CN1900796A - Liquid crystal display device and method of producing the same - Google Patents
Liquid crystal display device and method of producing the same Download PDFInfo
- Publication number
- CN1900796A CN1900796A CN 200610101818 CN200610101818A CN1900796A CN 1900796 A CN1900796 A CN 1900796A CN 200610101818 CN200610101818 CN 200610101818 CN 200610101818 A CN200610101818 A CN 200610101818A CN 1900796 A CN1900796 A CN 1900796A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- substrate
- orientation
- monomer
- crystal indicator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Liquid Crystal (AREA)
Abstract
A liquid crystal display device, in which a liquid crystal layer is supported by a liquid crystal substrate, in which an orientation-controlling layer is formed on a surface of the liquid crystal substrate to regulate an orientation of liquid crystal molecules in the liquid crystal layer in the predetermined direction, and the orientation-controlling layer is formed by an incorporated additive added to the liquid crystal.
Description
The application divides an application, and the application number of its original application is 03123883.1, and the applying date is on May 30th, 2003, and denomination of invention is " liquid crystal indicator and a production method thereof ".
Technical field
The present invention relates to a kind of liquid crystal indicator, more particularly, relate to a kind of liquid crystal indicator and the production method thereof of the degree of orientation that improves the liquid crystal molecule on the substrate to guarantee high display quality.The invention still further relates to a kind of liquid crystal indicator that can under high speed, move, for example be used to be exclusively used in the field preface driving that moving image shows, and a kind of method of producing described device.
Background technology
Liquid crystal indicator just is being widely used in PC, LCD TV, auto navigation, digital camera, video camera and the portable phone.In notebook computer and LCD TV, people expect that very it can relax the visual angle, promptly improve viewing angle characteristic and improve the fineness of image, to meet the needs of continuous increase screen size.In general, liquid crystal indicator has a kind of structure, in described structure, with sealing liquid crystal in a pair of insulated substrate for example between the glass substrate, like this then liquid crystal molecule wherein is pressed predetermined direction and is orientated, and then forms one deck alignment films at corresponding substrate on the one side of liquid crystal.As a kind of aligning film material, commonly used is polyimide or polyamic acid (for example, opening clear JP64-4720 referring to the spy).By making the orientation process process that is used to be provided with tilt angle (pretilt angle) of alignment films experience that forms on the insulated substrate, liquid crystal molecule can take place height-oriented, and described tilt angle is a contact angle between described liquid crystal molecule and the insulated substrate.In addition,, proposed many liquid crystal indicators, for example, proposed a kind of differentiation orientation panel (split orientation panel) structure, comprising multiple liquid crystal molecule with different orientation direction in order to improve viewing angle characteristic and screen fineness.
The production stage of conventional liquid crystal indicator has steps such as the alignment films of formation, orientation process, assembling substrate and encapsulated liquid crystals usually as shown in the graphic extension in the process flow diagram of Fig. 1.These production stages will further obtain describing.At first, the material that will be used for alignment films is coated in insulation component or CF (colorized optical filtering) substrate after the cleaning, and bakes described material to form alignment films.Then, can carry out friction treatment to alignment films for tilt angle is set, described friction treatment is promptly by using a kind of polishing cloth to come friction orientation film surface.By cleaning and dry alignment films, remove the powder, dust and the electrostatic attraction that produce by friction treatment, and finish described orientation process thus.After orientation process is finished, a kind of encapsulant (being generally a kind of bonding agent) is imprinted on the cell substrate, apply then or distribution (hereinafter being also referred to as " sprinkling ") a kind of isolated material, to obtain a gap with respect to optical filtering substrate.Then, cell substrate and optical filtering substrate are bonded together to be assembled into a crystal liquid substrate, then the injection port of liquid crystal by insulated substrate injected, and with the injection port sealing, described insulated substrate are formed by said method.One or two polaroid is installed in can makes a liquid crystal panel on the described optical filtering substrate, described liquid crystal panel has one deck and is sealed in liquid crystal between a pair of substrate, scribbles alignment films on the described a pair of substrate.After finishing a series of step, with predetermined circuit be assemblied in liquid crystal panel around, and make such as products such as notebook personal computer thus.
In above-mentioned a series of production stages, adopted friction treatment method in the orientation process that is used for being provided with tilt angle with polishing cloth friction orientation film surface, described tilt angle is a contact angle between liquid crystal molecule and the insulated substrate.Therefore, physics contact will produce dust and powder with friction, causes the damage of alignment films, and because the generation of electrostatic attraction and the surface of contaminating fluid crystal layer, cause the electrostatic breakdown of the thin film transistor (TFT) (TFT) that forms on the insulated substrate, thereby cause the finished product rate to descend.In order to address these problems, must implement post-processing step and for example clean, yet the enforcement of these steps can to cause increasing of procedure of processing inevitably with dry.In addition, increase along with screen size, owing on an insulated substrate, only form one or two liquid crystal panels, so depending on defective, the finished product rate whether exists, only show as two values promptly 0% and 100% or only to show as three values be 0%, 50% and 100%.In addition, because what need is the hi-vision fineness, so the number of the display element that forms on liquid crystal panel is, 640 * 480 dot matrix for example.Under the situation that three looks show, described dot matrix number may reach and amount to 920,000 elements, thereby the decline of the yield rate that causes owing to the generation of defective will become a serious problem.
For addressing this problem, a kind of optical orientation method that is used for being provided with the tilt angle of alignment films has been proposed, described method has adopted light rather than has relied on by contact the friction treatment (for example, seeing that the spy opens flat JP9-5747) that tilt angle is set with the physics of alignment layer surface.As mentioned above, the tilt angle representative is the contact angle of insulated substrate and liquid crystal molecule between.Therefore, the direction that usually claims to establish tilt angle is a vergence direction.
An example of optical orientation method is described below with reference to Fig. 2 A to 2C.
With reference to figure 2A, with aligning film material for example pi or polyamic acid be coated in an insulated substrate 51 for example on the glass substrate, thereby and baked and made it to form one deck alignment films 52.Then, adopting the polarization direction is the vertical described insulated substrate 51 of ultraviolet 54a vertical irradiation, to implement to be used to adjust the pre-exposure of the physical property of aligning film material.Then, shown in Fig. 2 B, with a predetermined angle [alpha] °, adopt the polarization direction to change the ultraviolet 54b irradiation insulated substrate 51 of 90 degree, be provided with the tilt angle α that tilts with ultraviolet direction of illumination in the alignment films 52 thus, and shown in Fig. 2 C, liquid crystal molecule 56 reaches on the angle identical with tilt angle in identical direction and is orientated.According to above method for orientation treatment, no longer need to implement friction, cleaning and drying and other steps, thereby solved the problems referred to above based on optical orientation.
But still there is a problem in this optical orientation method.For example, if attempt to adopt above-mentioned optical orientation method to realize to improve the differentiation oriented surface plate structure of liquid crystal panel viewing angle characteristic and screen picture fineness, then, must adopt the irradiation of the polarized UV rays of different direction of illuminations that a large amount of tilt angles is set in the alignment films zone by the direction of orientation decision of liquid crystal molecule.In order on same alignment films, a large amount of pitch angle to be set, then need to prepare the multiple optical mask that is used for transmission and cuts off polarized UV rays, and needing to use optical mask repeatedly to shine polarized UV rays with different irradiating angles, this makes orientation process need the extremely long time.
Further, when on substrate, forming alignment films, not only must increase production stage, special-purpose production equipment also must be installed simultaneously for example be used for the printing machine of printing direction-orienting membrane material and be used for the roaster of alignment films, thereby cause the expansion of the face of producing and the rising significantly of production cost inevitably.
Further, in order to reduce production stage and to improve yield rate, a kind of method of producing liquid crystal display cells has been proposed among the Te Kaiping JP11-95221, its liquid-crystal composition that will contain the orientation adminicle of being made up of the photocuring high molecular weight resin is sealed in the liquid crystal cells between the glass substrate, leave standstill liquid-crystal composition, adopt the surface energy of glass substrate that described orientation adminicle is adsorbed in the surface of substrate again, thereby form one deck alignment films.
Liquid crystal indicator for routine, someone proposes a kind of liquid crystal display (LCD) of using active matrix, such a LCD, use to such an extent that be the liquid crystal indicator of a kind of TN (twisted nematic) pattern more widely, in described device, under lighttight state, the liquid crystal material of positive dielectric anisotropy is a horizontal alignment with respect to the surface of a substrate, then turns round with respect to another piece substrate of opposition to turn 90 degrees.
The liquid crystal indicator of TN pattern has the problem of viewing angle characteristic difference, in order to make great efforts to improve its viewing angle characteristic, this has been carried out extensive studies.As another system optionally, developed a kind of MVA (multizone homeotropic alignment) system, according to this system, liquid crystal material with negative dielectric anisotropic is vertical orientated, and after applying voltage, the vergence direction of liquid crystal molecule can be controlled in a plurality of directions, thereby improve viewing angle characteristic widely, protrusion and slit that described system adopts substrate surface to form are controlled the vergence direction of liquid crystal molecule and need not be carried out friction treatment to alignment films.
Yet, vertical orientated in order to make liquid crystal material, not only in the liquid crystal indicator of TN pattern, and in the MVA system, must adopt material formation one deck alignment films such as pi too.The formation of alignment films needs printing, bakes and clean or the like step, and described step is the main hindering factor that reduces production stage and lower production cost.
In addition, as a kind of liquid crystal indicator that uses active matrix, adopt the liquid crystal indicator of nematic crystal to obtain using widely.In recent years, needed to provide a kind of driving liquid crystal indicator of field preface that motion picture shows that is used for for example being adapted to.This liquid crystal indicator needs the speed-sensitive switch of liquid crystal molecule.Therefore, press for a kind of liquid crystal indicator with higher response speed is provided.
In the liquid crystal indicator that uses nematic crystal, dwindle the thickness of liquid crystal cells and increase tilt angle very effective for improving response speed of liquid crystal.Usually, by adopt polishing cloth rub organic alignment films for example the film that forms of pi or polyamic acid realize the pre-dumping of liquid crystal.But adopt friction treatment to be difficult to obtain even and bigger tilt angle.In general, its tilt angle upper limit is about 6 to 7 degree.In addition, friction treatment has produced powder and dust, also causes a such problem simultaneously, and promptly element can damage because of static.Therefore, concerning active substrate, hope can adopt other method rather than friction to carry out orientation process especially.
Further, adopt organic alignment films that comprises a large amount of a kind of alkyl groups and the density that improves the described alkyl group of alignment layer surface, can obtain bigger tilt angle effectively.Yet, when obtaining bigger tilt angle, can produce a problem by the said method attempt, promptly shade can be owing to the scattering in the tilt angle on the plane becomes outstanding, and striped can become eye-catching because of friction.
As a kind of method for alignment outside the friction treatment, a kind of optical orientation method that the method for weir structure is provided and above describes with reference to figure 2A to 2C at alignment layer surface has been proposed.According to the method that the weir structure is provided at alignment layer surface, on the alignment films of a substrate, form the first striped weir, on the alignment films of another piece substrate, form parallel but deviate from the second striped weir of the first striped panel.It utilizes the liquid crystal molecule between the first striped weir and the second striped weir to have vertical orientated this fact of character in these striped weirs, has controlled the orientation of whole liquid crystal molecules.
Yet, provide the method for weir structure to can be applicable to vertical orientating type liquid crystal display device, and can't be applied to described TN type liquid crystal indicator.Say that further according to the optical orientation method, it adopts the alignment films of ultraviolet ray irradiation pi or polyamic acid can make the alignment layer surface anisotropy, thereby makes liquid crystal molecular orientation.Yet, when adopting the optical orientation method, the power of enforcement of its restriction orientation a little less than, and be difficult to realize bigger tilt angle.For example, when adopting the optical orientation method, its tilt angle that can reach is about 1 degree.
