CN102346324A - Method of manufacturing liquid crystal display element and liquid crystal display element - Google Patents
Method of manufacturing liquid crystal display element and liquid crystal display element Download PDFInfo
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- CN102346324A CN102346324A CN2011102109467A CN201110210946A CN102346324A CN 102346324 A CN102346324 A CN 102346324A CN 2011102109467 A CN2011102109467 A CN 2011102109467A CN 201110210946 A CN201110210946 A CN 201110210946A CN 102346324 A CN102346324 A CN 102346324A
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- liquid crystal
- crystal display
- display cells
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- transparency electrode
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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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
-
- 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
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
-
- 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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
-
- 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
- G02F1/1341—Filling or closing of cells
Abstract
The invention relates to a liquid crystal display element and the manufacturing method thereof. The liquid crystal display element has the advantages of simple electrode structure, wide angle, high brightness, excellent liquid crystal orientation and electrical characteristics. According to the manufacturing method of the liquid crystal display element, two substrates are disposed opposite to each other so as to from a liquid crystal box and then the liquid crystal box is irradiated with polarized radiation rays. One surface of at least one of the substrates is equipped with a transparent electrode. The above substrates of the liquid crystal box with an oppositely arranged structure are arranged opposite to each other through reactive liquid crystal with light polymerization property and a liquid crystal composition layer. Therefore, one surface of at least one of the substrates is equipped with a transparent electrode arranged toward the liquid crystal composition layer.
Description
Technical field
The present invention relates to the manufacturing approach and the liquid crystal display cells of liquid crystal display cells.
Background technology
At present, various liquid crystal display cells such as known TN (twisted nematic) type, STN (STN Super TN) type, VA (vertical orientated) type, IPS (face intra) type, OCB (optical compensation curved) type.
In these; In the VA type liquid crystal display cells; Known at orientation such as the thrust that narrow slit structure, wire are set on the substrate or on transparency electrode control works; Thereby the liquid crystal aligning direction in the time of will applying voltage is controlled on the different directions in the pixel; Thus, can realize the liquid crystal display cells (patent documentation 1) of MVA (multi-domain vertical alignment) mode at wide visual angle.The liquid crystal display cells of this MVA mode has the excellent advantage of viewing angle characteristic, but owing to there is orientation control works, therefore exists white brightness to reduce, show darker shortcoming.
In order to realize wide visual angle and high brightness, and VA type liquid crystal display cells that can high-speed response, the use polymkeric substance has been proposed, the method for the vergence direction the when tilt angle of regulation liquid crystal and voltage apply (patent documentation 2 and 3).The method of in these patent documentations, putting down in writing is to have between two substrates of the electrode that is processed into complicated shape; Clamping by contain can photopolymerization or the liquid-crystal composition of the monomer of thermal polymerization and liquid crystal constitute layer; Between above-mentioned electrode, apply voltage; Thereby under the state that liquid crystal tilts; Apply light or heat to this liquid-crystal composition layer; Make monomer polymerization form polymkeric substance, make the direction of orientation and the fixing technology of tilt angle of liquid crystal through this polymkeric substance.This technology can make the corresponding speed of light and shade accelerate and since the vergence direction of liquid crystal also can be controlled at through the shape of electrode multi-direction on, therefore also can realize wide visual angle, and then the problem of the brightness excellent technology that also can be solved.Yet; According to this technology; In order to control the orientation of liquid crystal; Need on substrate, form the electrode of complicated shape, it is complicated that the electrode manufacturing procedure becomes, and the manufacturing cost of liquid crystal display cells increases; In addition in the polymerization of monomer; The rayed or the high temperature that need the heavy exposure amount, therefore in the manufacture process of liquid crystal display cells, the problem that exists the electrical characteristics of element to suffer damage.
In view of this fact, in VA type liquid crystal display cells, need not to use the electrode of complicated shape, requirement can embody the liquid crystal display cells of patent documentation 2 and 3 advantageous effects.That is, require not use the electrode of complicated shape, can control direction of orientation, embody good liquid crystal aligning property and have wide visual angle and high brightness concurrently, also can not damage the liquid crystal display cells of electrical characteristics in addition through above-mentioned rayed through rayed.
