Cholesteric liquid crystal composition, liquid crystal display panel and preparation method thereof
10093858 ยท 2018-10-09
Assignee
- Boe Technology Group Co., Ltd. (Beijing, CN)
- Beijing Boe Optoelectronics Technology Co., Ltd. (Beijing, CN)
Inventors
- Kun Jiang (Beijing, CN)
- Jian Wang (Beijing, CN)
- Chunlei Wang (Beijing, CN)
- Wei Zhao (Beijing, CN)
- Na Li (Beijing, CN)
- Xuechao Song (Beijing, CN)
- Ruichen Zhang (Beijing, CN)
- Shaowu Ma (Beijing, CN)
- Lin Han (Beijing, CN)
- Kangdi Zhou (Beijing, CN)
- Lanjun Guo (Beijing, CN)
Cpc classification
C09K19/42
CHEMISTRY; METALLURGY
G02F1/13718
PHYSICS
C09K19/3066
CHEMISTRY; METALLURGY
International classification
C09K19/42
CHEMISTRY; METALLURGY
G02F1/137
PHYSICS
Abstract
Provided are a cholesteric liquid crystal composition, and a liquid crystal display panel including the composition, and their preparation methods. The cholesteric liquid crystal composition contains a block copolymer and a cholesteric liquid crystal, wherein the block copolymer has a block A including a chiral group M.sub.1 and a block B including a chiral group M.sub.2, and the cholesteric liquid crystal has at least two different pitches. The display panel includes an array substrate and a counter substrate placed by cell assembly, and a liquid crystal layer disposed between the array substrate and the counter substrate, wherein the liquid crystal layer comprises the cholesteric liquid crystal composition. The liquid crystal layer in the planar texture is capable of reflecting light of at least two wavelengths in the visible light region.
Claims
1. A cholesteric liquid crystal composition comprising a block copolymer and a cholesteric liquid crystal, wherein: the block copolymer comprises a block A containing a chiral group M.sub.1 and a block B containing a chiral group M.sub.2; the cholesteric liquid crystal has at least two different pitches; the block A comprises a repeating unit of a formula (I): ##STR00010## wherein R.sub.1 is independently selected from hydrogen and C.sub.1-20 alkyl; and n.sub.1 is an integer indicating the number of repeating units; the block B comprises a repeating unit of a formula (II): ##STR00011## wherein R.sub.2 is independently selected from hydrogen and C.sub.1-20 alkyl; and n.sub.2 is an integer indicating the number of repeating units; and the chiral group M.sub.1 and the chiral group M.sub.2 are each independently selected from the group consisting of: ##STR00012##
2. The cholesteric liquid crystal composition of claim 1, wherein the optical rotation of the block A is different from that of the block B.
3. The cholesteric liquid crystal composition of claim 1, wherein the content of the chiral group M.sub.1 in the block A is from 5 to 100 mol %.
4. The cholesteric liquid crystal composition of claim 1, wherein the content of the chiral group M.sub.2 in the block B is from 5 to 100 mol %.
5. The cholesteric liquid crystal composition of claim 1, wherein the chiral group M.sub.1 is different from the chiral group M.sub.2.
6. The cholesteric liquid crystal composition of claim 1, wherein the content of the chiral group M.sub.1 in the block A and the content of the chiral group M.sub.2 in the block B are the same or different.
7. The cholesteric liquid crystal composition of claim 1, wherein the molecular weight of the block copolymer is from about 1000 daltons to about 300,000 daltons.
8. A display panel, comprising an array substrate and a counter substrate placed by cell assembly, and a liquid crystal layer disposed between the array substrate and the counter substrate, wherein the liquid crystal layer comprises the cholesteric liquid crystal composition according to claim 1.
9. The display panel of claim 8, wherein the array substrate has a plurality of pixel regions; the cholesteric liquid crystal composition is evenly distributed in each pixel region and is capable of reflecting light of at least two wavelengths in the visible light region.
10. A method for preparing the cholesteric liquid crystal composition of claim 1, comprising: providing the block copolymer; and mixing the block copolymer with an initial liquid crystal molecule.
11. The method of claim 10, wherein the block copolymer is provided by forming the block A and the block B in the block copolymer sequentially; or forming a polymer A containing the block A and a polymer B containing the block B respectively, and then connecting the polymer A with the polymer B.