In addition, with regard to the orientation control technology of liquid crystal indicator, Te Kaiping JP5-173138 has lectured the method for differentiation orientation, the spy opens flat JP9-146096 and then discloses a kind of liquid crystal indicator, alignment films has wherein comprised the vertical orientated zone of striated and the parallel-oriented zone of striated, both alternately arrange, and described alignment films is through friction treatment, and the frictional direction of described friction treatment is perpendicular to vertical orientated zone and parallel-oriented zone.
Summary of the invention
As mentioned above, Chang Gui liquid crystal indicator is still comprising problem demanding prompt solution.The present invention is devoted to address these problems.
At first, target of the present invention is, a kind of liquid crystal indicator and production method thereof are provided, described device is realized high-quality display characteristic by the orientation of control liquid crystal molecule is for example vertical orientated or parallel-oriented, simultaneously do not need alignment films is provided separately, thereby successfully reduced production stage, lowered production cost and reduced raw materials for production.
Secondly, target of the present invention also is, a kind of liquid crystal indicator is provided, and it is characterized by to have fabulous response speed, is not furnished with the substrate of active matrix structure and do not need to rub.
Except these targets, target of the present invention also is, solve the problems that exist in the conventional liquid crystal indicator, in described conventional liquid crystal indicator, must on each piece substrate of the paired substrate of forming liquid crystal indicator, form alignment films, alignment layer surface must be handled through friction treatment or optical orientation simultaneously, thereby has wherein related to the problem of many relevant production stages, production cost and management process.More precisely:
Therefore, target of the present invention is, a kind of liquid crystal indicator is provided, and described device need not form the step of alignment films on the liquid crystal side substrate.
Further, target of the present invention is, a kind of liquid crystal indicator is provided, and described device has simple composition, and simply makes with the cost that lowers.
Further, target of the present invention is, a kind of production high-performance is provided but can guarantees the method for the liquid crystal indicator of yield rate simultaneously again.
By hereinafter detailed description, can easily understand above-mentioned target of the present invention and other targets to the present invention.
First aspect of the present invention is a kind of liquid crystal indicator, wherein, liquid crystal layer is supported by a crystal liquid substrate, it is characterized in that, form one deck on the surface of crystal liquid substrate and be used for controlling the orientation key-course that the liquid crystal layer liquid crystal molecule is orientated on predetermined direction, and described orientation key-course forms by a kind of fusion adjuvant is added liquid crystal.
In this respect, the present invention also is a kind of method of producing liquid crystal indicator, wherein, liquid crystal layer is supported by crystal liquid substrate, it is characterized in that by adding the liquid crystal of adjuvant and formed liquid crystal layer on the surface at crystal liquid substrate thus in injection between the crystal liquid substrate, described adjuvant has the performance that the control liquid crystal molecule is orientated by predetermined direction, and described liquid crystal layer has the orientation key-course of being made up of described adjuvant.
Second aspect of the present invention is a kind of liquid crystal indicator, described device has comprised a pair of relative thirty years of age substrate, one deck substrate on the orientation key-course that forms, one deck be arranged in substrate between liquid crystal layer and an electrode that is used for applying electric field to liquid crystal layer, wherein said orientation key-course is formed at this at least one substrate in the substrate, and comprised a plurality of first elongated orientation area, the described first elongated orientation area is used to make liquid crystal molecule to be orientated by the direction perpendicular to substrate surface almost, also comprised a plurality of second elongated orientation area, the described second elongated orientation area is used to make liquid crystal molecule to be orientated by the direction that almost is parallel to substrate surface, described first orientation area and second orientation area are alternately arranged, and the part liquid crystal that is positioned at first orientation area is orientated continuously with the part liquid crystal that is positioned at second orientation area.
Form according to this, the part liquid crystal that is positioned at first orientation area is orientated continuously with the part liquid crystal that is positioned at second orientation area, also influence each other simultaneously, and this has just realized having the liquid crystal indicator of big tilt angle and high response speed.
The 3rd aspect of the present invention is a kind of liquid crystal indicator with panel construction, described device has wherein comprised a pair of substrate that is arranged relative to each other and has been sealed in liquid crystal between these substrates, wherein, described resin bed is inserted described liquid crystal and the described liquid crystal panel that contacts with liquid crystal form interface between the element, described resin bed is by curable adjuvant is solidified to form, described curable adjuvant comprises a kind of monomer and a kind of multi-functional monomer of simple function group, and the functional group that is contained in the vertical orientated expression on the monomer in the curable additives derives out from the surface of described resin bed.
Aspect this, the invention reside in the method that a kind of production has the liquid crystal indicator of panel construction, described device has comprised a pair of substrate that is arranged relative to each other and has been sealed in liquid crystal between these substrates, and wherein said method comprises the steps:
The potpourri of described liquid crystal and a kind of curable adjuvant is injected between the described substrate, and described curable additives comprises a kind of simple function group monomer and a kind of polyfunctional monomer; And
Apply energy so that described curable additives is solidified, and optionally form resin bed thus with sieve texture at the interface that described liquid crystal and the liquid crystal panel that contacts with described liquid crystal are formed between the element, and, derive the functional group of the vertical orientated expression that is contained in the monomer in the described curable additives from the surface of described resin bed.
In liquid crystal indicator according to the present invention and production method thereof, curable additives be for can adopt the various energy to be cured, the monomer of preferred light curing, heat curing or electronic beam curing, oligomer and other adjuvants.
Description of drawings
Fig. 1 is a process flow diagram, is used to illustrate the production stage of conventional display panels;
Fig. 2 A to 2C is one group of sectional view, its diagram and the conventional method of optical orientation has been described successively;
Fig. 3 is a view, and it illustrates liquid crystal indicator of the present invention, and described device is in such state, promptly joins adjuvant in the liquid crystal by the surface adsorption of crystal liquid substrate;
Fig. 4 A is a sectional view, and it illustrates a kind of liquid crystal indicator of routine;
Fig. 4 B is a sectional view, and it illustrates according to a kind of liquid crystal indicator of the present invention;
Fig. 5 A to 5C is one group of sectional view, and it illustrates the step that makes liquid crystal vertical-tropism, wherein by ultraviolet irradiation adjuvant is added described liquid crystal;
Fig. 6 is a view, and it illustrates a kind of state, promptly according to second embodiment of the present invention, forms two kinds of orientation key-courses on the surface of glass substrate;
Fig. 7 is a sectional view, and it illustrates a kind of liquid crystal indicator that first embodiment according to the present invention forms;
Fig. 8 is a sectional view, and it illustrates the ruuning situation of one deck alignment films on second glass substrate in the liquid crystal indicator of Fig. 7;
Fig. 9 is a sheet of planar figure, and it has illustrated the alignment films on the pixel electrode on second glass substrate among Fig. 7;
Figure 10 is a synoptic diagram, and it has illustrated from the tilt angle of the observed liquid crystal after liquid crystal indicator is finished of arrow A direction of Fig. 9;
Figure 11 is a sectional view, and it illustrates the liquid crystal indicator that second embodiment according to the present invention forms;
Figure 12 is a synoptic diagram, and it illustrates first and second glass substrates according to the embodiment of Figure 11;
Figure 13 is a synoptic diagram, and it is with the B part of sizing specification Figure 12 of amplification;
Figure 14 is a sheet of planar figure, and it has illustrated the example of a change of second glass substrate;
Figure 15 A is a synoptic diagram, and it has illustrated ashing (ashing) structure before;
Figure 15 B is a synoptic diagram, and it has illustrated the structure after the ashing;
Figure 16 is a sectional view, and it illustrates according to second glass substrate in the liquid crystal indicator of the 3rd embodiment of the present invention;
Figure 17 is a sectional view, and it illustrates the liquid crystal indicator that the 4th embodiment according to the present invention forms;
Figure 18 is a sectional view, and it illustrates the operation of the liquid crystal indicator among Figure 17;
Figure 19 is a sectional view, and it illustrates the liquid crystal indicator that the 5th embodiment according to the present invention forms;
Figure 20 is a sectional view, and it illustrates the main composition according to panchromatic TFT liquid crystal indicator of the present invention;
Figure 21 is a sectional view, and it illustrates a kind of state of resin bed in the liquid crystal indicator among Figure 20;
Figure 22 is a sectional view, and it illustrates a kind of state of orientation near the liquid crystal molecule of the resin bed of Figure 21;
Figure 23 is a process flow diagram, and it has illustrated the production stage according to a kind of display panels of the present invention;
Figure 24 A and 24B are one group of sectional view, and it has illustrated the formation step according to resin bed of the present invention successively;
Figure 25 A and 25B are one group of sectional view, and it has illustrated two embodiments in addition according to liquid crystal indicator of the present invention;
Figure 26 A and 26B are respectively a sheet of planar figure and a sectional view, and it has illustrated another embodiment according to liquid crystal indicator of the present invention;
Figure 27 is a sectional view, and it has illustrated another embodiment according to liquid crystal indicator of the present invention;
Figure 28 is a sectional view, and it has illustrated another embodiment according to liquid crystal indicator of the present invention;
Figure 29 is a sectional view, and it has illustrated another embodiment according to liquid crystal indicator of the present invention;
Figure 30 is a sectional view, and it has illustrated another embodiment according to liquid crystal indicator of the present invention; And
Figure 31 is a sectional view, and it has illustrated another embodiment according to liquid crystal indicator of the present invention.
Embodiment
The liquid crystal indicator of each aspect and production method can with various embodiments, advantageously be implemented within the scope of the invention according to the present invention.With reference to corresponding accompanying drawing the preferred embodiments of the invention are described.Yet, should be noted in the discussion above that and the present invention only must not be confined to following embodiment.
Of the present invention aspect first in, liquid crystal indicator is the device that a kind of liquid crystal layer is supported by crystal liquid substrate.Described liquid crystal layer has comprised a kind of adjuvant that is blended in the liquid crystal, and described liquid crystal layer has the orientation key-course that one deck forms on its surface, and described orientation key-course is used to control the orientation of liquid crystal molecule on predetermined direction.
Under the preferred situation, described liquid crystal indicator is the device that a kind of liquid crystal layer is supported by crystal liquid substrate, described liquid crystal layer has comprised a kind of liquid crystal B, the addition of C that has added fusion among the described liquid crystal B, described addition of C has the characteristic that the control liquid crystal molecule is orientated on predetermined direction, and has following relational expression:
(v
AB-v
AC)/v
BC＞-1
Satisfy under the preferred situation:
(v
AB-v
AC)/v
BC＞1
V wherein
ABBe when liquid crystal B wetting surface A, the variable quantity of the surface energy on the surfaces A, v
ACBe when addition of C wetting surface A, the variable quantity of the surface energy on the surfaces A, and v
BCBe when liquid crystal B contacts with addition of C, the variable quantity of the surface energy on the liquid crystal B.
At first, described below is main points of the present invention.
To apply and to form under the prerequisite of alignment films not needing, the function that obtains being equal to the function of the alignment films of routine is the basis, the inventor attempts controlling the adjuvant that liquid crystal molecule is orientated be blended in the liquid crystal on predetermined direction a kind of, and uses above-mentioned liquid crystal to reach the purpose that forms liquid crystal layer.Therefore, described method might make the orientation key-course of the identical function that has conventional alignment films in fact, near when liquid crystal layer forms, on the surface of liquid crystal layer, form automatically, and need not apply and form alignment films, described coating and formation alignment films are finished the necessary condition of conventional liquid crystal indicator just.
In order to inject the liquid crystal that contains the fusion adjuvant, to form a kind of orientation key-course on the liquid crystal layer surface, as mentioned above, adjuvant must be in the surface portion of liquid crystal layer partly, the surface of crystal liquid substrate must be wetting with adjuvant, and therefore adsorb described adjuvant.Then, in order to realize above main points of the present invention, the inventor by analysis relation between relation, crystal liquid substrate surface and the liquid crystal between crystal liquid substrate surface and the adjuvant and the relation between liquid crystal and the adjuvant, and designed a so-called formula of having ready conditions qualitatively at above-mentioned relation, as described below.