On the other hand; In the liquid crystal display cells beyond the VA types such as TN type, STN type, IPS type, OCB type,, adopt the method for polishing usually in order in liquid crystal orientation film, to give the liquid crystal aligning ability; It is many that the process number that liquid crystal display cells is made becomes, and on manufacturing cost, has problems.
In order to omit the polishing operation of liquid crystal display cells in making, studied optical alignment method, but the research example of employing optical alignment method does not have basically in TN type etc., and several examples (for example patent documentation 4) are only arranged.In addition, according to the technology of present proposition, light orientation TN type liquid crystal display cells is not enough to the orientation limitations power of liquid crystal, as yet practicability not.
Therefore, in the liquid crystal display cells beyond the VA type, require not simple procedures, just can obtain to realize the manufacturing approach of the liquid crystal display cells of strong liquid crystal aligning control through polishing.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 8-43825 communique
Patent documentation 2: TOHKEMY 2003-307720 communique
Patent documentation 3: TOHKEMY 2002-23199 communique
Patent documentation 4: japanese kokai publication hei 9-297313 communique
Summary of the invention
The present invention makes in view of the above fact, and its objective is provides respectively that a kind of electrode structure is simple in VA type liquid crystal display cells, and has the preparation method of the excellent liquid crystal display cells of wide visual angle and high brightness, especially liquid crystal aligning property and electrical characteristics concurrently; And
A kind of in the liquid crystal display cells except that the VA type, just can realize the preparation method of the liquid crystal display cells of strong liquid crystal aligning control through the simple procedures that need not to polish.
According to the present invention; Above-mentioned purpose of the present invention and advantage realize by the manufacture method of following liquid crystal display cells; Through following operation: the substrate that will be made of two substrates is to forming the liquid crystal cell that subtend is provided with structure; Again to above-mentioned liquid crystal cell irradiation polarisation radioactive ray; Wherein, At least one Zhang Zaiqi in these substrates simultaneously goes up and forms transparency electrode; The liquid crystal cell that this subtend is provided with structure by make contain can photopolymerisable reactive mesogen and the layer of the liquid-crystal composition of liquid crystal be clipped in aforesaid substrate between; Make aforesaid substrate to relatively; So that one side is formed with the face of this transparency electrode of formation of the substrate of transparency electrode therein, towards the direction of the layer of above-mentioned liquid-crystal composition.
The method according to this invention; It is simple to make electrode structure; And have wide visual angle and high brightness concurrently; Especially the excellent VA type liquid crystal display cells of liquid crystal aligning property and electrical characteristics; And the simple procedures through need not to polish, just can make liquid crystal display cells such as the TN type that can embody strong liquid crystal aligning control, STN type, IPS type, OCB type.
Embodiment
<substrate >
In the method for the invention, as a pair of, wherein, at least one Zhang Zaiqi in these substrates simultaneously forms transparency electrode with two substrates.Can in constituting the right substrate of substrate, only have a substrate on its one side, to form transparency electrode, and another have transparency electrode, can also be to constitute two right substrates of substrate all on its one side, to form transparency electrode.
Material as constituting aforesaid substrate can use for example by the glass like float glass, alkali glass; The transparency carrier that constitutes like the plastics of the addition polymer of the ring-opening polymerization polymer of polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, cyclic olefin and hydrogenation thing thereof, cyclic olefin, aromatic polyether, polyimide etc.In these substrates, need not to be used to control the slit-shaped pattern etc. of the direction of orientation of liquid crystal, from the viewpoint of manufacturing cost, preferably need not to have this specific pattern.
As above-mentioned transparency electrode, can use for example has In
2O
3-SnO
2The ITO film that constitutes, SnO is arranged
2NESA (registered trademark) film that constitutes etc.Two substrates right at the formation substrate all form under the situation of transparency electrode on its one side, and these transparency electrodes can not have pattern, perhaps also can form pattern as required.In constituting the right substrate of substrate, only there is a substrate on its one side, to form transparency electrode, another does not have under the situation of transparency electrode, preferably on the one side of a substrate, makes the pair of electrodes combination non-contactly each other with zigzag shape.In the formation pattern of transparency electrode, can be after formation have the transparency electrode of pattern, through photo-engraving process, sputtering method etc. form method of patterning, when forming transparency electrode, use the method etc. of mask to carry out with desired pattern.Yet, in the present invention, there is no need like the pattern of complicated shapes of patent documentation 2 and 3 records.