12. The method of claim 10, wherein the initial liquid crystal molecule comprises a nematic liquid crystal molecule.
13. A method for preparing a display panel, comprising: providing an array substrate and a counter substrate, forming a liquid crystal layer between the array substrate and the counter substrate by using the cholesteric liquid crystal composition of claim 1.
14. A method for manufacturing the display panel of claim 8, comprising: providing a polymer A having the block A and a polymer B having the block B, mixing the polymer A and the polymer B with an initial liquid crystal molecule to obtain an initial liquid crystal composition, disposing the initial liquid crystal composition between an array substrate and a counter substrate placed by cell assembly, and connecting the polymer A and the polymer B in the initial liquid crystal composition to form the block copolymer, thereby forming the cholesteric liquid crystal composition.
15. The method of claim 14, wherein the initial liquid crystal molecule comprises a nematic liquid crystal molecule.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) In order to clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings of the embodiments will be briefly described in the following. It is apparent that the described drawings are only related to some embodiments of the present disclosure and thus are not intended to limit the invention.
(2)
(3)
(4)
(5)
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(7)
DETAILED DESCRIPTION
(8) In order to make objects, technical details and advantages of the embodiments of the present disclosure apparent, the technical solutions of the embodiments will be described in a clearly and fully understandable manner in connection with the drawings. It is obvious that the described embodiments are just a part of but not all of the embodiments of the present disclosure. Based on the described embodiments herein, those skilled in the art can, without any inventive work, obtain other embodiments, which should be within the protection scope of the present invention.
(9)
(10) The left side of
(11) In general, the cholesteric liquid crystal has a pitch of about 300 to 400 nm, for example, about 300 nm, and a refractive index of about 1 to 2, for example, 1.60, so that the cholesteric liquid crystal can reflect light at a wavelength of about 300 to 800 nm. In a practical embodiment, the reflection wavelength may be about 380 to 780 nm, just covering the wavelength of the visible light. However, since the cholesteric liquid crystal has a characteristic of a selective reflection, a cholesteric liquid crystal with a single pitch reflects only light of a single wavelength, and thus a single color is displayed.
(12)
(13) The bistable liquid crystal display shown in
(14) Embodiments of the present invention provide a cholesteric liquid crystal composition comprising a block copolymer and a cholesteric liquid crystal, wherein the block copolymer comprises a block A containing a chiral group M.sub.1 and a block B containing a chiral group M.sub.2, and the cholesteric liquid crystal has at least two different pitches.
(15) In some embodiments of the cholesteric liquid crystal composition, the block A comprises a repeating unit of the following formula (I):
(16) ##STR00001##
wherein R.sub.1 is each independently selected from hydrogen, C.sub.1-20 alkyl and the like, and n.sub.1 is an integer indicating the number of repeating units.
(17) In some embodiments, the block B comprises a repeating unit of the following formula (II):
(18) ##STR00002##
wherein R.sub.2 is each independently selected from hydrogen, C.sub.1-20 alkyl and the like, and n.sub.2 is an integer indicating the number of repeating units.
(19) The term C.sub.1-20alkyl herein represents an alkyl group having 1 to 20 carbon atoms, which may comprise C.sub.1 alkyl, C.sub.2 alkyl, C.sub.3 alkyl, C.sub.4 alkyl, C.sub.5 alkyl, C.sub.6 alkyl, C.sub.7 alkyl, C.sub.8 alkyl, C.sub.9 alkyl, C.sub.10 alkyl, C.sub.11 alkyl, C.sub.12 alkyl, C.sub.13 alkyl, C.sub.14 alkyl, C.sub.15 alkyl, C.sub.16 alkyl, C.sub.17 alkyl, C.sub.18 alkyl, C.sub.19 alkyl, and C.sub.20 alkyl. The integer n.sub.1 or n.sub.2 may be 10 to 100000, for example 100 to 10000, for example 500 to 5000. It should be noted that n.sub.1 or n.sub.2 represents the number of occurrences of the repeating unit of the formula (I) or the formula (II) in the block A or the block B. However, n.sub.1 or n.sub.2 does not indicate that there is no other repeating unit between two adjacent repeating units of the formula (I) or the formula (II). That is to say, there may be other repeating units between two adjacent repeating units of the formula (I) or the formula (II).
