CN109651543B - Liquid crystal cell, method for producing same, and photopolymerizable composition - Google Patents
Liquid crystal cell, method for producing same, and photopolymerizable composition Download PDFInfo
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 95
- 210000002858 crystal cell Anatomy 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 219
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 22
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims description 84
- 150000001875 compounds Chemical class 0.000 claims description 16
- 230000001678 irradiating effect Effects 0.000 claims description 12
- 125000000129 anionic group Chemical group 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 9
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 9
- 239000003211 polymerization photoinitiator Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 3
- 230000008569 process Effects 0.000 abstract description 16
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 description 32
- 239000000758 substrate Substances 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical class 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
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- 239000003999 initiator Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
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- 238000006845 Michael addition reaction Methods 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
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Abstract
The application provides a liquid crystal cell, a manufacturing method thereof and a photo-polymerization composition, wherein a first polymer and a second polymer are respectively formed through anionic polymerization and free radical polymerization, and the forming processes of the first polymer and the second polymer do not interfere with each other.
Description
Technical Field
The application relates to the technical field of display, in particular to a liquid crystal box, a manufacturing method thereof and a photopolymerizable composition.
Background
The addition of Polymer monomer to Liquid Crystal is an important technology for a new Liquid Crystal display mode, and the initiation of polymerization of Polymer monomer under certain conditions can make the Liquid Crystal display realize many interesting display modes, such as Polymer Dispersed Liquid Crystal (PDLC), fast response Liquid Crystal system, and Polymer stabilized vertical Alignment system (PSVA), etc., wherein the Polymer stabilized vertical Alignment system is formed by adding Polymer monomer and photoinitiator to Liquid Crystal, the Polymer monomer and photoinitiator form Polymer bumps (Polymer bumps) after being irradiated by ultraviolet rays, and the Polymer bumps are used for fixing Liquid Crystal to form a pretilt angle.
In the field of flexible display, the Liquid Crystal polymer retaining wall (PWLC) technology adjusts the chemical structures and the composition ratios of Liquid Crystal and polymer monomers, so that the polymer monomer can form a polymer retaining wall with a proper width between two substrates forming a Liquid Crystal display after being exposed by collimation ultraviolet light, the position of the polymer retaining wall is related to an area irradiated by the ultraviolet light, and the area irradiated by the ultraviolet light can be controlled by the design of a photomask. The polymer formed by the polymer retaining wall technology can play a role in adhering between two substrates forming the liquid crystal display and can better play a role in maintaining the cell thickness of the liquid crystal display. Moreover, through proper design, the formed polymer retaining wall can effectively control the flow of liquid crystal and can eliminate the phenomenon of uneven brightness display (Mura) caused by external force and gravity.
At present, the polymer stable vertical alignment system and the liquid crystal polymer retaining wall technology are mainly based on free radical polymerization to form a polymer, namely, a photoinitiator generates free radicals through ultraviolet irradiation, the formed free radicals initiate a polymer monomer to generate a free radical reaction to form the polymer, the polymer and liquid crystal are subjected to phase separation along with the increase of the chain length of the polymer, so that a functional structure is generated, and meanwhile, when the free radical polymerization is adopted to form the liquid crystal polymer retaining wall and the polymer bulge, the forming processes of the polymer retaining wall and the polymer bulge can interfere with each other.
Disclosure of Invention
The present application is directed to a liquid crystal cell and a method of manufacturing the same, in which the formation processes of polymer barriers and polymer protrusions of the liquid crystal cell do not interfere with each other.
In order to achieve the purpose, the technical scheme is as follows.