The inventor finds that when satisfying following relational expression, the adjuvant that is blended in the liquid crystal will be adsorbed in the surface of crystal liquid substrate:
(v
AB-v
AC)/v
BC＞-1 ---(1)
V wherein
ABBe when liquid crystal B wetting surface A, the variable quantity of the surface energy on the surfaces A, v
ACBe when addition of C wetting surface A, the variable quantity of the surface energy on the surfaces A, and v
BCBe when liquid crystal B contacts with addition of C, the variable quantity of the surface energy on the liquid crystal B
An object lesson has been described among Fig. 3, and crystal liquid substrate wherein is a transparency electrode 102, its surface adsorption a kind of adjuvant 201 of fusion.
The inventor further finds, when satisfying following relational expression, described adjuvant will be more suitable for to crystal liquid substrate adsorbed, and spread:
(v
AB-v
AC)/v
BC＞1 ---(2)
When having comprised two or more materials in the described adjuvant, can use the above formula of having ready conditions, select any attractive material.
For described adjuvant, required concrete property comprises having at least a part to present vertical orientated characteristic in the described adjuvant and also can form chemical bond with the surface of crystal liquid substrate; Described adjuvant can be the surperficial adsorbed of crystal liquid substrate physically and form chemical bond with the surface; Described adjuvant can and can form chemical bond physically for the surperficial adsorbed of crystal liquid substrate between adjuvant; And described adjuvant has comprised a kind of monomer material, and can be the surperficial adsorbed of crystal liquid substrate physically, and can form Polymer Structure with as the orientation key-course.
The specific embodiments that is based on the bare bones of the invention described above described below.
Now will describe embodiment in detail, focus on the formation of describing the orientation key-course, particularly when forming liquid crystal layer.In the present embodiment, the surface energy variation amount on the surface of crystal liquid substrate, liquid crystal and adjuvant surface all satisfies above formula (1) and (2).
(first embodiment)
Fig. 4 A and 4B are one group of sectional view, it illustrates the liquid crystal indicator according to an embodiment of comparing with conventional liquid crystal indicator, wherein Fig. 4 A explanation is conventional equipment, and what Fig. 4 B illustrated is embodiment of the present invention, and wherein public mark is represented identical element.
In the liquid crystal indicator of routine, shown in Fig. 4 A, ITO (indium tin oxide) ELD 102 forms on the surface of a pair of glass substrate 101.On ELD 102, also formed the orientation texture that is used to control orientation, i.e. weir shape structure 104, its height is 1.5 μ m, wide is 10 μ m.Gap between the described weir is 25 μ m.
As orientation texture, can on ELD 102, form slit or tiny slit with replenishing or replace weir structure 104 as weir structure 104 (referring to JP2000-295266; People such as S.Kataoka, Digest of SID01, p.1066 (2001); People such as A.Tanaka, Digest of SID99, p.206 (1999); People such as A.Tanaka, Digest of SID98, p.1077 (1998)).
On weir shape structure 104, formed vertical alignment layer 103.Thickness is fixed between the vertical alignment layer 103 for about 4 μ m for example and the liquid crystal layer 105 that comprises negative liquid crystal, and weir shape structure 104 makes liquid crystal molecule 105a in θ p angular direction run-off the straight.
On the other hand, in liquid crystal indicator according to embodiment of the present invention, shown in Fig. 4 B, adopt fusion the liquid crystal of adjuvant 201 form liquid crystal layer 105, and do not need to form vertical oriented layer 103.In this case, can form orientation key-course 202 on the surface of liquid crystal layer 105, to realize a stable vertical orientated structure effectively.In this case, can provide weir shape structure 104 (or slit or tiny slit) and the orientation texture of replenishing of conduct orientation key-course 202, in order to the orientation of control liquid crystal molecule in θ p direction.
In the present embodiment, described liquid crystal is negative liquid crystal, and the adjuvant that is used for fusion is for example to have a kind of bifunctional acrylate's monomer of liquid crystal type skeleton.In described liquid crystal, added a kind of ultraviolet polymerization initiator in addition.When on the surface that sticks to ELD 102 under the situation of adjuvant 201 at ultraviolet irradiating liquid crystal, can on the surface of liquid crystal layer 105, form a kind of polymer architecture and as orientation key-course 202.According to estimates, bifunctional acrylate's monomer segment ground of adhesion and glass substrate 101 have formed chemical bond.In the present embodiment, the surface of crystal liquid substrate is an ELD 102, yet the also available final diaphragm of described ELD 102 is SiN or glass substrate replacement for example.In this case, further, can also realize horizontal alignment by the character of conversion monomer.In addition, make a kind ofly to have the simple function group acrylate monomer generation graft polymerization of vertical orientated group and form a kind of brush polymer, also might realize a kind of stable and effective orientation.
Fig. 5 A to 5C is one group of sectional view, and it illustrates under ultraviolet irradiation, makes the liquid crystal that added adjuvant that vertical orientated step take place.
Under the irradiation of ultraviolet ray 302, liquid crystal molecule 105a little by little is tending towards vertical orientated state from the initial state shown in Fig. 5 A, the liquid crystal 301 that added adjuvant in the initial state of described Fig. 5 A is sealed, and Fig. 5 B shown be to begin to form orientation key-course 202.Then, shown in Fig. 5 C, liquid crystal molecule 105a takes place vertical orientated, and has almost formed orientation key-course 202 at the same time.
At this moment, in bifunctional acrylate's monomer generation polymerization,, can also make the orientation of described liquid crystal molecule further reach stable by liquid crystal is applied predetermined voltage.
The surface of crystal liquid substrate can also use oxygen plasma or the ultraviolet ray of excite state atom to modify in advance, so that it can more effectively adsorb described adjuvant.For example, the surface of crystal liquid substrate can be handled 1 minute under 500 watts oxygen plasma.
The surface of crystal liquid substrate can also use in advance hydrophilic agent for example the basic surface activating agent modify so that it can more effectively adsorb described adjuvant.Representational surfactant comprises Alkonox and other matrix washing agent.
(second embodiment)
In the present embodiment, the adjuvant that is used for fusion is a kind of monomer and a kind of potpourri with monomer that contains simple function methacryl group of straight chained alkyl with difunctionality acryloyl group.In addition, also in liquid crystal, added a kind of ultraviolet polymerization initiator.
As shown in Figure 6, under the situation of ultraviolet irradiating liquid crystal, the acryloyl monomer with high response is at first adsorbed for glass substrate 101, and forms the first orientation key-course 401.Then, on the first orientation key-course 401, form the second orientation key-course of forming by the lower methacryl monomer of reactivity 402.Because the effect of the straight chained alkyl that forms is gone up on the surface, described liquid crystal molecule can take place vertical orientated.
(the 3rd embodiment)
In the present embodiment, described liquid crystal is negative liquid crystal, and the adjuvant that is used for fusion is the silicon halide with a straight chained alkyl.In this case, the OH group that is present in the nesa coating can react with halogen.Because the oxygen in silane and the glass substrate forms chemical bond, so straight chained alkyl is in the surface of crystal liquid substrate, and the liquid crystal molecule generation is vertical orientated thus.
(the 4th embodiment)
In the present embodiment, described adjuvant is a kind of sorbitan monooleate (ProductName, Reodol SP-010), and this adjuvant is a kind of non-ionics of being produced by Kao company.SP-010 is added liquid crystal, and its consumption level is for accounting for liquid crystal 2 weight %.By the surface adsorption of glass substrate, liquid crystal molecule then takes place vertical orientated described surfactant physically.SP-010 is a kind of non-ionics, and it shows favorable conductive character.
Under the situation of physisorption, the orientation of the liquid crystal molecule relative less stable that seems.Therefore, can near cleaning point (nematic isotropic), carry out annealing in process to liquid crystal, and make the orientation texture of liquid crystal be issued to stable in the prerequisite of not being damaged.
(the 5th embodiment)
In the present embodiment, SP-010 is added liquid crystal, its consumption level is the 2 weight % that account for liquid crystal, and described SP-010 is a ProductName of Kao company, and it can for example add acryloyl group in the anhydrosorbitol and obtain at polar group.Then, add a kind of Photoepolymerizationinitiater initiater in potpourri, its consumption accounts for about 1 weight % of total amount.Under ultraviolet irradiation, can form chemical bond between the acryloyl group and between acryloyl group and the crystal liquid substrate surface.At the ultraviolet irradiating liquid crystal of use and under it applies voltage condition, described monomer is comply with the orientation generation polymerization of liquid crystal, thereby stablizes described orientation.
(the 6th embodiment)
In the present embodiment, a kind of bifunctional acrylate's monomer with liquid crystal type skeleton adds liquid crystal as a kind of adjuvant, and its consumption is the 0.3 weight % that accounts for liquid crystal.Add a kind of Photoepolymerizationinitiater initiater then, its consumption is the about 2 weight % that account for described bifunctional acrylate's monomer.Add SP-010 again with as a kind of adjuvant, its consumption is the 2 weight % that account for liquid crystal, and described SP-010 is a ProductName of Kao company.After adding adjuvant, liquid crystal promptly takes place vertical orientated.At the ultraviolet irradiating liquid crystal of use and under it applies voltage condition, described monomer is comply with the orientation generation polymerization of liquid crystal, thereby stablizes described orientation.
(the 7th embodiment)
In the present embodiment, a kind of simple function group acrylate monomer that will have the liquid crystal type skeleton mixes with liquid crystal with a kind of acrylate monomer with three or more functional groups.Then, add a kind of Photoepolymerizationinitiater initiater in potpourri, its consumption accounts for about 1 weight % of total amount.Because the cause of trifunctional group acrylate's monomer can obtain stable orientation texture.At the ultraviolet irradiating liquid crystal of use and under it applies voltage condition, described monomer is comply with the orientation generation polymerization of liquid crystal
(the 8th embodiment)
In the present embodiment, a kind of alkyl is added liquid crystal with as side chain, and a kind of acid anhydrides is added wherein with as main chain, make both that polymerization all take place in liquid crystal.Like this then make liquid crystal molecule that firm orientation take place.Further, surperficial adsorbable a kind of polymkeric substance of crystal liquid substrate and make the orientation of liquid crystal molecule more stable, described polymkeric substance have comprised as side chain and compatible with liquid crystal alkyl and as the acid anhydrides of main chain.
Embodiment according to the invention described above, can be under the prerequisite that alignment films is not provided separately control for example being orientated the horizontal alignment of the vertical orientated or liquid crystal molecule of liquid crystal molecule, so just production stage, production cost and raw materials for production might be reduced, but still high display characteristic can be obtained.
From as can be known above-mentioned, according to the present invention, it provides a kind of liquid crystal indicator, it can be under the prerequisite that alignment films is not provided be separately controlled for example being orientated the horizontal alignment of the vertical orientated or liquid crystal molecule of liquid crystal molecule, so just production stage, production cost and raw materials for production might be reduced, but still high display characteristic can be obtained.
In aspect second of the present invention, described liquid crystal indicator has comprised a pair of relative thirty years of age substrate, one deck substrate on the orientation key-course that forms, one deck be arranged in substrate between liquid crystal layer and an electrode that is used for applying electric field to liquid crystal layer, wherein said orientation key-course is formed at this at least one substrate in the substrate, and comprised a plurality of first elongated orientation area, it is used to make liquid crystal molecule to be orientated by the direction perpendicular to substrate surface almost, also comprised a plurality of second elongated orientation area, it is used to make liquid crystal molecule to be orientated by the direction that almost is parallel to substrate surface, described first orientation area and second orientation area are alternately arranged, and the part liquid crystal that is positioned at first orientation area is orientated continuously with the part liquid crystal that is positioned at second orientation area.
Fig. 7 is a cross-sectional view, and it illustrates the basic module of the liquid crystal indicator that first embodiment of the invention provides.Liquid crystal indicator 110 has comprised a pair of opposed transparent glass substrate 112 and 114 and be inserted in this to the liquid crystal layer between glass substrate 112 and 114.Have a common electrode 118 and one deck alignment films (promptly being orientated key-course) 120 on first glass substrate 112.Have a pixel electrode 122 and one deck alignment films (promptly being orientated key-course) 124 on second glass substrate 114.Described second glass substrate 114 comprises a kind of active matrix structure.
