represents an unsaturated cyclic structure selected fromA group of (a);
B1and B2Each independently represents-COO-, -OCO-, -OCOO-, -OCH2-、-CH2O-、-CF2O-、-(CH2)2-、-C≡C-、-CH＝CH-、-CF2CF2-or-CF ═ CF —;
m is 0, 1 or 2.
4. The liquid-crystalline medium according to claim 1, wherein the polymerizable group is CH2＝C(R3) -COO-, wherein R3Is CH3、CH2CH3Or H.
5. The liquid-crystalline medium according to claim 1, characterized in that the second component is present in a mass percentage of not more than 5%.
6. The liquid-crystalline medium according to claim 2, characterized in that the third component is present in a mass percentage of not more than 5%.
7. Liquid-crystalline medium according to any of claims 1 to 6, characterized in that the optical anisotropy Δ n of the liquid-crystalline medium is greater than 0.1.
8. A polarizing separation film comprising the liquid-crystalline medium according to any one of claims 1 to 7, the polarizing separation film comprising:
the light source comprises a base layer, a light source and a light source, wherein the base layer is provided with a light inlet surface and a light outlet surface, and the light outlet surface is provided with microstructures which are arranged in parallel; and
the surface of the birefringent layer is seamlessly and tightly combined with the light emergent surface of the base layer, the birefringent layer is formed by polymerizing the liquid crystal medium, the optical axis direction of the birefringent layer is basically parallel to the long axis direction of the microstructure,
the natural light entering the polarization separation film from the light incident surface can realize polarization separation, and the polarized light with the required polarization direction is emitted.
9. The polarization separation film of claim 8, wherein the polarization contrast ratio of the polarization separation film is greater than 3.
10. A method for producing a polarization separation film according to claim 8 or 9, comprising the steps of:
forming an alignment layer on a substrate;
applying a liquid crystalline medium according to any of claims 1 to 7 on said alignment layer to form a liquid crystalline birefringent layer;
attaching the liquid crystal state birefringent layer to the base layer;
aligning the liquid crystal medium in the liquid crystal state birefringent layer;
polymerizing and curing the liquid crystal state birefringent layer; and
removing the substrate and the alignment layer.
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Application publication date: 20190503 |