A method of manufacturing a liquid crystal cell, the method comprising the steps of:
mixing a photoinitiator A1, a photoinitiator A2, a polymer monomer B1 and a polymer monomer B2 to obtain a mixture;
injecting the mixture into a containing cavity of the liquid crystal box to obtain a liquid crystal box with the mixture;
irradiating the liquid crystal cell with the mixture with light of a first wavelength to initiate anionic polymerization of the photoinitiator a1, the polymer monomer B1, and the polymer monomer B2 to form a first polymer on the inner walls of the containment cavity of the liquid crystal cell;
irradiating the liquid crystal box with the first polymer by using light with a second wavelength, and initiating free radical polymerization of the photoinitiator A2 and the polymer monomer B1 to form a second polymer on the inner wall of a containing cavity of the liquid crystal box;
the photoinitiator A1 is an anionic photoinitiator, the photoinitiator A2 is a free radical polymerization photoinitiator, the polymer monomer B1 is at least one of acrylate, acrylate derivative, methacrylate derivative, epoxy resin and styrene, the polymer monomer B2 is a mercapto compound, and the first polymer and the second polymer are different and are respectively one of a polymer retaining wall or a polymer bump.
In the method for manufacturing the liquid crystal cell, the first wavelength is 400 nm-500 nm, and the second wavelength is 280 nm-370 nm.
In the method for manufacturing the liquid crystal cell, the photoinitiator a1 is selected from at least one of the following compounds:
(ii) a Wherein R1 and R2 each independently represent H, a hydrocarbon group or a substituted hydrocarbon group, and R3 represents a hydrocarbon group or a substituted hydrocarbon group.
In the method for manufacturing the liquid crystal cell, the photoinitiator a2 is selected from at least one of the following compounds:
a liquid crystal cell having a receiving cavity and first and second polymers disposed on the inner walls of the receiving cavity,
the first polymer is formed by mixing a photoinitiator A1, a photoinitiator A2, a polymer monomer B1 and a polymer monomer B2, injecting the mixture into a containing cavity of the liquid crystal cell, irradiating the liquid crystal cell with light with a first wavelength to initiate anionic polymerization of the photoinitiator A1, the polymer monomer B1 and the polymer monomer B2,
the second polymer is formed by irradiating the liquid crystal box with the first polymer by using light with a second wavelength to initiate free radical polymerization of the photoinitiator A2 and the polymer monomer B1;
the photoinitiator A1 is an anionic photoinitiator, the photoinitiator A2 is a free radical polymerization photoinitiator, the polymer monomer B1 is at least one of acrylate, acrylate derivative, methacrylate derivative, epoxy resin and styrene, the polymer monomer B2 is a mercapto compound, and the first polymer and the second polymer are different and are respectively one of a polymer retaining wall or a polymer bump.
In the liquid crystal cell, the first wavelength is 400 nm-500 nm, and the second wavelength is 280 nm-370 nm.
In the above liquid crystal cell, the photoinitiator a1 is selected from at least one of the following compounds:
(ii) a Wherein R1 and R2 each independently represent H, a hydrocarbon group or a substituted hydrocarbon group, and R3 represents a hydrocarbon group or a substituted hydrocarbon group.
In the above liquid crystal cell, the photoinitiator a2 is selected from at least one of the following compounds:
in the above liquid crystal cell, the liquid crystal cell further includes a liquid crystal filled in the accommodation cavity of the liquid crystal cell.
It is still another object of the present application to provide a photopolymerizable composition.
A photopolymerizable composition comprising a photoinitiator A1, a photoinitiator A2, a polymer monomer B1, and a polymer monomer B2,
the photoinitiator A1, the polymer monomer B1, and the polymer monomer B2 are used for anionic polymerization under irradiation of light of a first wavelength to form a first polymer;
the photoinitiator A2 and the polymer monomer B1 are used for free radical polymerization under irradiation of light of a second wavelength to form a second polymer;
the photoinitiator A1 is an anionic photoinitiator, the photoinitiator A2 is a free radical polymerization photoinitiator, the polymer monomer B1 is at least one of acrylate, acrylate derivative, methacrylate derivative, epoxy resin and styrene, and the polymer monomer B2 is a mercapto compound.