Fig. 8 is a cross-sectional view, and it illustrates the ruuning situation of the alignment films 124 on second glass substrate 114 of liquid crystal indicator among Fig. 7.Fig. 9 is a synoptic diagram, and it illustrates a part of the alignment films 124 on the pixel electrode 122 on second glass substrate 114 among Fig. 7.In Fig. 9, on the display pixel area, alignment films 124 has comprised a plurality of first elongated orientation area 124V, wherein liquid crystal molecule is by being orientated near the direction perpendicular to substrate surface, also comprised a plurality of second elongated orientation area 124H, wherein liquid crystal molecule is by being orientated near the direction that is parallel to substrate surface.The first elongated area 124V and the second elongated area 124H all have a kind of vertical bar line form, and alternately arrangement parallel to each other.
Figure 10 is a synoptic diagram, and it has illustrated from the tilt angle of the observed liquid crystal after liquid crystal indicator 110 is finished of arrow A direction of Fig. 9.In Figure 10, the tilt angle of liquid crystal molecule in the first orientation area 124V is with θ
vExpression, and the tilt angle of liquid crystal molecule in the second orientation area 124H is with θ
hExpression.θ
vAlmost vertical with substrate surface, and θ
hAlmost parallel with substrate surface.In addition, the pitch angle in the body part (be the major part between alignment films 120 and 124 in the liquid crystal layer 116, remove that a part of liquid crystal that directly contacts with alignment films 120 and 124) of liquid crystal layer 116 is with θ
bExpression.In the present invention, the liquid crystal of liquid crystal layer 116 body parts has taken place near uniform orientation, and keeps a relational expression θ
h＜θ
b＜θ
v
In Fig. 8, at the liquid crystal that is arranged on the first orientation area 124V of alignment films 120, with the 116Va liquid crystal partly that the first orientation area 124V directly contacts almost vertical with substrate surface orientation has taken place.At the liquid crystal that is arranged on the first orientation area 124V of alignment films 120, be in liquid crystal away from 116Vb part in the body part of the first orientation area 124V and obtained orientation with the substrate surface bevel.On the other hand, at the liquid crystal that is arranged on the second orientation area 124H of alignment films 120, with the 116Ha liquid crystal partly that the second orientation area 124H directly contacts almost parallel with substrate surface orientation has taken place.In this case, described liquid crystal can with the direction of the parallel longitudinal in 124V zone and 124H zone on be orientated.At the liquid crystal that is arranged on the second orientation area 124H of alignment films 120, be in liquid crystal away from 116Hb part in the body part of the second orientation area 124H and obtained orientation with the substrate surface bevel.
In the present invention, be positioned at the first orientation area 124V body part 116Vb part liquid crystal and be positioned at the liquid crystal of 116Hb part of the body part of the second orientation area 124H, both interact and make the orientation in the body part of liquid crystal layer 116 obtain on average, thereby the liquid crystal that is positioned at the 116Vb of the first orientation area 124V and the second orientation area 124H and 116Hb part can take place continuously and near orientation uniformly.
In this case, if one side or both sides among the first orientation area 124V and the second orientation area 124H have relatively large width, it is less that this part liquid crystal that then is positioned at these regional centers is positioned at the influence of that part of liquid crystal of adjacent domain.Thus, the orientation of the body part of liquid crystal layer 116 can't obtain on average, and liquid crystal will be with horizontal or vertical orientation in whole zone.Therefore, the width of the first orientation area 124V and the second orientation area 124H must be very narrow and small, can interact so that wherein be positioned at that part of liquid crystal of body part.The width of the preferred first orientation area 124V and the second orientation area 124H is not more than 10 μ m, under the preferred situation, is not more than 5 μ m.
Therefore,, provide the substrate that has the active matrix structure to realize bigger tilt angle, and do not need to carry out friction treatment, the like this then liquid crystal indicator that might realize having fabulous response speed according to the present invention.Further, this also feasible yield rate and turnout that might improve production run.This also makes might provide a kind of liquid crystal indicator that a preface drives that is used for, and described preface drives and be suitable for combining with narrow crack.
In above-mentioned structure, the first orientation area 124V and the second orientation area 124H can be made by the different orientation membrane material respectively.Alternatively, the first orientation area 124V and the second orientation area 124H can be made by a kind of single aligning film material, and can optionally handle.In this case, can use compound as a kind of material that forms alignment films 124, and the second orientation area 124H can have a kind of dense alkyl structure of the first orientation area 124V that is not so good as with straight chained alkyl structure.To have zone of hanging down dense alkyl structure and zone in order forming, can to reduce alkyl at the low dense area repels alkyl of needs or by post-processing approach with dense alkyl structure.Specifically, can be in the following ways.
(a) on the second orientation area 124H, form a kind of structure, then a kind of vertical alignment layer is coated in whole surface on second substrate 114 to form alignment films 124.Selected structure does not almost have adhesive attraction for vertical orientated membrane material, and promptly described structure is repelled described vertical orientated membrane material.In the zone of no described structure, the consumption of desirable increase applies vertical orientated membrane material, and in the zone that has described structure, the consumption of desirable minimizing applies vertical orientated membrane material, has then determined the first orientation area 124V and the second orientation area 124H thus.Have the surface energy that is not more than 50mN/m when described structure is formed, and repel vertical orientated membrane material.Described structure will be repelled partially oriented film and make alkyl become not dense, and can be divided into different zones to alignment films.The height of described structure does not have significant meaning, can be not more than 1 μ m.The surface of alignment films can be owing to provide described structure to become uneven, but when aligning film material is mobile, its can become again smooth (seeing Figure 15 A and 15B).
(b) after alignment films 124 forms, use the ultraviolet ray irradiation second orientation area 124H, to excise alkyl and to apply horizontal orientation.
(c) compound that will have a straight chained alkyl adds liquid crystal, and described liquid crystal is injected between the substrate, so that described compound can be adsorbed for two substrates.The compound layer of absorption can be brought into play the function of orientation key-course, and it demonstrates vertical orientated effect, and the feasible step that might save coating and form alignment films.In this case, from the foothold of stability, preferred described compound with straight chained alkyl comprises a photoreactive groups.After injection comprised the liquid crystal of described compound with straight chained alkyl, described compound optionally was or the first orientation area 124V or the second orientation area 124H adsorbed (or adsorbed for arbitrary limit in these zones with bigger amount).In this case, described structure also can form the zone of different polarity on substrate, maybe can adopt ultraviolet ray that it is optionally shone.
Figure 11 is a cross-sectional view, and it illustrates the liquid crystal indicator 110 that forms according to second embodiment of the invention.In Fig. 8, the description of the orientation of liquid crystal is only depended on the relation of the alignment films 124 on second glass substrate 114.Hence one can see that, and the alignment films 120 on first glass substrate 112 can be formed in many ways.In Figure 11, to the description of the orientation of liquid crystal based on the relation between the alignment films 124 on the alignment films 120 on first glass substrate 112 and second substrate 114.
In Figure 11, structure 132 is arranged between pixel electrode 122 and the alignment films 124.Described structure 132 stretches with the striated form as the second orientation area 124H among Fig. 9, and is covered by alignment films 124.As mentioned above, selected structure 132 does not almost have adhesive attraction for vertical orientated membrane material, and has played the effect of repelling vertical orientated membrane material.Preferably make described structure 132 have the surface energy that is not more than 50mN/m.Thus, alignment films 124 has comprised first orientation area 124V that is in two gaps between the structure 132 and the second orientation area 124H that is on the described structure 132.As above with reference to figure 7 to what Figure 10 explained, the first orientation area 124V described herein demonstrates identical effect with the second orientation area 124H.
Figure 12 is a synoptic diagram, and it illustrates given first and second glass substrates 112 and 114 of Figure 11 embodiments shown.Figure 13 is a synoptic diagram, its with the sizing specification of amplifying the B part among Figure 12.Figure 12 has illustrated first glass substrate 112 and second glass substrate 114.Described second glass substrate has pixel electrode 122.With reference to Figure 13, the first orientation area 124V and the second orientation area 124H on each pixel electrode 122, have been formed.In other words, a plurality of slim-lined constructions 132 on each pixel electrode 122, have been formed.The first orientation area 124V has played the effect that makes liquid crystal molecule almost vertical orientated with substrate surface, and the second orientation area 124H has played the effect that makes liquid crystal molecule almost parallel-oriented with substrate surface.
Figure 14 is a sheet of planar figure, and it has illustrated the example of a change of second glass substrate 114.In Figure 14, second glass substrate 114 has comprised pixel electrode 122, gate bus line (gatebus lines) 126, data bus line 128 and TFTs 130.Alignment films 124 comprises the first orientation area 124V and the second orientation area 124H.The first orientation area 124V and the second orientation area 124H form with the form of vertical bar line, and alternately arrangement parallel to each other.The first orientation area 124V and the second orientation area 124H are to form near 45 angles of spending with respect to gate bus line 126 and data bus line 128.The width of pixel electrode 122 is about 50 μ m, and the width of the first orientation area 124V and the second orientation area 124H is about 6 to 7 μ m.Arrow R represent the to rub direction of the alignment films 120 on first glass substrate 112.The first orientation area 124V and the second orientation area 124H are forming near on the rectangular direction with frictional direction R.
Then, described below is the method and the ruuning situation thereof of producing the liquid crystal indicator 110 among Figure 11.The Resist S1808 that adopts Shipley company to produce, forming width on the pixel electrode 122 of the ITO on second glass substrate 114 is the structure 132 of 5 μ m, and keeps identical with it gap width.Herein, the height of described structure 132 is 0.7 μ m.To comprise on second glass substrate 114 of structure 132 by the JALS-2004 type vertical alignment layer coated materials that JSR company produces, and forming one deck alignment films 124 thus.
The AL-3046 type horizontal alignment film coated materials that JSR company is produced is on first glass substrate 112, to form one deck alignment films 120.Described alignment films 120 is carried out friction treatment on the direction of being represented by arrow R.In this case, the structure 132 that forms on selected frictional direction and the opposing substrates 114 vertical becomes 85 degree.Two glass substrates 112 and 114 are bonded together, and positive liquid crystal (positive dielectric anisotropy) is injected wherein, make a liquid crystal cells.
Prepare four kinds of liquid crystal cells samples, it has identical structure and only changes the width of contained structure 132.The width of described structure 132 is respectively 5 μ m, 7.5 μ m, 10 μ m and 12.5 μ m.The width in the gap between two structures 132 is identical with the width of described structure 132.
Observation to the orientation of these liquid crystal cells discloses, and in comprising the liquid crystal indicator 110 of structure 132 that width is 5 μ m and 7.5 μ m, its lining, zone (the second orientation area 124H) that forms structure 132 has formed the orientation of twisted nematic (TN) pattern.On the other hand, then formed the orientation of hydridization (HAN) pattern in lining, the gap of these structures 132 (the first orientation area 124V).
110 of liquid crystal indicators that comprise width and be the structure 132 of 10 μ m and 12.5 μ m have a kind of orientation texture of alternately arranging, be horizontal alignment promptly, then be the hydridization orientation in lining, the gap of these structures 132 (the first orientation area 124V) in the lining, zone (the second orientation area 124H) that forms structure 132.
To comprising the liquid crystal indicator 110 that width is the structure 132 of 5 μ m, adopt and survey its tilt angle based on the tilt angle measurement mechanism of crystal spinning solution, found that its tilt angle is about 10 degree.Further, the tilt angle that comprises horizontal alignment zone in the liquid crystal indicator 110 of structure 132 that width is 12.5 μ m is measured, be found that its tilt angle is about 2 degree.
Then, described below is example at a change of liquid crystal indicator among Figure 11 110.Liquid crystal indicator 110 has identical composition among the liquid crystal indicator 110 of manufacturing and Figure 11.In the example of this change, vertical orientated membrane material has the identical molecular structure of producing with JSR company of the vertical orientated membrane material of JALS-2004 type, but the amount of vertical orientated component has wherein reduced to the lower limit of vertical assembling liquid crystal.Observation to the orientation of the liquid crystal cells of manufacturing like this discloses, in comprising the liquid crystal indicator 110 of structure 132 that width is 5 μ m, 7.5 μ m and 10 μ m, its lining, zone (the second orientation area 124H) that forms structure 132 has formed the orientation of twisted nematic (TN) pattern.On the other hand, then formed the orientation of hydridization (HAN) pattern in lining, the gap of these structures 132 (the first orientation area 124V).