(20) In some embodiments, the content of the chiral group M.sub.1 in the block A is from 5 to 100 mol %, preferably from 5 mol % to 30 mol %. The content is not particularly limited, for example, may be 8 mol %, 10 mol %, 12 mol %, 15 mol %, 18 mol %, 20 mol %, 22 mol %, 25 mol %, 28 mol %, 30 mol %, 40 mol %, 50 mol %, 60 mol %, 70 mol %, 80 mol %, and the like. Here, mol % refers to the number of moles of repeating units with the chiral group M.sub.1 in the block A divided by the total number of moles of repeating units in the block A. In general, the content of the chiral group M.sub.1 in the block A depends on the proportion of the monomer containing the chiral group M.sub.1 in the monomer raw materials forming the block A, and for example, is consistent with the proportion of monomers containing the chiral group M.sub.1.
(21) In some embodiments, the content of the chiral group M.sub.2 in the block B is from 5 to 100 mol %, preferably from 5 mol % to 30 mol %. The content is not particularly limited, for example, 8 mol %, 10 mol %, 12 mol %, 15 mol %, 18 mol %, 20 mol %, 22 mol %, 25 mol %, 28 mol %, 30 mol %, 40 mol %, 50 mol %, 60 mol %, 70 mol %, 80 mol %, and the like. Here, mol % refers to the number of moles of repeating units with the chiral group M.sub.2 in the block B divided by the total number of moles of repeating units in the block B. In general, the content of the chiral group M.sub.2 in the block B depends on the proportion of the monomer containing the chiral group M.sub.2 in the monomer raw materials forming the block B, and for example, is consistent with the proportion of monomers containing the chiral group M.sub.2.
(22) In some embodiments, the chiral group M.sub.1 is different from the chiral group M.sub.2; in other embodiments, the chiral group M.sub.1 is the same as the chiral group M.sub.2.
(23) In some embodiments, the content of the chiral group M.sub.1 in the block A is the same as or different from the content of the chiral group M.sub.2 in the block B.
(24) In some embodiments, the optical rotation of the block A is different from the optical rotation of the block B. Difference between the optical rotation of the block A and that of the block B can be achieved by making the chiral group M.sub.1 different from the chiral group M.sub.2, and/or making the content of the chiral group M.sub.1 in the block A different from the content of the chiral group M.sub.2 in the block B. That is to say, the optical rotation of the block A can be made different from the optical rotation of the block B by selecting at least one of the type and content of the chiral group M.sub.1 and the chiral group M.sub.2.
(25) In some embodiments, the molecular weight of the block copolymer is from 1000 to 300000 daltons. The molecular weight of the block copolymer is not particularly limited as long as it can be dissolved in a liquid crystal molecule used subsequently. In general, the molecular weight within this range may be 3000, 5000, 8000, 10000, 12000, 15000, 18000, 20000, 25000 daltons, and the like.
(26) In some embodiments, the chiral group M.sub.1 and the chiral group M.sub.2 are each independently selected from:
(27) ##STR00003##
(28) Embodiments of the present invention also provide a display panel comprising an array substrate and a counter substrate placed by cell assembly and a liquid crystal layer disposed between the array substrate and the counter substrate, wherein the liquid crystal layer comprises the cholesteric liquid crystal composition as described above.
(29) The array substrate in embodiments of the present invention may include a plurality of gate lines and a plurality of data lines. These gate lines and data lines cross each other thereby defining the pixel units arranged in a matrix. Each pixel unit includes a thin film transistor as a switching element and a pixel electrode and a common electrode for applying an electric field. For example, the gate of the thin film transistor of each pixel is electrically connected or integrally formed with the corresponding gate line; the source is electrically connected or integrally formed with the corresponding data line; and the drain is electrically connected or integrally formed with the corresponding pixel electrode. The array substrate and the counter substrate are placed opposite to each other to form a liquid crystal cell, and the liquid crystal cell is filled with a liquid crystal material.
(30) The display panel of the present invention may be of a reflective type. In order to display black in a non-display area, a background composed of a light-absorbing material such as a black material may be formed on the non-display side. For example, a background composed of a light-absorbing material such as a black material is formed on the side of the array substrate or the counter substrate facing the liquid crystal layer.
(31) In some embodiments of the display panel, the array substrate has a plurality of pixel regions. The cholesteric liquid crystal composition is evenly distributed in each pixel region and is capable of reflecting light of at least two wavelengths in the visible light region.