Has the advantages that: the application provides a liquid crystal cell, a manufacturing method thereof and a photo-polymerization composition, wherein a first polymer and a second polymer are respectively formed through anionic polymerization and free radical polymerization, and the forming processes of the first polymer and the second polymer do not interfere with each other.
Drawings
FIG. 1 is a flow chart of a method of manufacturing a liquid crystal cell according to the present application;
fig. 2A-2E are process diagrams of the flowchart shown in fig. 1.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application provides a photopolymerizable composition, which comprises a photoinitiator A1, a photoinitiator A2, a polymer monomer B1 and a polymer monomer B2,
the photoinitiator A1, the polymer monomer B1 and the polymer monomer B2 are used for carrying out anionic polymerization under the irradiation of light with a first wavelength to form a first polymer;
the photoinitiator A2 and the polymer monomer B1 are used for carrying out free radical polymerization under the irradiation of light with a second wavelength to form a second polymer;
the photoinitiator A1 is an anionic photoinitiator, the photoinitiator A2 is a free radical polymerization photoinitiator, the polymer monomer B1 is at least one of acrylate, acrylate derivative, methacrylate derivative, epoxy resin and styrene, and the polymer monomer B2 is a mercapto compound.
In some embodiments, the light of the first wavelength may be ultraviolet light, and may also be visible light. When the light with the first wavelength is visible light, the first wavelength is 400-500 nm, for example, the first wavelength is 410 nm, 430 nm and 480 nm. When the first wavelength is 400-500 nm, the light irradiation time of the first wavelength is 15-60min, for example, the light irradiation time is 15min, 30min or 45 min; the light irradiation intensity of the first wavelength is 1-50mW/cm2For example, the irradiation intensity is 10mW/cm2，25mW/cm2Or 45mW/cm2. The photoinitiator A1 is selected from at least one of the following compounds when the first wavelength is 400 nm-500 nm:
wherein R1 and R2 each independently represent H, a hydrocarbyl group or a substituted hydrocarbyl group, and R3 represents a hydrocarbyl group or a substituted hydrocarbyl group. Hydrocarbyl includes, but is not limited to, alkyl, cycloalkyl, and aryl groups, and the like, and substituted hydrocarbyl includes, but is not limited to, halo-substituted hydrocarbyl, heteroatom (e.g., oxygen, nitrogen, sulfur) -substituted hydrocarbyl. In particular, R1 and R2 both represent ethyl, or, R1 represents a hydrogen atom, R2 represents n-hexyl; r3 represents-C [ N (CH)3)2]2。
In some embodiments, the light of the second wavelength may be ultraviolet light, and may also be visible light. When the light with the second wavelength is ultraviolet light, the second wavelength is 280-370 nm, for example, the second wavelength is 280 nm, 320 nm or 360 nm. When the second wavelength is 280-370 nm, the irradiation time of the light with the second wavelength is 5-60min, such as 8min, 25min and 40 min; the light of the second wavelength has an irradiation intensity of 0.1-10mW/cm2For example, the irradiation intensity is 0.2mW/cm2、4mW/cm2、8mW/cm2. When the second wavelength is 280-370 nm, the photoinitiator A2 is selected from at least one of the following compounds:
the photopolymerizable composition described above will be described below with reference to specific examples.
In the first example, the composition of the photopolymerizable composition and the conditions for forming the first polymer and the second polymer from the photopolymerizable composition are shown in table 1.
TABLE 1 composition of photopolymerizable composition of the first example and conditions for forming first and second polymers from the photopolymerizable composition
In a second example, the composition of the photopolymerizable composition and the conditions for forming the first polymer and the second polymer from the photopolymerizable composition are shown in table 2.
TABLE 2 composition of photopolymerizable composition of the second example and conditions for forming first and second polymers from the photopolymerizable composition
In a third example, the composition of the photopolymerizable composition and the conditions for forming the first polymer and the second polymer from the photopolymerizable composition are shown in table 3.