On the transparency electrode that the substrate that the present invention uses has, need not to be used to control the structure of overshooting shape of the direction of orientation of liquid crystal, from the viewpoint of brightness and manufacturing cost, the preferred transparency electrode of this structure not.
, in the method for the invention, preferably constitute right above-mentioned of substrate and form among at least one in the substrate of transparency electrode it directly being used for method of the present invention like above-mentioned substrate, on this transparency electrode, also form film in one side.In addition, in substrate one does not have under the situation of transparency electrode, and preferably this does not have the substrate of transparency electrode on its one side, to form film.
Forming under the situation of transparency electrode on the one side of two substrates, can only form film on the transparency electrode of a substrate therein, perhaps also can on the transparency electrode of two substrates, form film.Most preferably two substrates form transparency electrode and film successively on its one side.
As the film that on above-mentioned transparency electrode, forms, can be any of organic membrane and inoranic membrane.Yet under the situation of VA type liquid crystal display cells made according to the method for the present invention, preferred body reveals the film of vertical orientated property, more preferably embodies the organic membrane of vertical orientated property.Under the situation of making the liquid crystal display cells except that the VA type, preferred organic membrane does not more preferably embody the organic membrane of vertical orientated property.
As above-mentioned organic membrane, for example can enumerate with polyamic acid, polyimide, poly amic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, gather acetal, polystyrene derivative, gather (styrene-phenyl maleimide) derivant, gather polymkeric substance such as (methyl) acrylate or their potpourri is the film of major component.Wherein, the polymkeric substance of more than one that select in the group that constitutes by polyamic acid, polyimide and polysiloxane as the film of major component for preferred.In addition, above-mentioned so-called polyimide is the notion that also comprises the part imidizate thing of polyamic acid.
Above-mentioned organic membrane can also be chosen wantonly and contain light enhanced sensitivity property composition.Above-mentioned organic membrane is through containing light enhanced sensitivity property composition, thereby can promote near the light reaction of the reactive mesogen of organic membrane, therefore can embody the exposure of the needed minimizing polarisation of the application's desired effects radioactive ray, is preferred.
This light enhanced sensitivity property composition is the composition with light enhanced sensitivity property structure.As the light enhanced sensitivity property structure that light enhanced sensitivity property composition has, for example can enumerate acetophenone structure, benzophenone structure, anthraquinone ring, biphenyl structural, carbazole structure, nitro aryl structure, fluorene structured, naphthalene structure, anthracene structure, acridine structure, indole structure etc.
The ratio that exists as light enhanced sensitivity property structure in the organic membrane with respect to the total weight of organic membrane, is preferably below the 20 weight %, more preferably below the 10 weight %.Through making the total weight of light enhanced sensitivity property structure with respect to organic membrane, preferably exist more than the 0.01 weight %, more preferably more than the 0.05 weight %, thereby can embody desired effect.
Light enhanced sensitivity property composition can be used as free compound and exists in organic membrane, perhaps exists to be bonded to as the main chain of the polymkeric substance of organic membrane master composition or the state on the side chain.
In order on substrate of the present invention, to form as above-mentioned organic membrane; Preferably contain the polymkeric substance of expectation and the polymer composition of the compound of choosing wantonly with light enhanced sensitivity property structure (light enhanced sensitivity property compound) through the known method coating, the method that is heated is then carried out.As above-mentioned polymer composition, for example can directly use, or use after in commercially available aligning agent for liquid crystal, mixing compound with light enhanced sensitivity property structure as the commercially available material of aligning agent for liquid crystal.
As the optional light enhanced sensitivity property compound that mixes in polymer composition, can enumerate the compound following formula (1)～(3) for example represented respectively etc.
Can carry out through for example appropriate method such as rolling method, spin-coating method, print process at coated polymeric composition on the substrate or on the transparency electrode of substrate.Then the heating of carrying out can be according to the suitably settings such as composition of polymer composition.Preferably behind the solvent of removing through prebake in filming, cure after carrying out.The condition of prebake for example is under 40～120 ℃, to carry out 0.1～5 minute.After cure and can for example under 80～300 ℃, preferred 120～250 ℃, carry out for example 5～200 minutes, preferred 10～100 minutes.
Forming a film thickness of preferably
more preferably
more preferably
< liquid-crystal composition >
The liquid-crystal composition that uses in the method for the present invention contains can photopolymerisable reactive mesogen and liquid crystal.