110 of liquid crystal indicators that comprise width and be the structure 132 of 12.5 μ m have a kind of orientation texture of alternately arranging, be horizontal alignment promptly, then be the hydridization orientation in lining, the gap of these structures 132 (the first orientation area 124V) in the lining, zone (the second orientation area 124H) that forms structure 132.
Described below is the example that further changes at of liquid crystal indicator among Figure 11 110.Liquid crystal indicator 110 has identical composition among the liquid crystal indicator 110 of manufacturing and Figure 11.Yet, in the example of this change, after structure 132 forms,, second glass substrate 114 has been carried out the plasma ashing processing in order to change the surface tension of described structure 132.Then, on described substrate, apply vertical orientated membrane material.
Figure 15 A and 15B are one group of synoptic diagram, and it has illustrated before the ashing and the structure 132 after the ashing.Figure 15 A explanation be structure 132 before the ashing, Figure 15 B explanation be structure 132 after the ashing.Structure 132 after the ashing has hard surface, the surface tension of the structure 132 of its surface tension that shows before greater than ashing.The surface tension of the structure 132 before the ashing is 42mN/m, and its saturated back is 65mN/m.Observation to the orientation of the liquid crystal cells that obtains thus discloses, and when its surface tension is not more than 50mN/m, forms the orientation of twisted nematic (TN) pattern, and when its surface tension is not less than 50mN/m, forms hydridization and be orientated.
Figure 16 is a sectional view, and it illustrates second glass substrate 114 of the liquid crystal indicator that the 3rd embodiment according to the present invention forms.In the present embodiment, adopt ultraviolet selecting ground irradiation alignment films 124, and need not form structure 132.In order to form alignment films 124, can be on the pixel electrode 122 on second glass substrate 114 with the JALS-2004 type vertical alignment layer coated materials of producing by JSR company.Place a mask 134 on described alignment films 124, in order to form slit pattern, described slit width is 5 μ m, 7.5 μ m, 10 μ m and 12.5 μ m, shines with ultraviolet ray subsequently.In the ultraviolet radiation zone territory, the excision alkyl also weakens vertical orientated structure.The AL-3046 horizontal alignment film coated materials that to produce by JSR company on first glass substrate 112, thereby form alignment films 120, described alignment films 120 then rubs.Selected frictional direction becomes 85 degree with the slit pattern direction of mask 134.Two glass substrates 112 and 114 are bonded together, and inject positive liquid crystal (positive dielectric anisotropy) therein and make liquid crystal cells.
Observation to the orientation of described liquid crystal cells discloses, and as the embodiment of Figure 11, has wherein formed the orientation of twisted nematic (TN) pattern.
Figure 17 is a sectional view, and it illustrates the liquid crystal indicator that forms according to the 4th embodiment of the present invention.In the present embodiment,, structure 132 is arranged between pixel electrode 122 and the alignment films 124 as the embodiment of Figure 11.Further, structure 136 is arranged between the pixel electrode 118 and alignment films 120 on first glass substrate 112.Formed structure 136 is identical with the pattern of structure 132, and meets at right angles with structure 132 or become 85 degree angles.In this case, first glass substrate is not made friction treatment.
In the process of making described liquid crystal indicator, adopt the ResistS1818 of Shipley company on the electrode 118 and 122 on first and second glass substrates 112 and 114, to form the structure 132 and 136 that width is 5 μ m respectively, keep identical with it gap simultaneously, the generation type of described structure is under the vertically rectangular each other situation of both patterns, and its graphics is lumped together.Herein, structure 132 and 136 height are 0.7 μ m.The vertical orientated membrane material of JALS-2004 type that coating is produced by JSR company is so that covered structure 132 and 136, thereby forms alignment films 120 and 124.Two glass substrates 112 and 114 are bonded together, and injection has the positive liquid crystal of chirality therein, thereby make liquid crystal cells.
Figure 18 is a sectional view, and it illustrates the ruuning situation of the liquid crystal indicator 110 among Figure 17.Observation to the orientation of described liquid crystal cells discloses, and the lining, zone (the second orientation area 124H) that forms structure (132,136) has formed the orientation of twisted nematic (TN) pattern.On the other hand, then formed vertical orientated in lining, the gap of these structures 132 and 136 (the first orientation area 124V).
Figure 19 is a sectional view, and it illustrates the liquid crystal indicator that forms according to the 5th embodiment of the present invention.In Figure 19, embodiment as Figure 17, adopt the Resist S1818 of Shipley company on first and second glass substrates 112 and 114, to form the structure 132 and 136 that width is 5 μ m respectively, keep identical with it gap simultaneously, the generation type of described structure for both pattern vertically each other in 85 degree.Structure 132 and 136 height are 0.7 μ m.In the present embodiment, do not apply alignment films 120 and 124, but first and second glass substrates 112 and 114 directly are bonded together.Then, in bonding thus unit, inject the liquid crystal that added the compound that contains alkyl, shine with ultraviolet ray subsequently.The described compound that adds liquid crystal comprises following acrylate monomer A and B, and its ratio is 15: 1.
Monomer A:
CH
2:COO(CH
2)
17CH
3
Monomers B:
CH
2:CHCOO(CH
2)
9OCOH:CH
2
Vertical orientated component in the described compound is that first and second glass substrates 112 and 114 are adsorbed, thereby forms orientation key-course 138 and 140.Adopt a kind of compound with straight chained alkyl structure as the unit of forming orientation key-course 138 and 140, and be used to make liquid crystal molecule that the straight chained alkyl structure that the second orientation area 124H near horizontal alignment had takes place to take place to come densely near the first vertical orientated orientation area 124V not as being used to make liquid crystal molecule.
As mentioned above, the liquid crystal of described interpolation being crossed the compound with straight chained alkyl injects between first and second glass substrates 112 and 114, so that described compound can be adsorbed for first and second glass substrates 112 and 114.The compound layer of absorption can be used as orientation key-course 138 and 140, and its vertical orientated effect that demonstrates makes might save the step that is used to apply and form alignment films 120 and 124.In this case, from the foothold of stability, preferred described compound with straight chained alkyl comprises a photoreactive groups.After injection comprised the liquid crystal of described compound with straight chained alkyl, described compound optionally was or the first orientation area 124V or the second orientation area 124H adsorbed (or adsorbed for arbitrary limit in these zones with bigger amount).In this case, described structure 132 also can form different polarity zones with 136 on substrate 112 and 114, maybe can adopt ultraviolet ray that it is optionally shone to change its polarity.In structure 132 and 136, the zone of adsorbing a small amount of described compound is defined as the second orientation area 124H.When having adopted the compound with photoreactive groups, the polarity of injecting behind the liquid crystal and using ultraviolet postradiation substrate is just depended in the formation of the first orientation area 124V and the second orientation area 124H.
Observation to the orientation of the liquid crystal cells of acquisition like this discloses, and has formed the orientation of twisted nematic (TN) pattern in the lining, zone (in the second orientation area 124H) of ultraviolet ray irradiation.On the other hand, the lining, gap (the first orientation area 124V) between the zone of these ultraviolet ray irradiations has then formed vertical orientated (VA).
From as can be known above-mentioned, according to the present invention, do not carrying out under the situation of friction treatment, can on having the substrate of active matrix, at least one obtain big tilt angle.This has just realized having the liquid crystal indicator of fabulous response speed.This makes might provide a kind of high-quality liquid crystal indicator that has in the yield rate and turnout that improve production run.Further, this also makes and might (be meant certainly and remove the friction system) that employing has the compound of alkyl and particularly a kind of material with acrylate group obtains bigger tilt angle under the situation that need not apply and form alignment films.
First and second aspects just as described above, formed according to a third aspect of the invention we liquid crystal indicator can have basically and the identical structure of normally used all kinds liquid crystal indicator.Yet the liquid crystal indicator of the third aspect is characterised in that described device does not comprise alignment films or oriented layer, the substitute is a kind of irradiation of using up and the curing resin layer that forms after liquid crystal injects.For example, if according to display mode classification, liquid crystal indicator of the present invention can be any in emission type, reflection-type or the porjection type.For example, the liquid crystal indicator of emission type can pass through the modulation to the intensity backlight of display panels back, display image on described display panels.
Figure 20 is a sectional view, and it has illustrated the main composition of a kind of panchromatic TFT (thin film transistor (TFT)) liquid crystal indicator, and described device is according to emission type liquid crystal indicator of the present invention.Described liquid crystal indicator has comprised that (CF, colorfilter) substrate is deposited in a kind of display panels that makes together by a TFT substrate and a colorized optical filtering.
On a transparent glass substrate 11 forming the TFT substrate, formed a plurality of pixel electrodes 15 by an insulation course 14, and formed the described pixel electrode 15 of resin bed 16 coverings of appointment of the present invention.Available liquid crystal impregnating resin layer 16.Insulation course 14 for example can adopt material such as silicon dioxide film to form, and pixel electrode 15 for example can adopt material such as ITO (indium-tin-oxide) film to form.
To be stacked in successively on another piece transparent glass substrate 12 according to color filter 18 of the present invention, common electrode 19 and resin bed 17, thereby form the CF substrate.Resin bed 17 can flood with liquid crystal.For instance, color filter 18 can be by a kind of coloured material of printing dyestuff and forming for example.In addition, common electrode 19 can be formed by for example ITO film.
Though not explanation herein, but still need a kind of isolated material is inserted between the substrate, so that keep a gap between the substrate consistently and keep a uniform space to be used to inject liquid crystal.In addition, also need provide a kind of encapsulant, be in sealing state and can not leak to keep flowing into liquid crystal between the substrate at the external margin of substrate.
In the liquid crystal indicator of Figure 20, resin bed 16 (17) is inserted between liquid crystal layer 13 and the transparency carrier 11, described transparency carrier 11 is that a liquid crystal panel is formed element.Yet in liquid crystal indicator of the present invention, liquid crystal panel is formed element and is not limited in substrate.In other words, except that substrate, liquid crystal panel is formed element and comprise the seal that is used for encapsulated liquid crystals, the isolated material that is used to keep the gap between substrate, the electrode that forms or other element on substrate.Resin bed can be inserted interface between the element in liquid crystal and these elements and maybe can be inserted into interface between two or more elements in liquid crystal and these elements.In the present invention importantly, the mode of action of wherein included resin bed is consistent with conventional alignment films.In addition, this effect can show at an easy rate and need not to introduce complicated technology, for example required friction treatment or the optical orientation of alignment films.For the purpose of the present invention, no longer need the alignment films always used so far.Specifically, because the present invention does not need to form alignment films by printing process and additive method, thereby obtained many advantages, for example it makes and might form thin resin bed, prevents that organic solvent is blended in the resin bed and prevents to form such as patterns such as sieve shapes etc. in printing process.Below will specifically describe it.
After liquid crystal is injected the intermediate product of liquid crystal indicator, described resin bed can form in the process that a kind of curable adjuvant solidifies, described curable additives has comprised the combination of a kind of simple function group monomer and a kind of polyfunctional monomer, described resin bed also has such feature, be that described resin bed has a kind of sieve shape or reticulate texture, the formation of described resin bed has covered the surface of liquid crystal element, and the functional group that forms the vertical orientated expression in the molecule of curable additives is derived from the surface of resin bed and approximate with the contact angle surface tilt of substrate relatively for example.Herein, described " curable adjuvant " refers to, and anyly can be used as adjuvant and the compound that solidifies takes place applying under the situation of any energy, for example the monomer of photocuring, heat curing or electronic beam curing, oligomer and other compounds.Wherein the compound of photocuring is effective especially.