TABLE 3 composition of photopolymerizable composition of the third example and conditions for forming first and second polymers from the photopolymerizable composition
In the first, second and third embodiments, the photoinitiator a1, the polymer monomer B1 and the polymer monomer B2 are anionically polymerized under light irradiation of a first wavelength to form a first polymer, the photoinitiator a2 and the polymer monomer B1 are radically polymerized under light irradiation of a second wavelength to form a second polymer, the first polymer and the second polymer are formed by different mechanisms, the active centers in the formation process are different, and the formation process of the first polymer and the formation process of the second polymer do not interfere with each other.
The application utilizes the photo-polymerization composition to respectively form a polymerization retaining wall and a polymer bump of a liquid crystal box, wherein the polymer retaining wall is used for controlling the flow of liquid crystal and simultaneously controlling the thickness of the liquid crystal box; when the polymer bumps are used for fixing liquid crystal in the liquid crystal box, a pretilt angle is formed. It is understood that the photopolymerizable composition may also be applied to the manufacture of other polymeric functional structures, and the present application is not specifically limited.
A method of manufacturing a liquid crystal cell, the method having a flow chart as shown in fig. 1, the method comprising the steps of:
s10 mixing the photoinitiator A1101, the photoinitiator A2102, the polymer monomer B1104 and the polymer monomer B2103 to obtain a mixture.
The photoinitiator a1101 is an anionic photoinitiator, also called a photobase generator, which generates anionic active centers under irradiation of light of a certain wavelength to initiate anionic polymerization.
The photoinitiator a2102 is a radical initiator which generates radical active centers to initiate radical polymerization under irradiation of light of a certain wavelength.
The polymer monomer B1104 forms a polymer by addition of a carbon-carbon double bond or ring-opening addition of an epoxy group. The polymer monomer B1104 is at least one of acrylate, acrylate derivative, methacrylate derivative, epoxy resin, and styrene.
The polymer monomer B2103 is a mercapto compound, and may be a compound having one mercapto group or a compound having a plurality of mercapto groups.
And S11, as shown in fig. 2A, injecting the mixture into the receiving cavity of the liquid crystal cell to obtain the liquid crystal cell with the mixture.
Specifically, after the mixture was injected into the receiving cavity of the liquid crystal cell, the photoinitiator a1101, the photoinitiator a2102, the polymer monomer B1104, and the polymer monomer B2103 constituting the mixture were uniformly dispersed in the receiving cavity. Methods of injecting the mixture into the liquid crystal cell include, but are not limited to, perfusion and One Drop Filling (ODF).
The liquid crystal box comprises a first substrate 105, a second substrate 106 and frame sealing glue for connecting the first substrate 105 and the second substrate 106, wherein the inner surface of the first substrate 105, the inner surface of the second substrate 106 and the frame sealing glue enclose a containing cavity of the liquid crystal box.
S12, irradiating the liquid crystal box by using light with a first wavelength, and initiating anionic polymerization of the photoinitiator A1101, the polymer monomer B1104 and the polymer monomer B2103 to form the first polymer 107 on the inner wall of the accommodating cavity of the liquid crystal box.
The light of the first wavelength may be ultraviolet light or visible light, and different photoinitiators are selected to initiate anionic polymerization according to different wavelengths of the irradiated light. The first polymer 107 may be a polymer retaining wall or a polymer bump.