As above-mentioned liquid crystal, be preferably nematic crystal.
Under the situation of the liquid crystal display cells of making the VA type through method of the present invention; The preferred dielectric anisotropy of using is negative nematic crystal; Under the situation of making the liquid crystal display cells except that the VA type, preferably using dielectric anisotropy is positive nematic crystal.
As above-mentioned nematic crystal, can enumerate bar-shaped nematic crystal and discoid liquid crystal, can use to be selected from wherein more than one.As the nematic crystal among the present invention, from irradiation, set out thereby effectively produce the viewpoint that lags behind in the face through the polarisation radioactive ray, preferably use more than one bar-shaped nematic crystal.
As the commercially available article of dielectric anisotropy, can enumerate for example MLC-6608, MLC-6609, MLC-6610, MLC-2037, MLC-2038, MLC-2039 (above is メ Le Network manufactured) etc. for negative nematic crystal;
As dielectric anisotropy is the commercially available article of positive nematic crystal, for example can enumerate ZLI-3086, ZLI-4792, ZLI-5080, ZLI-5081, MLC-2001, MLC-2002, MLC-2003, MLC-2004, MLC-2016, MLC-2017, MLC-2018, MLC-2019, MLC-6221 (above be メ Le Network manufactured); LIXON5035XX, LIXON5036XX, LIXON5037XX, LIXON5038XX, LIXON5039XX, LIXON5040XX, LIXON5041XX, LIXON5043XX, LIXON5044XX, LIXON5046XX, LIXON5047XX, LIXON5049XX, LIXON5050XX, LIXON5051XX, LIXON5052XX (above is that チ Star ソ (strain) makes) etc.
As the photopolymerisable reactive mesogen of above-mentioned ability, so long as can carry out polymerization through rayed, and in molecule, have the compound of liquid crystal similar structures, just can use unqualifiedly.As this compound, can be in molecule, to have at least a group (polymerizable group) and the liquid crystal similar structures of selecting in the group that constitutes by group with polymerism carbon-to-carbon double bond and group more than respectively with epoxy construction.As above-mentioned epoxy construction, be preferably by 1,2-epoxy construction and 1, it is at least a that the 3-epoxy construction is selected, and more preferably 1, the 2-epoxy construction.This polymerizable group, preferably at molecular memory at 1～4, from embodying the viewpoint of good liquid crystal aligning property, more preferably at molecular memory at two.
As the photopolymerisable reactive mesogen of this ability, can enumerate the for example compound of following formula (M) expression,
P
1-A
1-(Z-A
2)
n-P
2(M)
(in formula (M), P
1And P
2Be acryloxy, methacryloxy, vinyl or ethyleneoxy independently of one another, or have the group of epoxy construction,
A
1And A
2Be 1 independently of one another, 4-phenylene or naphthalene-2,6-two bases,
Z be singly-bound ,-COO-
*Or-OCO-
*(more than, have the connecting key and the A of " * "
2Bonding),
N is 0～2 integer, wherein, is 2 o'clock at n, a plurality of A of existence
2With Z can be identical, also can be different).
As the epoxy construction P that has in the following formula (M)
1And P
2Group, can enumerate for example glycidyl, 3-glycidyl ether oxygen base propyl group, 2-(3,4-epoxy cyclohexyloxy) ethyl etc.
Z in the following formula (M) is preferably singly-bound, and n is preferably 0 or 1.
As the compound of following formula (M) expression, can enumerate the compound that is preferably following formula (M-1)～(M-3) expression,
(in formula (M-1)～(M-3), P
1And P
2Identical with above-mentioned formula (M) respectively), can use wherein at least a.
As the P in the following formula (M)
1And P
2, be preferably acryloxy or methacryloxy respectively.
As preferred compound, the compound that can enumerate following formula (M-1-1) and (M-1-2) represent
The photopolymerisable reactive mesogen of this ability with respect to the total weight of liquid-crystal composition, preferably uses in the scope of 0.01～1 weight %, more preferably in the scope of 0.01～0.5 weight %, uses.
The photopolymerisable reactive mesogen of ability, preferred dissolution contains in liquid-crystal composition.