(32) In some embodiments of the display panel, the block copolymer is evenly distributed in the liquid crystal layer. The block copolymer evenly distributed in the liquid crystal layer allows the cholesteric liquid crystal to have at least two pitches evenly so that the liquid crystal layer in a planar texture can uniformly reflect visible light having at least two colors, thereby increasing the brightness and contrast of the display panel. In these embodiments, the cholesteric liquid crystal having at least two pitches and the block copolymer are evenly distributed in each pixel region of the liquid crystal layer. It should be noted that the reflected light having at least two colors can show a combined color, such as white, for the human eye. In some embodiments, the difference in wavelength between two colors is greater than 50 nm, for example greater than 100 nm, or greater than 120 nm. For example, if the reflected light having at least two colors is light having two complementary colors, such as blue (or blue violet) and yellow, or cyan and orange, the human eye sees white (or almost white). If the reflected light having at least two colors includes red light, green light and blue light, then the human eye would see white light. If the spectrum of the reflected light can cover the entire visible area, then the human eye would also see white light.
(33) In some embodiments, the array substrate has a plurality of pixel regions. The cholesteric liquid crystal composition is evenly distributed in each pixel region and comprises a cholesteric liquid crystal having at least three pitches that is capable of reflecting light of at least three wavelengths in the visible light region. Compared with the case of reflecting light of two wavelengths, the reflected light is visually closer to white in the case of reflecting light of at least three wavelengths, and the brightness and contrast can be further improved.
(34)
(35) As shown in
(36) Embodiments of the present invention also provide a method for preparing the cholesteric liquid crystal composition described above, comprising the steps of: providing the block copolymer and mixing (e.g., dissolving) the block copolymer with an initial liquid crystal molecule.
(37) In the method for preparing the cholesteric liquid crystal composition described above, the block A and the block B in the block copolymer may be sequentially formed to provide the block copolymer. Alternatively, a polymer A containing the block A and a polymer B containing the block B are formed respectively, and then the polymer A and the polymer B are connected together to form the block copolymer.
(38) In the method for preparing the cholesteric liquid crystal composition described above, the block A may be formed by grafting a graft monomer A containing a chiral group M.sub.1 onto a polymer, or using a polymerizable monomer A containing a chiral group M.sub.1.
(39) In the method for preparing the cholesteric liquid crystal composition described above, the block B may be formed by grafting a graft monomer B containing a chiral group M.sub.2 onto a polymer, or using a polymerizable monomer B containing a chiral group M.sub.2.
(40) Embodiments of the present invention also provide a method for preparing the block copolymer having blocks A and B, which comprises: forming a polymer A containing the block A, forming a polymer B containing the block B, and then forming a bond between the polymer A containing the block A and the polymer B containing the block B to obtain the block copolymer.
(41)
(42) Therefore, embodiments of the present invention also provide a method for preparing a display panel, which comprises providing an array substrate and a counter substrate, and forming a liquid crystal layer between the array substrate and the counter substrate by using the cholesteric liquid crystal composition described above.
(43)
(44) The embodiment of the present invention also provides a method for preparing the above-described display panel, which comprises: providing a polymer A having a block A and a polymer B having a block B; mixing (e.g., dissolving) the polymer A and the polymer B with an initial liquid crystal molecule to obtain an initial liquid crystal composition; disposing the initial liquid crystal composition between an array substrate and a counter substrate placed by cell assembly; and connecting the polymer A and the polymer B in the initial liquid crystal composition to form the block copolymer, thereby forming the cholesteric liquid crystal composition.
(45) In some embodiments, the initial liquid crystal molecule comprises a nematic liquid crystal molecule.
Example 1
(46) The following materials were used in this example (the starting materials used in the present application were commercially available or can be prepared by conventional methods):
(47) Initiator: Butyl Lithium (P);
(48) ##STR00004##
Monomer 1:
(49) ##STR00005##
Monomer 2:
(50) ##STR00006##
Monomer 3:
(51) Step 1: constructing an anionic active polymerization system wherein a molar ratio of P:R1 was 1:10, and initiating a polymerization reaction by heating;
(52) Step 2: After reacting for 3 to 5 hours (the monomers were basically consumed), adding a mixture 1 of the monomer 1 and the monomer 2, wherein the amount of the mixture 1 was equal to the amount of R1 in step 1 in moles; and a molar ratio of R1:R2 in the mixture 1 was 10:1;
(53) Step 3: After reacting for 3 to 5 hours (the monomers were basically consumed), adding a mixture 2 of the monomer 1 and the monomer 3, wherein the amount of the mixture 2 was equal to the amount of monomer 1 in step 1 in moles; and a molar ratio of R1:R3 in the mixture 2 was 10:1;
(54) Step 4: After reacting for 3 to 5 hours (the monomers were basically consumed), terminating the reaction by adding a terminator.