For illustrative purposes, the light of the first wavelength is visible light, the first wavelength is 400 nm to 500 nm, for example, the first wavelength is 410 nm, 430 nm, or 480 nm. The first polymer 107 is a polymer retaining wall formed between the first substrate 105 and the second substrate 106. When the first wavelength is 400-500 nm, the photoinitiator A1101 is selected from at least one of the following compounds:
wherein R1 and R2 each independently represent H, a hydrocarbyl group or a substituted hydrocarbyl group, and R3 represents a hydrocarbyl group or a substituted hydrocarbyl group. Hydrocarbyl includes, but is not limited to, alkyl, cycloalkyl, and aryl groups, and the like, and substituted hydrocarbyl includes, but is not limited to, halo-substituted hydrocarbyl, heteroatom (e.g., oxygen, nitrogen, sulfur) -substituted hydrocarbyl. In particular, R1 and R2 both represent ethyl, or, R1 represents a hydrogen atom, R2 represents n-hexyl; r3 represents-C [ N (CH)3)2]2。
Specifically, as shown in FIGS. 2B and 2C, a photo mask is placed on one side of the liquid crystal cell, and the photo mask is irradiated with light of a first wavelength (400 nm-500 nm) for 15-60min at an intensity of 1-50mW/cm2The light of the first wavelength passing through the mask gap irradiates the cell initiator a1101, the polymer monomer B1104 and the polymer monomer B2103 to perform anionic polymerization so as to form a polymer retaining wall between the first substrate 105 and the second substrate 106. Wherein the reaction between polymer monomer B1104 and polymer monomer B2103 is a thiol-Michael addition reaction.
S13, irradiating the liquid crystal box with the first polymer 107 by using light with a second wavelength, and initiating the free radical polymerization of the photoinitiator A2102 and the polymer monomer B1104 to form a second polymer 108 on the inner wall of the accommodating cavity of the liquid crystal box.
The light with the second wavelength can be ultraviolet light or visible light; the second polymer 108 may be a polymer retaining wall or a polymer bump. The first polymer 107 and the second polymer 108 are different and are respectively one of a polymer retaining wall or a polymer bump, that is, when the first polymer 107 is a polymer retaining wall, the second polymer 108 is a polymer bump; when the first polymer 107 is a polymer bump, the second polymer 108 is a polymer retaining wall.
For illustrative purposes, the second wavelength is 280 nanometers to 370 nanometers, such as 280 nanometers, 320 nanometers, or 360 nanometers. The second polymer 108 is a polymer bump. And when the second wavelength is 280 nm-370 nm, the photoinitiator A2 is selected from at least one of the following compounds:
specifically, as shown in FIGS. 2D and 2E, the liquid crystal cell having the first polymer is irradiated with light of a second wavelength (280 nm to 370 nm) for 5 to 60min at an intensity of 0.1 to 10mW/cm2The photoinitiator a2102 and the polymer monomer B1104 are radical-polymerized under irradiation of light of the second wavelength to form polymer bumps on the inner walls of the first substrate 105 and the second substrate 106.
The liquid crystal box is irradiated by light with a first wavelength to enable a photoinitiator A1, a polymer monomer B1 and a polymer monomer B2 to carry out anionic polymerization so as to form a polymer retaining wall between two substrates forming the liquid crystal box, and the liquid crystal box is irradiated by light with a second wavelength to enable a photoinitiator A2 and a polymer monomer B1 to carry out free radical polymerization so as to form polymer bumps on the inner walls of the two substrates forming the liquid crystal box. The anion active center in the process of forming the first polymer and the radical active center in the process of forming the second polymer do not interfere with each other, so the process of forming the first polymer and the process of forming the second polymer do not interfere with each other.
It is understood that the second polymer may be formed as the polymer retaining wall and the first polymer may be formed as the polymer bump, that is, only the irradiation sequence of the light with the first wavelength and the light with the second wavelength needs to be adjusted.
The present application also provides a liquid crystal cell having a receiving cavity and first and second polymers disposed on an inner wall of the receiving cavity,
the first polymer is formed by mixing a photoinitiator A1, a photoinitiator A2, a polymer monomer B1 and a polymer monomer B2, injecting the mixture into a containing cavity of a liquid crystal cell, irradiating the liquid crystal cell with light of a first wavelength to initiate anionic polymerization of the photoinitiator A1, the polymer monomer B1 and the polymer monomer B2,
the second polymer is formed by irradiating the liquid crystal box with the first polymer by using light with a second wavelength to initiate free radical polymerization of the photoinitiator A2 and the polymer monomer B1;
the photoinitiator A1 is an anionic photoinitiator, the photoinitiator A2 is a free radical polymerization initiator, the polymer monomer B1 is at least one of acrylate, acrylate derivative, methacrylate derivative, epoxy resin and styrene, the polymer monomer B2 is a mercapto compound, and the first polymer and the second polymer are different and are respectively one of a polymer retaining wall or a polymer bump.