< manufacturing approach of liquid crystal display cells >
The manufacturing approach of liquid crystal display cells of the present invention is characterised in that; Through following operation: form the liquid crystal cell that the substrate that is made up of two substrates with above-mentioned that kind constitutes the subtend setting; Again to above-mentioned liquid crystal cell irradiation polarisation radioactive ray; Wherein, Through make as above-mentioned liquid-crystal composition the layer be clipped in aforesaid substrate between; Make aforesaid substrate to relatively, in one side forms the substrate of transparency electrode, make the face that forms this transparency electrode, towards the direction of the layer of above-mentioned liquid-crystal composition.
In order to form the liquid crystal cell of this structure, can enumerate two kinds of for example following methods.
As first method, can be through gap (box gap), two substrate subtends are provided with; With sealant the periphery of two substrates is fitted; After in the box interval of cutting apart through substrate surface and sealant, injecting the filling liquid crystal composition, the sealing filling orifice, thus make liquid crystal cell.
Perhaps; As second method; On the regulation position of a substrate in two substrates; Be coated with the for example sealant of curing type; The liquid crystal that on the several positions on the substrate, drips again, another substrate of fitting is then simultaneously expanded liquid crystal on whole of substrate; Curing sealant then, thus liquid crystal cell can be made.
Under above-mentioned arbitrary situation, when two substrate subtends are provided with, on one side, form in the substrate of transparency electrode, the face that forms this transparency electrode is disposed towards the direction of another substrate.Do not have transparency electrode, on one side, form the substrate of film, the face that forms this film is disposed towards the direction of another substrate.In addition, under above-mentioned arbitrary situation,, can use and for example contain hardening agent and as epoxy resin of the alumina balls of pad etc. as sealant.
As liquid-crystal composition the layer thickness, be preferably 2～8 μ m, more preferably 3～6 μ m.
Then, irradiation polarisation radioactive ray on liquid crystal cell.Wherein, preferably not under the state that applies voltage on the liquid crystal cell, to above-mentioned liquid crystal cell irradiation polarisation radioactive ray.
Wherein, so-called " not applying the state of voltage to liquid crystal cell " is as long as (all simultaneously form under the situation of transparency electrode at it at two right substrates of formation substrate, be meant between these two transparency electrodes between the transparency electrode that constitutes liquid crystal cell; In constituting the right substrate of substrate only one simultaneously form under the situation of transparency electrode at it, be meant between a pair of zigzag transparency electrode that forms on the one side of this substrate) do not have the state of voltage to get final product in essence, be not the voltage of forbidding applying a little.Between two transparency electrodes, apply direct current or interchange, for example below the 500mV, be preferably below the 100mV, more preferably below the 10mV, be preferably especially under the following voltage condition of 1mV, also should be understood to be equivalent to " not applying the state of voltage " to liquid crystal cell.
As above-mentioned polarisation radioactive ray; Can enumerate luminous ray, ultraviolet ray, far ultraviolet, electron beam, X ray of polarisation for example etc.; The polarisation radioactive ray of optimal wavelength in 150～800nm scope; The more preferably polarisation radioactive ray of wavelength in 240～500nm scope, especially preferably comprising wavelength is the polarisation ultraviolet ray of the open-wire line of 280～350nm.As the polarisation of polarisation radioactive ray, can enumerate for example linear polarization, rotatory polarization etc., preferred linear polarization.As the light source of the above-mentioned polarisation radioactive ray of radiation, can enumerate for example Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc.
As direction to liquid crystal cell irradiation polarisation radioactive ray, preferably shine obliquely with real estate, preferably from real estate be 30～60 ° direction irradiation.
The exposure of polarisation radioactive ray is preferably 0.01～50J/cm
2, 0.1～20J/cm more preferably
2Wherein, the organic membrane in liquid crystal cell contains under the situation of light enhanced sensitivity property composition, even the exposure of polarisation radioactive ray is at 15J/cm
2Below so at 12J/cm
2Below, also can demonstrate fully the application's desired effects.
The polarisation radioactive ray to the irradiation of liquid crystal cell preferably in not enough liquid-crystal composition contained liquid crystal etc. carry out under the temperature of side's temperature.As irradiation temperature, be preferably 20～60 ℃, more preferably 25～50 ℃.
In addition, the two sides through the liquid crystal cell behind radiation exposure is provided with Polarizer, thereby can obtain liquid crystal display cells.In liquid crystal display cells of the present invention, except Polarizer, wavelength plate, light-diffusing films, driving circuit etc. can also be installed.