Illustrate the above-mentioned feature of described resin among Figure 21.That is, the described resin bed 16 (17) with sieve texture forms and covers its surface on substrate 11 (12).The formation of the sieve texture of described resin bed 16 (17) is crosslinked based on the polyfunctional monomer that is used for curable adjuvant mainly.In addition, sieve texture existence also realized its state by the liquid crystal dipping.For simplicity, the resin of described description of drawings directly contacts with substrate.Yet for example insulation course, color filter or electrode insert between substrate and the resin bed a kind of liquid crystal panel can be formed element usually.In addition, vertical orientated expression functional group A is stretched out from the surface of resin bed 16 (17).Vertical orientated expression functional group A is included in the monomer molecule, and described monomer is included in the adjuvant.Preferred vertical orientation is expressed functional group A and is included in the simple function group monomer as described below.In described embodiment, described vertical orientated expression functional group A derives out with the surface tilt of a relative substrate 11 (12) of predetermined angle by approximate.As mentioned above, owing to have the vertical orientated expression functional group A that contacts with liquid crystal layer, thereby liquid crystal indicator of the present invention can move and make liquid crystal molecule 3 generations vertical orientated, and keep as stability illustrated among Figure 22.Described vertical orientated expression functional group A can be derived and obtained by the Surface Vertical of relative substrate 11 (12), perhaps tilts to derive and vertical mode of deriving with mixing coexists.
In enforcement of the present invention, by the decision of forming of additive material, curable additives can experience curing because of being heated, in other words, it can be by various light ultraviolet irradiation or experience curing by the irradiation of electron beam for example, and resin bed can obtain by any method.The conform to the principle of simplicity starting point of single job, a kind of suitable light source that is used to solidify is ultraviolet ray.Therefore, the following description of the present invention is special relevant with the adjuvant of ultraviolet-curing.
Simple function group monomer and polyfunctional monomer as curable additives can be monomers commonly used in the various polymeric chemical.Be applicable to that monomer of the invention process has carboxylic acid, for example (methyl) acrylic acid; Alkene, for example ethene, propylene, vinyl chloride and styrene or the like.In these monomers, from curability and curing controllability, (methyl) acrylic acid is particularly suitable for implementing the present invention.
Although do not limit especially herein, (methyl) acrylic acid simple function group monomer that can be used for enforcement of the present invention is preferably represented with following general formula (I):
R wherein
1Be a hydrogen atom or a low-grade alkyl group, for example methyl or ethyl, and A is a functional group, vertical orientated functional group (indication of the present invention vertical orientated expression functional group) takes place in preferably a kind of liquid crystal molecule that can make when it is used for liquid crystal panel, or comprises a unit (also can be referred to as part) of this functional group.
Described functional group A is preferably with general formula-OR
2Be representative, wherein R
2Be an alkyl, and preferably chain alkyl, alkoxy or halogen atom and preferably fluorine atom.Described chain alkyl is preferably with general formula-C
mH
2m+1Represent that wherein m is an integer, usually from about 8 to about 18, and preferably from about 10 to about 15.Described simple function group monomer can use separately or use together with two or more monomers.
At the light of scheduled volume for example under the ultraviolet irradiation, general formula changes poly-[(methyl) acrylate] by following general formula (II) expression into for (methyl) acrylic acid simple function group monomer of (I):
R wherein
1Identical with A, and 1 be integer with above-mentioned definition, preferably from about 20 to about 200.Described curable adjuvant has a vertical orientated expression functional group A at its chain part, and as Figure 22 is described before, it can make the orientation of liquid crystal molecule generation perpendicular to substrate.
For instance, can comprise following monomer by the simple function group monomer that above-mentioned general formula is represented.
MF-1：
CH
2＝CHCOO-C
12H
25
MF-2：
CH
2＝CHCOO-F
In curable additives, the simple function group monomer in conjunction with above-mentioned has also used a kind of polyfunctional monomer.The purpose that adopts described polyfunctional monomer is for when it solidifies in curable additives, it can form a kind of sieve texture and effectively support curable additives based on simple function group on substrate, and the surface of covered substrate and the surface that other liquid crystal panels are formed elements effectively and effectively.Therefore, described polyfunctional monomer does not need to carry vertical orientated expression functional group in its molecule, but must have two or more functional groups of solidifying of helping, for example acryloyl group or methacryl.As described below, preferred polyfunctional monomer generally includes bifunctional monomer, trifunctional monomer and four-functional group monomer.The same with above-mentioned simple function group, described polyfunctional monomer can use separately or use together in conjunction with two or more monomers.When two or more polyfunctional monomers are mixed use, to monomer whose blending ratio and unrestricted.
Although do not limit especially, can be used for (methyl) of the invention process acrylic acid bifunctional monomer and preferably represent herein with following general formula (III):
R wherein
1And R
2Can be identical or different, can be hydrogen atom or low alkyl group for example methyl or ethyl, and B is the unit (perhaps can be referred to as part or coupling group) of an energy definite skeleton in the curable additives that obtains, and for example one replaces or unsubstituted straight chained alkyl.The bifunctional monomer presents the function that is different from the simple function group monomer that uses together in conjunction with it.Therefore, the unit B of described composition bifunctional monomer molecule does not comprise essential vertical orientated expression functional group for the simple function group monomer.
General formula (III) represented bifunctional monomer preferably represent with following general formula (III-1):
R wherein
1And R
2Can be identical or different, can be hydrogen atom or low alkyl group for example methyl or ethyl, R
1And R
2Can be identical or different, can be for example vinyl, propenyl or butenyl group of light alkene group, R is a kind of straight chain or branched chain aliphatic alkyl, a kind of replacement or unsubstituted aromatic hydrocarbyl or replacement or unsubstituted alicyclic alkyl, and m and n are the integers of independently of one another and from 0 to 4.
Bifunctional monomer by above-mentioned general formula (III-1) representative comprises following monomer:
PF-1
CH
2＝CHCOO-(CH
2)
6-OCOCH＝CH
2
PF-2
CH
2＝CHCOO-(CH
2)
10-OCOCH＝CH
2
Further, the bifunctional monomer of general formula (III) expression also preferably represents with following general formula (III-2):
R wherein
1And R
2Can be identical or different, can be hydrogen atom or low alkyl group for example methyl or ethyl, R
1Be for example vinyl, propenyl or butenyl group of a light alkene group, n is one from 0 to 12 a integer.
For instance, the bifunctional monomer by above-mentioned general formula (III-2) expression comprises following monomer.
PF-11
CH
2＝CHCOO-(C
2H
4O)
2-COCH＝CH
2
PF-12
CH
2＝CHCOO-(C
2H
4O)
8-COCH＝CH
2
PF-13
CH
2＝CHCOO-(C
3H
6O)
3-COCH＝CH
2
Further, by the bifunctional monomer of general formula (III) expression, also preferably represent with following general formula (III-3).
R wherein
1And R
2Can be identical or different, can be hydrogen atom or low alkyl group for example methyl or ethyl, R, R ' and R " can be identical or different; can be straight chain or branched chain aliphatic alkyl, replacement or unsubstituted aromatic hydrocarbyl or replacement or unsubstituted alicyclic alkyl, and m and n are independent of each other 0 or 1.
Bifunctional monomer by above-mentioned general formula (III-3) expression comprises following monomer
Although do not have special in addition restriction herein, can be used for (methyl) of the invention process acrylic acid trifunctional monomer and preferably represent with following general formula (IV):
R wherein
1, R
2And R
3Can be identical or different, can be hydrogen atom or low alkyl group for example methyl or ethyl, R
1, R
2And R
3Can be identical or different, can be for example vinyl, propenyl or butenyl group of light alkene group, R is a kind of straight chain or branched chain aliphatic alkyl, a kind of replacement or unsubstituted aromatic hydrocarbyl or replacement or unsubstituted alicyclic alkyl, and l, m and n are 0 to 3 integers independent of each other.
Trifunctional monomer by above-mentioned general formula (IV) expression comprises following monomer.
Although do not have special in addition restriction herein, can be used for (methyl) of the invention process acrylic acid four-functional group monomer and preferably represent with following general formula (V):
R wherein
1, R
2, R
3And R
4Can be identical or different, can be hydrogen atom or low alkyl group for example methyl or ethyl, R
1, R
2, R
3And R
4Can be identical or different, can be for example vinyl, propenyl or butenyl group of light alkene group, R is a kind of straight chain or branched chain aliphatic alkyl, a kind of replacement or unsubstituted aromatic hydrocarbyl or replacement or unsubstituted alicyclic alkyl, and k, l, m and n are 0 to 2 integers independent of each other.
Four-functional group monomer by above-mentioned general formula (V) expression comprises following monomer.
In being used to form the curable additives of resin bed, simple function group monomer and polyfunctional monomer can be mixed the back use with various ratios, its blending ratio depends on required vertical orientated distribution and the required effect that reaches of expressing functional group.Usually, the mole dosage of the preferred simple function group monomer that uses is approximately equal to or greater than the mole dosage of polyfunctional monomer.When the consumption of simple function group monomer during less than the consumption of polyfunctional monomer, in other words, when the consumption of polyfunctional monomer during greater than the consumption of simple function group monomer, then will no longer may make the functional group of vertical orientated expression obtain required distribution, thereby with inaccessible enough vertical orientated degree.The ratio of described simple function group monomer and the molar weight of polyfunctional monomer preferably about 1: 1 to about 50: 1 scope, under the preferred situation, at about 5: 1 to about 50: 1 scope.
Described resin bed is made up of the cured resin that comes from above curable additives fully, and can comprise any other additional resin by required effect, for example come from the light-cured resin of light thermoset material, the thermoset resin that comes from thermosets or other resins.For instance, preferred a kind of additional resin can be a double pentaerythritol methacrylate (DPHA) etc.When adding so a kind of resin, then can expect to occur such as reinforcing effects such as sieve texture, shortening reaction time.Although there is not in addition special restriction herein, the amount of added additional resin usually should be at about 1 weight % of the total amount that accounts for cured resin to the scope of about 10 weight %.
Further, described resin bed forms by solidifying described curable additives, thereby its thickness is less than the thickness of conventional alignment films, although and its thickness decrease, demonstrate the performance that can be equal to or be better than conventional alignment films with conventional alignment films.In fact, the thickness of alignment films is generally 80nm.On the other hand, the thickness of resin bed of the present invention is generally half of above thickness or is not more than half, that is, its thickness is in about scope of 5 to about 40nm, and preferred in about scope of 10 to about 40nm.
In addition, although for forming conventional alignment films, the use of solvent is essential, and described resin bed now can form under solvent-free condition.Owing to do not use solvent, Here it is make might get rid of problem of environmental pollution, reduce cost and avoid liquid crystal and solvent between unnecessary reaction takes place.
In addition, different with conventional alignment films, described resin bed is not to form by printing on the surface of substrate.In other words, described resin bed can use existing equipment to form by simple method, and need not be through the system film step that causes production stage to increase or equipment scale enlarges.Preferably, apply energy to it again by between substrate, injecting the potpourri of liquid crystal and curable additives, for example ultraviolet and form described resin bed.
When the potpourri with liquid crystal and curable additives injected between the substrate, the ratio of liquid crystal and curable additives can change in the scope of a broad, and its ratio depends on the composition of described liquid crystal and described curable additives.The ratio of described liquid crystal and curable additives usually about 10: 1 to about 400: 1 scope, under the preferred situation, at about 20: 1 to about 200: 1 scope.When the ratio of liquid crystal less than or greater than above scope, then resulting display panels can not give expression to gratifying Presentation Function.
Described below is the liquid crystal layer that is arranged between the substrate respect to one another.Do not have special restriction for the liquid crystal material of forming liquid crystal layer herein, can in many liquid crystal materials well known in the art, select any material that is suitable for drive system and liquid crystal indicator like this most.Particularly, in enforcement of the present invention, use a kind of negative dielectric anisotropic that shows as, and wherein the major axis of liquid crystal molecule will be more favourable not applying liquid crystal material vertical with substrate proximate under the voltage condition.In the present invention, importantly, described liquid crystal layer can be made up of liquid crystal material separately, and need not use the conventional expensive high molecular dispersion type liquid crystal of using.What in other words, the present invention used is the non-dispersive type liquid crystal of high molecular.