In some embodiments, the light of the first wavelength may be ultraviolet light, and may also be visible light. The light of the second wavelength may be ultraviolet light or visible light. The first wavelength is 400 nm-500 nm and the second wavelength is 280 nm-370 nm when the light of the first wavelength is visible light and the light of the second wavelength is ultraviolet light.
The photoinitiator A1 is selected from at least one of the following compounds when the first wavelength is 400 nm-500 nm:
wherein R1 and R2 each independently represent H, a hydrocarbon group or a substituted hydrocarbon group, and R3 represents a hydrocarbon group or a substituted hydrocarbon group. Hydrocarbyl includes, but is not limited to, alkyl, cycloalkyl, and aryl groups, and the like, and substituted hydrocarbyl includes, but is not limited to, halo-substituted hydrocarbyl, heteroatom (e.g., oxygen, nitrogen, sulfur) -substituted hydrocarbyl. In particular, R1 and R2 both represent ethyl, or, R1 represents a hydrogen atom, R2 represents n-hexyl; r3 represents-C [ N (CH)3)2]2。
And when the second wavelength is 280 nm-370 nm, the photoinitiator A2 is selected from at least one of the following compounds:
further, the liquid crystal cell further includes liquid crystal (not shown), and the liquid crystal is filled in the receiving cavity of the liquid crystal cell. The Liquid Crystal is a vertically aligned Liquid Crystal (Vertical alignment Liquid Crystal).
The first polymer and the second polymer in the liquid crystal box are respectively formed by anionic polymerization and cationic polymerization, and an anionic active center in the process of forming the first polymer and a free radical active center in the process of forming the second polymer cannot interfere with each other, so that the process of forming the first polymer and the process of forming the second polymer cannot interfere with each other.
The above description of the embodiments is only for assisting understanding of the technical solutions and the core ideas thereof; those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present disclosure as defined by the appended claims.
Claims (10)
1. A method of manufacturing a liquid crystal cell, comprising the steps of:
mixing a photoinitiator A1, a photoinitiator A2, a polymer monomer B1 and a polymer monomer B2 to obtain a mixture;
injecting the mixture into a containing cavity of the liquid crystal box to obtain a liquid crystal box with the mixture;
irradiating the liquid crystal cell with the mixture with light of a first wavelength to initiate anionic polymerization of the photoinitiator a1, the polymer monomer B1, and the polymer monomer B2 to form a first polymer on the inner walls of the containment cavity of the liquid crystal cell;
irradiating the liquid crystal box with the first polymer by using light with a second wavelength, and initiating free radical polymerization of the photoinitiator A2 and the polymer monomer B1 to form a second polymer on the inner wall of a containing cavity of the liquid crystal box;
the photoinitiator A1 is an anionic photoinitiator, the photoinitiator A2 is a free radical polymerization photoinitiator, the polymer monomer B1 is at least one of acrylate, acrylate derivative, methacrylate and methacrylate derivative, the polymer monomer B2 is a multi-mercapto compound, and the first polymer and the second polymer are different and are respectively one of a polymer retaining wall or a polymer bump.
2. The method of manufacturing a liquid crystal cell according to claim 1, wherein the first wavelength is 400 nm to 500 nm and the second wavelength is 280 nm to 370 nm.