< liquid crystal display cells >
As the liquid crystal display cells of above-mentioned manufacturing as after shown in the embodiment that states, electrical characteristics are excellent, under the situation of simple electrode structure, liquid crystal aligning property is also excellent, can have wide visual angle and high brightness concurrently.
It is not open in detail as yet that liquid crystal display cells through the inventive method manufacturing can embody the mechanism of liquid crystal aligning control, and the inventor infers that it is following.Promptly; The reactive mesogen of Shi Yonging has anisotropy in the absorption of light in the methods of the invention; Therefore through the ultraviolet ray of irradiation polarisation; Thereby the polymerization on anisotropy of this reactive mesogen is positioned near the substrate that part of and can embodies the liquid crystal aligning control in the polymkeric substance of this reactive mesogen.
Liquid crystal display cells of the present invention can be preferred for various devices, for example is dynamic menu display device of representative etc. with the LCD TV.
Embodiment
< manufacturing of liquid crystal display cells and evaluation >
Embodiment 1
[preparation of liquid-crystal composition]
In 99.7 weight portion negative type liquid crystals (メ Le Network manufactured, trade name " MLC-6608 "), mix the compound and the dissolving of the expression of 0.3 weight portion following formula (M-1-1), thereby prepared liquid-crystal composition.
[preparation of liquid crystal display cells]
On the transparency electrode face of the glass substrate that constitutes by the ITO film with transparency electrode; Use spinner coating commercially available " AL60101 " (JSR (strain) manufacturing) as aligning agent for liquid crystal; With 80 ℃ hot plate prebake 1 minute; Then with nitrogen replacement in the baking oven of chamber; After 200 ℃, cured 1 hour, and formed the organic membrane of thickness 0.1 μ m.Repeat same operation, obtain a pair of (two) have transparency electrode and organic membrane successively in one side substrate.
On the periphery of the face in aforesaid substrate with an organic membrane; The epoxy adhesive that has added the alumina balls of diameter 5.5 μ m through the screen printing coating; Two substrates is set then presses and attach, each organic membrane that makes a pair of substrate in the face of to, 150 ℃ of following hot setting adhesives 1 hour.Then; In the gap of two substrates, add the liquid-crystal composition of above-mentioned preparation by liquid crystal injecting port, seal inlet, then with its flow orientation when 150 ℃ heating is injected to remove liquid-crystal composition down with epoxy adhesive; Slowly cool to room temperature then, form liquid crystal cell.
Then; In the above-mentioned liquid crystal cell that obtains; Is the ultraviolet ray of the linear polarization of light source from being 45 ° direction irradiation with substrate with the high-pressure mercury-vapor lamp; The plane of polarisation that makes linear polarization is with ultraviolet to go into reflecting surface (face that is limited incident direction vector and reflection direction vector) consistent, and to make the shadow surface under the wavelength 313nm be 20J/cm
2, two Polarizers of on the two sides, the outside of liquid crystal cell, fitting again are perpendicular to one another its polarization direction, and the ultraviolet incident direction of irradiation be 45 ° angle at the projecting direction of real estate, thereby make liquid crystal display cells.
For this liquid crystal display cells, according to following evaluation.
[evaluation of liquid crystal display cells]
(1) evaluation of liquid crystal aligning property
In the liquid crystal display cells of above-mentioned manufacturing, visualization light and shade when switch (apply, remove) 5V voltage has or not abnormal area in changing.
To when voltage closes, not observe light from box and leak, and when applying voltage, be shown as white in the box drive area, the average evaluation that other zone does not have light to reveal is liquid crystal aligning property " well "; Will be when voltage close, observe light by box and reveal, or when voltage is opened, the average evaluation that the regional observation beyond from the box drive area is revealed to light is liquid crystal aligning property " not good ", the liquid crystal aligning property of this liquid crystal display cells is " well ".
(2) evaluation of voltage retention
In the liquid crystal display cells of above-mentioned manufacturing, under 60 ℃,, apply the voltage of 5V through 167 milliseconds pulses with the application time of 60 microseconds, remove applying then, the voltage retention after measuring 167 milliseconds.The determinator of voltage retention uses the manufacturing of (strain) Dongyang テ Network ニ power, model " VHR-1 ".