Generally speaking, the liquid crystal material that is suitable for forming liquid crystal layer comprises nematic crystal, STN Super TN type liquid crystal, Chinrally nematic liquid crystal (cholesteryl liquid crystal), smectic crystal, discotic liquid crystal and high molecule liquid crystal.If the name with compound states that these liquid crystal materials are ester type, biphenyl type, cyclohexane type, phenyl pyrimidine type and the dioxane types in the compound.
Above liquid crystal material can use separately, but also two or more uses that combine.If desired for the more detailed description of the liquid crystal material that can be used for enforcement of the present invention, then should list of references, for example the spy opens flat JP6-211710 and JP11-116512.
The present invention not only is described liquid crystal indicator with panel construction, described panel construction has comprised a pair of substrate that is arranged relative to each other and has been sealed in liquid crystal between these substrates, in addition, the present invention also is a kind of method of producing above-mentioned liquid crystal indicator.That is, the method according to the described liquid crystal indicator of production of the present invention comprises:
A step of between substrate, injecting the potpourri of liquid crystal and curable additives, described curable additives has comprised a kind of simple function group monomer and a kind of polyfunctional monomer; And
One applies energy to solidify the step of described curable additives from the outside, for example when described adjuvant is a kind of light-cured resin, then use the light source of certain wavelength of scheduled volume, in the time that is enough to make described adjuvant to solidify, it is shone.After curable additives was solidified therefrom, with reference to Figure 21, as mentioned above, the resin bed with sieve texture optionally formed at the interface that liquid crystal and the liquid crystal panel that contacts with liquid crystal are formed between the element.Further, also as shown in figure 21, in described resin bed, vertical orientated the expressions functional group that forms in the molecule of curable additives can be by with a relative substrate surface inclination of predetermined angle and derive out from the surface of resin bed.In addition, as described before, the functional group of vertical orientated expression can also derive out with vertical or other directions from the surface of resin bed.
According to program shown in Figure 23, can obtain favourable enforcement usually according to the method for the described liquid crystal indicator of production of the present invention.That is, by following step, production method of the present invention can obtain favourable enforcement:
(1) cleaning and dry substrate;
(2) printing and sealing material (sealed binder);
(3) use isolated material;
(4) bonding optical filtering (CF) substrate;
(5) potpourri of injection liquid crystal and curable additives;
(6) encapsulated liquid crystals inlet;
(7) apply the energy that is used to solidify; And
(8) stick polaroid.
By sticking after polaroid finishes described display panels, make predetermined circuit and be centered around on the liquid crystal panel to finish described liquid crystal indicator.Herein, the liquid crystal indicator of mentioning among the present invention comprises various plate display device.Although be not limited to following those devices of listing, representational example comprises display device (desktop PC and notebook type PC), LCD TV, auto-navigation system, digital camera, video camera and the portable phone of PC.
In implementation process of the present invention, at first, prepare a pair of substrate.Herein, used substrate preferably clear insulated substrate.The insulated substrate that is suitable for comprises, for example, and glass substrate, silicon substrate and other substrates.If necessary, also can use plastic base.
Usually need clean and drying substrate, in order that remove polluter for example powder, dust and skin oil and fat.Described cleaning step can be, for example use detergent and pure water carry out ultrasonic cleaning and with an organic solvent for example isopropyl alcohol carry out submergence and clean.The enforcement of described drying steps can be undertaken by force drying, for example is blown into compression drying air or gas.
Then, on described substrate, form electrode.The electrode of formation described herein is, for example common electrode and pixel electrode.Also comprise contact electrode and transfer electrode in the kind of described electrode, described contact electrode and transfer electrode are to be used for electric power electrode being linked together, and for example common electrode and pixel electrode are linked together with electric power.Described these electrodes adopt ITO, indium oxide (IO) or tin oxide (NESA usually
TM) form by required pattern, and keep required thickness simultaneously.Described film can adopt sputtering method or evaporation method to form.
Then, as the device of encapsulated liquid crystals after liquid crystal is injected liquid crystal panel, the liquid crystal injecting port on substrate, a seal is printed on the outer edge portion of substrate.Seal used herein has comprised a kind of bonding agent usually, thereby can be referred to as a kind of sealed binder.Described sealed binder has comprised a kind of epoxy resin usually.For described sealed binder is printed onto predetermined zone on the substrate, the preferred herein for example silk screen print method of a kind of printing process of using.After being completed for printing of described sealed binder, using a kind of isolated material between the substrate with the gap between holding unit substrate (for example TFT substrate) and the CF substrate by the method for spraying.Described isolated material can be for example a kind of resin, a kind of glass or silicon dioxide.Described isolated material can have various ways when using, and it typically is bead or spillikin.
Then, fold another, be bonded together one in the substrate; For example, behind cell substrate (for example TFT substrate) and CF substrate calibrating position, fold for one and go up another, adopt the sealed binder that has printed to bond them together.Also preferred combination is implemented the method for heating so that effectively substrate junction is lumped together.Finished the panel construction (so-called " precursor of liquid crystal panel ") that liquid crystal can be injected wherein thus.
Then, the potpourri of liquid crystal and curable additives is injected by liquid crystal injecting port, obtain panel construction thus.Liquid crystal/curable additives used herein (potpourri) has comprised the above-mentioned various materials and the potpourri of various components.In addition, as a kind of method for implanting, can use various devices herein.Specifically, from the starting point of accurate control injection rate IR, preferably adopt drop type injector.Preferably under vacuum, implement to inject operation.
After finishing according to the injection of the liquid crystal/curable additives (potpourri) of aforesaid way, can be with liquid crystal injecting port sealing in the panel construction upper shed.The sealant that is suitable for can be sealed binder or other bonding agents of above-mentioned use, or other binder resins.
Then, shown in Figure 24 A, the liquid crystal/curable additives (potpourri) between the substrate of injection face plate structure is applied the energy that is used for curing additive from the outside.In illustrated embodiment, use photo-curing monomer with the formation resin bed, and adopt luminous energy h υ to shine.As shown, described panel construction has relative two substrates 11 and 12, and the liquid crystal/curable additives (potpourri) 23 that has comprised curable additives 2 and liquid crystal 3 places between the substrate.In stage before applying energy, curable additives 2 is disperseed in a kind of mode at random with liquid crystal 3.
When applying energy, curable additives has experienced curing reaction.At this moment, shown in Figure 24 B, the cured resin in the formation unexpectedly deposits to the surface migration of substrate and on substrate 11 and 12 and becomes resin bed 16 and 17, although also do not know its detailed mechanism.Described resin bed 16 and 17 forms with film effectively are combined on separately the substrate, and have sieve texture.Therefore, gap portion wherein will be flooded by described liquid crystal 3.In addition, described resin bed 16 and 17 has the vertical orientated expression group A that is arranged in its surface.
After resin bed formed as mentioned above, for example polaroid, polarizing coating and polarizing filter sticked to the outside of substrate in the panel construction with polarizer.
In liquid crystal indicator of the present invention, the resin bed that forms by the cure curable adjuvant can present various states within the scope of the present invention.With reference to Figure 21, described resin bed can present aforesaid form of single sheet.Even under the situation of single resin bed, described resin bed also can adopt and be divided into two-layer form composition in fact.Promptly, for instance, shown in Figure 25 A, described resin bed 16 can comprise the ground floor resin " a " of the functional group with vertical orientated expression, it mainly is distributed in the interface zone with respect to liquid crystal layer 13, also comprised the second layer resin " b " with sieve texture, it mainly is distributed in the interface zone with respect to substrate 11 (12).
Further, shown in Figure 25 B, resin bed 16 (or 17) can have the structure of two-layer, wherein comprised by forming with liquid crystal layer 13 contact positions and have first a resin bed 16a (or 17a) that the ground floor resin of vertical orientated expression functional group is formed, and by forming with substrate 11 (or 12) contact position and having second a resin bed 16b (or 17b) that the second layer resin of sieve texture is formed.
Resin bed with two-layer structure will further be described.Such resin bed is preferably formed by two or more curable additives, wherein a kind of curable additives to substrate for example glass substrate show good wetting state, and other curable additives show bad wetting state to substrate.Further, the required curable additives that substrate is shown good wetting state is a kind of polyfunctional group material, and it comprises a resin matrix unit and one and is bonded in the straight chained alkyl group on the skeleton and/or has a kind of horizontal alignment performance.Further, the required curable additives that substrate is shown bad wetting state has a kind of liquid crystal aligning control ability that is used to determine liquid crystal aligning, and under the preferred situation, it has a kind of vertical orientated expression performance.Under the preferred situation, so a kind of curable additives has an alkyl or alkoxy side chain or a fluorin radical as a vertical orientated expression unit.Might obtain a kind of resin bed 16 (or 17) with two-layer structure by using at least two kinds of such curable additives, making, typical two-layer structure is shown in Figure 25 B.
As described before, resin bed must have a surface that contacts with liquid crystal layer, and have another and form the surface that elements contact with one or more liquid crystal panels, described liquid crystal panel is formed element, substrate, be used for encapsulated liquid crystals encapsulant, be used to keep the isolated material of constant clearance between the substrate and the electrode that on substrate, forms.Herein, although be not limited only to described below those, can form at resin bed and liquid crystal panel and keep the liquid crystal panel of excellent contact relation comprise between the element:
(1) a kind of liquid crystal panel, its resin bed that has forms on the entire main surface of substrate respect to one another up and down;
(2) a kind of liquid crystal panel, its resin bed that has forms on the whole inner wall surface of liquid crystal panel;
(3) a kind of liquid crystal panel, its resin bed that has forms on the side of encapsulant, and described encapsulant is used for the gap between the upper and lower base plate of encapsulated liquid crystals display panel;
(4) a kind of liquid crystal panel, its resin bed that has forms on the surface of the isolated material that sprays, and described isolated material is used to keep the constant clearance between the upper and lower base plate of liquid crystal panel; And
(5) a kind of liquid crystal panel, its resin bed that has forms on the electrode surface of liquid crystal panel, for example a kind of liquid crystal panel, its resin bed that has forms in the side that connects flat tip electrode (so-called transfer electrode), and the formation of described connection flat tip electrode is in order to obtain for example common voltage and the electrical connection that realizes the electrode on the cell substrate of opposing substrates.
Figure 26 A and 26B have illustrated a preferred embodiment according to liquid crystal indicator of the present invention, and wherein Figure 26 A is a sheet of planar figure of the encapsulant of liquid crystal indicator, and Figure 26 B is a sectional view of B-B line in Figure 26 A.Should be appreciated that from Figure 26 A in this liquid crystal indicator, encapsulant 31 has the resin bed 36 that one deck is coated in its whole side.Should be appreciated that also that from Figure 26 B resin bed 36 has covered whole inwall fully, this inwall has been determined the liquid crystal layer 13 in the liquid crystal panel,, has covered the surface of substrate 11 and 12, the side of encapsulant 31 and the surface of isolated material 32 fully that is.
Therefore, in illustrated liquid crystal panel, resin bed forms on the whole surface of substrate, and does not represent the separatrix of its existence.With regard to conventional alignment films, it is by printing or apply the material of using the formation alignment films, and the marginal portion of the alignment films of Xing Chenging demonstrates stepped separatrix on substrate thus, thereby has caused and difference of the present invention.Separatrix on the ladder very likely can be caused bad influence to the display characteristic of liquid crystal indicator.Therefore, with regard to liquid crystal indicator of the present invention, it can obtain the orientation of unified appointment in the whole inner wall surface of liquid crystal panel.
Figure 27 is a view of illustrating another preferred embodiment of liquid crystal indicator of the present invention.Described liquid crystal indicator has a flat tip electrode (so-called transfer electrode) 33 that is used to be electrically connected the common electrode 15 on reverse electrode and the cell substrate 11, so that the voltage of the reverse electrode 19 of TFT substrate 12 can serve as a common voltage.The resin bed 36 on covered substrate 11 and 12 whole surface also forms in the side of flat tip electrode 33.The resin bed 36 that is formed at whole surface thus makes the orientation of liquid crystal on the whole inner wall surface that might unify the specified liquid crystal panel, thereby has avoided the undesired orientation that obviously takes place in conventional equipment.This be because, in the liquid crystal indicator that is equipped with alignment films of routine, although be not described, its side in flat tip electrode can't form alignment films, and there is not alignment films at the base portion of flat tip electrode (part that connects substrate) yet, this is the reason that causes undesired orientation, and described undesired orientation has also comprised the marginal portion of the alignment films that printing forms simultaneously.