(55)
(56) In this example, the chiral group M.sub.1 was
(57) ##STR00007##
and the chiral group M.sub.2 was
(58) ##STR00008##
Example 2
(59) The polymer obtained from Example 1 was added to a nematic liquid crystal stock (refractive index n=1.43, model: BHR-93500 liquid crystal, purchased from Beijing Bayishikong, Inc.) and mixed by heating and centrifugal shocking to obtain a cholesteric liquid crystal composition 1.
Comparative Example
(60) A small molecular photoactive chiral dopant:
(61) ##STR00009##
was added into a nematic liquid crystal stock (refractive index n=1.43, model: BHR-93500 liquid crystal, purchased from Beijing Bayishikong, Inc.), and mixed by heating and centrifugal shocking to obtain a cholesteric liquid crystal composition 2.
Example 3
(62) By injection, the cholesteric liquid crystal composition obtained from Example 2 or Comparative Example was infused between an array substrate and a counter substrate placed by cell assembly to form bistable liquid crystal display panel 1 or 2. The data of the reflection spectrum and brightness were obtained by testing under an ambient light of 600 nit (see Table 1 below and
(63) TABLE-US-00001 TABLE 1 bistable liquid crystal bistable liquid crystal display panel 1 display panel 2 cholesteric liquid cholesteric liquid cholesteric liquid crystal composition crystal composition 1 crystal composition 2 brightness 150 nit 50 nit spectrum about 450 nm and about about 450 nm 570 nm
(64) As shown by
Example 4
(65) In this example, firstly, a copolymer was synthesized with the same starting materials as in the Example 1, except that the following steps were used to obtain a block copolymer having three blocks of different optical rotations:
(66) Step 1: constructing an anionic active polymerization system wherein a molar ratio of P:R1 was 1:10, and initiating a polymerization reaction by heating;
(67) Step 2: After reacting for 3 to 5 hours (the monomers were basically consumed), gradually adding a mixture 3 of the monomer 1, the monomer 2 and the monomer 3 under reaction conditions, wherein the ratio of monomers in the mixture 3 was changed from R1:R2:R3=10:1:0 (a molar ratio) to R1:R2:R3=10:0.5:0.5 (a molar ratio), then to R1:R2:R3=10:0:1 (a molar ratio) over 6-10 hours;
(68) Step 3: terminating the reaction by adding a terminator to obtain a block copolymer having three blocks of different optical rotations.
(69) The obtained block copolymer having three blocks of different optical rotations was added to a nematic liquid crystal stock (refractive index n=1.43, model: BHR-93500 liquid crystal, purchased from Beijing Bayishikong, Inc.) and mixed by heating and centrifugal shocking to obtain a cholesteric liquid crystal composition 3.
(70) By injection, the obtained cholesteric liquid crystal composition 3 was infused between an array substrate and a counter substrate placed by cell assembly to form a bistable liquid crystal display panel 3. The data of the reflection spectrum and brightness were obtained by testing under an ambient light of 600 nit (see Table 2 below).
(71) TABLE-US-00002 TABLE 2 bistable liquid crystal display panel 3 cholesteric liquid cholesteric liquid crystal composition crystal composition 3 brightness 210 nit spectrum about 450 nm, about 520 nm, about 570 nm
(72) As shown in Table 2, the light reflected by the bistable liquid crystal display panel 3 included yellow light of about 570 nm, green light of 520 nm and blue light of about 450 nm, and white light was visually observed. The bistable liquid crystal display panel 3 displayed a higher brightness and thus a higher contrast, compared with the bistable liquid crystal display panel 1.
(73) The foregoing is merely illustrative of the present invention and is not intended to limit the scope of the invention. The scope of the invention is defined by the appended claims.
(74) The present application claims the priority of the Chinese Patent Application 201610124736.9 filed on Mar. 4, 2016, which is hereby incorporated by reference in its entirety as part of this application.