With voltage retention is that average evaluation more than 98% is voltage retention " well ", is " not good " with the average evaluation of less than 98%, and the voltage retention of this liquid crystal display cells is " well ".
Embodiment 2
The compound that in 99.7 weight portion negative type liquid crystals (メ Le Network manufactured, trade name " MLC-6608 "), mixes the expression of 0.3 weight portion following formula (M-1-2), thereby preparation liquid-crystal composition.
Except using this liquid-crystal composition, to estimate with the embodiment 1 same liquid crystal display cells of making, the liquid crystal aligning property of this liquid crystal display cells is " well ", voltage retention is " well ".
The foregoing description 1 and 2 liquid crystal display cells of making demonstrate good liquid crystal aligning property respectively, and viewing angle characteristic is also good.This liquid crystal display cells need not to use for the direction of orientation that determines liquid crystal the electrode of complicated shape, therefore compares with the liquid crystal display cells of 3 records with patent documentation 2, can make with being dirt cheap.In addition, need not to form thrust on the substrate or on the transparency electrode, therefore comparing with the liquid crystal display cells of MVA mode, brightness is higher.In addition, even confirm irradiation ultraviolet radiation in manufacturing process, can not damage the electrical characteristics of liquid crystal display cells yet.
Embodiment 3
In the foregoing description 1, except use as aligning agent for liquid crystal in commercially available " AL60101 ", be the compound that 0.1 weight % adds following formula (1) expression with the solid constituent ratio, the exposure of polarisation illuminated line is 10J/cm
2In addition, implement equally with embodiment 1, make liquid crystal display cells and estimate, the liquid crystal aligning property of this liquid crystal display cells is " well ", and voltage retention is " well ".
Claims (11)
1. the manufacture method of a liquid crystal display cells; It is characterized in that; Through following operation: the substrate that will be made of two substrates is to forming the liquid crystal cell that subtend is provided with structure; Again to above-mentioned liquid crystal cell irradiation polarisation radioactive ray; Wherein, At least one Zhang Zaiqi in these substrates simultaneously goes up and forms transparency electrode; The liquid crystal cell that this subtend is provided with structure by make contain can photopolymerisable reactive mesogen and the layer of the liquid-crystal composition of liquid crystal be clipped in aforesaid substrate between; Make aforesaid substrate to relatively so that therein one side be formed with transparency electrode the face of this transparency electrode of formation of substrate towards the direction of the layer of above-mentioned liquid-crystal composition.
2. the manufacturing approach of liquid crystal display cells as claimed in claim 1, wherein, at least one in the above-mentioned substrate that on one side, forms transparency electrode further forms film on this transparency electrode.
3. the manufacturing approach of liquid crystal display cells as claimed in claim 2, wherein, two aforesaid substrates all form transparency electrode and film successively on one side.
4. the manufacturing approach of liquid crystal display cells as claimed in claim 1, wherein, one in the aforesaid substrate does not have transparency electrode, and this does not have the substrate of transparency electrode on its one side, to form film.
5. like the manufacturing approach of each described liquid crystal display cells of claim 2～4, wherein, above-mentioned film is an organic membrane.
6. like the manufacturing approach of each described liquid crystal display cells of claim 1～4, wherein, the operation of above-mentioned irradiation polarisation radioactive ray is carried out under the state that does not apply voltage on the liquid crystal cell.
7. like the manufacturing approach of each described liquid crystal display cells of claim 1～4, wherein, the contained liquid crystal of above-mentioned liquid-crystal composition is that dielectric anisotropy is the nematic crystal of bearing.
8. the manufacturing approach of a liquid crystal display cells; Wherein, Form the liquid crystal cell that substrate is constituted the subtend configuration through following operation; In liquid crystal cell, do not apply under the state of voltage to above-mentioned liquid crystal cell irradiation polarisation radioactive ray; Wherein, This substrate is to being made up of two substrates that on one side, form transparency electrode and organic membrane successively; Through containing dielectric anisotropy, make aforesaid substrate relative to each organic membrane that has for the layer of negative nematic crystal with the liquid-crystal composition of the photopolymerisable reactive mesogen of ability.