3. The method for manufacturing a liquid crystal cell according to claim 2, wherein the photoinitiator a1 is selected from at least one of the following compounds:
wherein R1 and R2 both represent ethyl, or R1 represents a hydrogen atom, R2 represents N-hexyl, and R3 represents C [ N (CH)3)2]2。
4. The method for manufacturing a liquid crystal cell according to claim 2, wherein the photoinitiator a2 is selected from at least one of the following compounds:
5. a liquid crystal cell having a receiving cavity and first and second polymers disposed on the inner walls of the receiving cavity,
the first polymer is formed by mixing a photoinitiator A1, a photoinitiator A2, a polymer monomer B1 and a polymer monomer B2, injecting the mixture into a containing cavity of the liquid crystal cell, irradiating the liquid crystal cell with light with a first wavelength to initiate anionic polymerization of the photoinitiator A1, the polymer monomer B1 and the polymer monomer B2,
the second polymer is formed by irradiating the liquid crystal box with the first polymer by using light with a second wavelength to initiate free radical polymerization of the photoinitiator A2 and the polymer monomer B1;
the photoinitiator A1 is an anionic photoinitiator, the photoinitiator A2 is a free radical polymerization photoinitiator, the polymer monomer B1 is at least one of acrylate, acrylate derivative, methacrylate and methacrylate derivative, the polymer monomer B2 is a multi-mercapto compound, and the first polymer and the second polymer are different and are respectively one of a polymer retaining wall or a polymer bump.
6. The liquid crystal cell according to claim 5, wherein the first wavelength is from 400 nm to 500 nm and the second wavelength is from 280 nm to 370 nm.
7. The liquid crystal cell according to claim 6, wherein the photoinitiator A1 is selected from at least one of the following compounds:
wherein R1 and R2 both represent ethyl, or R1 represents a hydrogen atom, R2 represents N-hexyl, and R3 represents C [ N (CH)3)2]2。
8. The liquid crystal cell according to claim 6, wherein the photoinitiator A2 is selected from at least one of the following compounds:
9. the liquid crystal cell according to claim 5, further comprising a liquid crystal filled in the receiving cavity of the liquid crystal cell.
10. A photopolymerizable composition characterized by comprising a photoinitiator A1, a photoinitiator A2, a polymer monomer B1 and a polymer monomer B2,
the photoinitiator A1, the polymer monomer B1, and the polymer monomer B2 are used for anionic polymerization under irradiation of light of a first wavelength to form a first polymer;
the photoinitiator A2 and the polymer monomer B1 are used for free radical polymerization under irradiation of light of a second wavelength to form a second polymer;
the photoinitiator A1 is an anionic photoinitiator, the photoinitiator A2 is a free radical polymerization photoinitiator, the polymer monomer B1 is at least one of acrylate, acrylate derivative, methacrylate and methacrylate derivative, and the polymer monomer B2 is a multi-mercapto compound;
the first wavelength is 400 nm-500 nm and the second wavelength is 280 nm-370 nm.
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| CN201811573535.2A CN109651543B (en) | 2018-12-21 | 2018-12-21 | Liquid crystal cell, method for producing same, and photopolymerizable composition |
| PCT/CN2019/077597 WO2020124801A1 (en) | 2018-12-21 | 2019-03-11 | Liquid crystal cell, manufacturing method thereof, and photopolymerizable composition |
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| CN109976020B (en) * | 2019-04-24 | 2020-08-11 | 深圳市华星光电半导体显示技术有限公司 | Preparation method of flexible liquid crystal display panel |
| CN111983866A (en) * | 2019-05-24 | 2020-11-24 | 京东方科技集团股份有限公司 | Light modulation glass and preparation method thereof |
| CN110806662B (en) * | 2019-10-28 | 2023-03-17 | 武汉华星光电技术有限公司 | Display panel and manufacturing method thereof |
| US11422411B2 (en) | 2020-03-10 | 2022-08-23 | Tcl China Star Optoelectronics Technology Co., Ltd. | Liquid crystal material, liquid crystal display panel, and manufacturing method thereof |
| CN111258122B (en) * | 2020-03-10 | 2021-11-02 | Tcl华星光电技术有限公司 | Liquid crystal material, manufacturing method of liquid crystal display panel and liquid crystal display panel |
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| WO2020124801A1 (en) | 2020-06-25 |
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