9. like the manufacturing approach of claim 1～4,8 each described liquid crystal display cells, wherein, the photopolymerisable reactive mesogen of above-mentioned ability is the compound of following formula (M) expression,
P
1-A
1-(Z-A
2)
n-P
2(M)
In formula (M), P
1And P
2Be acryloxy, methacryloxy, vinyl or ethyleneoxy independently of one another, or have the group of epoxy construction,
A
1And A
2Be 1 independently of one another, 4-phenylene or naphthalene-2,6-two bases,
Z be singly-bound ,-COO-
*Or-OCO-
*, wherein have the bonding point and the A of " * "
2Bonding,
N is 0～2 integer, wherein, is 2 o'clock at n, a plurality of A of existence
2With Z can be identical, also can be different.
10. the manufacturing approach of liquid crystal display cells as claimed in claim 9, wherein, above-mentioned reactive mesogen that can polymerization is respectively select in the group that constitutes of the compound by following formula (M-1)～(M-3) expression at least a,
In formula (M-1)～(M-3), P
1And P
2Identical with following formula (M) definition respectively.
11. a liquid crystal display cells, it is through the manufacturing approach manufacturing of each described liquid crystal display cells of claim 1～10.
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| KR101997929B1 (en) * | 2012-06-25 | 2019-07-08 | 한양대학교 산학협력단 | Liquid Crystal Display Device |
| WO2014003415A1 (en) * | 2012-06-25 | 2014-01-03 | 한양대학교 산학협력단 | Liquid crystal composition |
| WO2014003413A1 (en) * | 2012-06-25 | 2014-01-03 | 한양대학교 산학협력단 | Liquid crystal display device and method for driving same |
| KR20140001071A (en) * | 2012-06-25 | 2014-01-06 | 한양대학교 산학협력단 | Liquid crystal compound |
| US9977294B2 (en) | 2012-06-25 | 2018-05-22 | Industry-University Cooperation Foundation Hanyang University | Liquid crystal display device |
| KR101997930B1 (en) * | 2012-06-25 | 2019-07-08 | 한양대학교 산학협력단 | Liquid Crystal Display Device |
| WO2014003417A1 (en) * | 2012-06-25 | 2014-01-03 | 한양대학교 산학협력단 | Liquid crystal display device |
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| CN1363852A (en) * | 2001-01-08 | 2002-08-14 | 达碁科技股份有限公司 | LCD with wide visual angle |
| US20100007833A1 (en) * | 2008-07-08 | 2010-01-14 | Chi Mei Optoelectronic Corp. | Liquid Crystal Display |
| WO2010032946A2 (en) * | 2008-09-17 | 2010-03-25 | Samsung Electronics Co., Ltd. | Alignment material, alignment layer, liquid crystal display device and manufacturing method thereof |
| US20100103357A1 (en) * | 2008-10-29 | 2010-04-29 | Samsung Electronics Co., Ltd | Liquid crystal display device and method of manufacturing the same |
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| JP2002131732A (en) * | 1996-09-25 | 2002-05-09 | Matsushita Electric Ind Co Ltd | Polymer dispersion type liquid crystal display device and method for manufacturing the same |
| US6128061A (en) * | 1997-12-08 | 2000-10-03 | Hyundai Electronics Industries Co., Ltd. | Liquid crystal display device |
| WO2001018594A2 (en) * | 1999-09-03 | 2001-03-15 | Kent State University | Fabrication of aligned liquid crystal cell/film by simultaneous alignment and phase separation |
| JP4175826B2 (en) | 2002-04-16 | 2008-11-05 | シャープ株式会社 | Liquid crystal display |
| US20110102720A1 (en) * | 2008-06-27 | 2011-05-05 | Masanobu Mizusaki | Liquid crystal display device and manufacturing method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1363852A (en) * | 2001-01-08 | 2002-08-14 | 达碁科技股份有限公司 | LCD with wide visual angle |
| US20100007833A1 (en) * | 2008-07-08 | 2010-01-14 | Chi Mei Optoelectronic Corp. | Liquid Crystal Display |
| WO2010032946A2 (en) * | 2008-09-17 | 2010-03-25 | Samsung Electronics Co., Ltd. | Alignment material, alignment layer, liquid crystal display device and manufacturing method thereof |
| US20100103357A1 (en) * | 2008-10-29 | 2010-04-29 | Samsung Electronics Co., Ltd | Liquid crystal display device and method of manufacturing the same |
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| KR101809987B1 (en) | 2017-12-18 |
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