Further, though described resin bed can be applied to all liquid crystal panels of the present invention, it also may be reduced to less than the thickness of resin bed other regional thickness or may reduce the consumption of resin with respect to other parts on the inside surface of black matrix" or TFT bus.In other words, in these parts, cured resin exist probability less relatively.
Also might do many improvement and modification to liquid crystal indicator of the present invention within the scope of the present invention.For example, in liquid crystal indicator of the present invention, preferably form convex pattern (so-called weir structure) or concavity pattern (so-called narrow slit structure) on substrate, both can use or combine use separately.In order to obtain pixel region can being divided into the zone that two or more have the convex pattern or have the concavity pattern to improve the significant advantage that viewing angle characteristic is representative, form a plurality of zones thus, liquid crystal molecule has different orientations in described zone.
Can be on substrate with the form of ridge, form the weir structure, described ridge has triangle, corrugated or trapezoidal cross-sectional shape or with any other protruding shape.By on substrate, applying for example photoresist of a kind of photosensitive material, adopt photoetching process that described photosensitive material is exposed under the illumination again, implement immediately to develop and printing, then can advantageously generate the weir structure.The size of weir structure can have the variation range of a broad, and it is usually wide to be about 5 to about 20 μ m, and height is about 0.5 to 3 μ m.In the process of the weir structure more than preparation, raised design can duplicate on the resin layer surface on the substrate, and and then the predetermined orientation differentiation of realization.
In above-mentioned weir structure, realize that the orientation process of differentiation is as will be explained hereinafter.In liquid crystal panel of the present invention, the resin that forms on substrate surface might make the relative substrate of the liquid crystal molecule in the liquid crystal layer that is fixed between the substrate vertical orientated.The position of weir structure is provided on substrate, and liquid crystal molecule weir structure relatively is vertical orientated and relative substrate becomes tilted alignment.Described weir structure has the side of inclination in its both sides.Therefore, relatively a side of weir structure becomes the direction of orientation of liquid crystal molecule of the vertical orientation of direction of orientation result and the side one-tenth of an opposite side of relative same weir structure of liquid crystal molecule of vertical orientation opposite.Make thus and might in a pixel region, realize the orientation differentiation.
Described narrow slit structure can form by the groove that forms striated or any other shape on substrate surface.With the weir inverted configuration, it is interior triangle or interior trapezoidal pattern that groove is usually designed to xsect, or is made as its xsect square from design class like the starting point of the electrode pattern of slit.Preferably when being designed on substrate the pattern that forms electrode or form narrow slit structure afterwards.The size of narrow slit structure can have certain variation range, but usually wide be about 5 to 20 μ m, be about 0.02 to 3 μ m deeply.When on substrate, forming so a narrow slit structure, can be on substrate with the described slit pattern of copying surface of the resin bed of liquid crystal dipping, so that realize required orientation differentiation.The mechanism of described differentiation orientation is identical with differentiation orientation mechanism in the above-mentioned weir structure basically, or is caused by the orientation that causes from the formed transverse electric field of electrode that points to slit.
What Figure 28 to 30 illustrated is the preferred embodiment of liquid crystal indicator of the present invention, and it is used to improve the surface of the resin bed that can flood according to the liquid crystal of said method differentiation orientation.
In the liquid crystal panel of Figure 28, slit 26 forms on one side of cell substrate 11.Described slit 26 comes from the striated groove that forms in the pixel electrode on cell substrate 11 15 in advance.Resin bed 16 on the pixel electrode 15 has duplicated groove pattern, and has determined slit 26.Facing to the middle part between two slits 26 on that face of cell substrate 11, it is the leg-of-mutton weir structure 25 that is similar to that xsect is provided at CF substrate 12.Usually provide described weir structure 25 in data bus line and position in parallel corresponding to cell substrate 11.On the common electrode on the CF substrate 12 19, form weir structure 25, and the resin bed 17 of the dipping of the liquid crystal on common electrode duplicates leg-of-mutton protrusion pattern.
In the liquid crystal panel of Figure 29, as the liquid crystal panel of Figure 28, slit 26 forms on one side of cell substrate 11.Described slit 26 comes from the striated groove that forms in the pixel electrode on cell substrate 11 15 in advance.Resin bed 16 on the pixel electrode 15 has duplicated groove pattern, and has determined slit 26.Facing on that face of cell substrate 11, neither provide narrow slit structure that the weir structure is not provided yet at CF substrate 12.That is, on CF substrate 12, form common electrode 19, and on common electrode 19, form resin bed 17.
In the liquid crystal panel of Figure 30, as the liquid crystal panel of Figure 28 and 29, slit 26 forms on one side of cell substrate 11.Described slit 26 comes from the striated groove that forms in the pixel electrode on cell substrate 11 15 in advance.Resin bed 16 on the pixel electrode 15 has duplicated groove pattern, and has determined slit 26.Further face toward and form slit 26 on that face of cell substrate 11 at CF substrate 12.That is, on CF substrate 12, form common electrode 19, and on common electrode 19, form resin bed 17.Described slit 26 is on the cell substrate 11 medium position between two slits 26.
In addition, with regard to a normal liquid crystal panel, CF substrate and cell substrate for example TFT substrate are arranged relative to each other, and allow a color filter is combined with the one side of cell substrate, though color filter is to combine with reverse substrate up to now.
Figure 31 has illustrated an exemplary embodiments of this liquid crystal indicator.Described liquid crystal indicator 10 comprises a pair of insulated substrate respect to one another (transparent glass substrate) 11 and 12,, keep predetermined gap between two substrates, and liquid crystal layer 13 is fixed between these substrates.Thereby color filter 18 and pixel electrode 15 form the TFT substrate shown in forming successively on a transparent glass substrate 11, form resin bed of the present invention in order to cover pixel electrode 15.
With regard to this liquid crystal indicator, need on opposing substrates, not form CF or black matrix" (BM).Therefore, resin bed 17 of the present invention forms on another piece transparent glass substrate 12 on one side of liquid crystal layer 13 simply.So, when the form with illumination applies energy and forms resin bed 16 and 17, the light that passes glass substrate 12 can be guided to the zone between substrate 11 and 12 and is not subjected to any obstruction; That is, resin bed 16 and 17 will form in more effective and uniform mode.Further, when described device is formed thus, then might avoid a kind of phenomenon, promptly be used to the deepening when producing liquid crystal display of the light that shows, thereby obtained a kind of more uniform display effect.
From as can be known above-mentioned, according to the present invention, it can provide a kind of high performance liquid crystal indicator under the situation of not using alignment films, and described alignment films is necessary to the liquid crystal indicator of routine, thereby, it demonstrates many advantages, described advantage originates from film forming step, orientation step (friction, optical orientation etc.) and bakes the omission of step etc., in other words, number and production time that it has reduced production stage significantly, reduced production cost significantly and improved step management method and yield rate.
Further, different with alignment films is that the formation of resin bed of the present invention does not rely on print process or cladding process, and can't form unwanted pattern on its surface thereupon, for example sieve shape pattern (causing), thereby avoided its characteristic is caused harmful effect by used screen cloth.
Further, in liquid crystal indicator of the present invention, its vertical orientated resin bed that comes from, and can under interference-free situation, keep all even stable.
Embodiment
The present invention will be described under the situation of reference example further.Should be noted in the discussion above that the present invention never only limits to these embodiment.Although do not use, for the purpose of simplifying description, the curable additives in following embodiment can be as required with pi and polyamic acid with suitable ratio blend, or they are partly introduced the structure of curable additives.
Embodiment 1
Prepare two glass substrates (trade name " OA-2 ", by Nihon Denki Garasu company produce), use IPA respectively cleaning base plate the surface and make it dry.That adopts that encapsulant (trade name XN-21F is produced by Mitsui Kagaku company) applies a substrate encloses the edge zone, and forms a kind of seal form in its surface.At a kind of preparing spherical SiO 2 isolated material of the surface sprinkling of another piece substrate, its diameter is 4 μ m (being produced by Sekisui Fine Chemical company) and is soaked by ethanol.The substrate that will have encapsulant then is in the same place with the base plate bonding with isolated material, its bonding mode be encapsulant and isolated material in inside, in vacuum, two substrates are compressed, and bake in 130 ℃.Bake and carry out 90 minutes.Obtain a hollow panel thus, it has two glass substrates that are bonded together and a cavity that is used to inject liquid crystal between the two.
With the simple function group monomer that can represent by following molecular formula (trade name " SR-335 " is produced by Nihon Kayaku company):
CH
2＝CHCOO-C
12H
25
With a bifunctional monomer that can represent by following molecular formula, 1,6 hexanediol diacrylate (trade name " HDDA " is produced by Nihon Kayaku company):
CH
2＝CHCOO-(CH
2)
6-OCOCH＝CH
2
Ratio with 15: 1 mixes.The monomer mixture of gained is mixed with consumption that accounts for 2 weight % and the nematic crystal with negative dielectric anisotropic (trade name " MLC2002 " is produced by Merck company).In addition, also a kind of Photoepolymerizationinitiater initiater (trade name " Irgacure184 ", by Ciba Speciality Chemicals company produce) is sneaked into the potpourri of liquid crystal and monomer with the consumption of the 1 weight % that accounts for the monomer total amount.
The potpourri of gained is injected hollow panel by the opening in the encapsulant.Described opening is sealed with epoxy resin immediately.Then, to the liquid crystal panel of the potpourri that comprised the liquid crystal that is sealed in wherein and monomer, adopt ultraviolet ray (wavelength: 300 to the 450nm) irradiation 3 minutes of 10mw.Described ultraviolet irradiation at room temperature carries out.
By observation, confirm to have formed the resin bed (about 40nm) of form of film by the polymerization of above-mentioned two kinds of monomers to liquid crystal layer in the display panels that obtains.By observation, find that further monomer molecule is dispersed in the liquid crystal molecule before the ultraviolet ray irradiation, and independent liquid crystal molecule is approximated to parallel orientation with the surface of substrate to the molecular state of liquid crystal in the liquid crystal layer that obtains.Yet after the ultraviolet ray irradiation, as the result of monomer polymerization, liquid crystal layer solely is made up of liquid crystal molecule, and liquid crystal molecule is approximated to vertical orientation with the surface of substrate.The display panels of Sheng Chaning also demonstrates fabulous drive characteristic and viewing angle characteristic thus, and can show meticulous coloured image satisfactorily.
Embodiment 2
Repeat the method for description among the above embodiment 1.In the present embodiment, simple function group monomer and bifunctional monomer's blending ratio changed 1: 1 into from 15: 1.
Observe liquid crystal layer in the resulting liquid crystal panel in the mode identical, with the formation of the resin bed of determining the interface upper film form (about 40nm) between corresponding substrate and liquid crystal layer with embodiment 1.Can determine that further before the ultraviolet ray irradiation, the single liquid crystal molecule in the liquid crystal layer is approximated to parallel orientation with the surface of substrate.Yet after the ultraviolet ray irradiation, liquid crystal molecule is approximated to vertical orientation with the surface of substrate.In addition, described display panels also demonstrates fabulous drive characteristic and viewing angle characteristic, and can show meticulous coloured image satisfactorily.
Repeat the method for description among the above embodiment 1.In the present embodiment, simple function group monomer and bifunctional monomer's blending ratio changed 50: 1 into from 15: 1.
Observe liquid crystal layer in the resulting liquid crystal panel in the mode identical, with the formation of the resin bed of determining the interface upper film form (about 40nm) between corresponding substrate and liquid crystal layer with embodiment 1.Can determine that further before the ultraviolet ray irradiation, liquid crystal molecule single in the liquid crystal layer is approximated to parallel orientation with the surface of substrate.Yet after the ultraviolet ray irradiation, liquid crystal molecule is approximated to vertical orientation with the surface of substrate.In addition, described display panels also demonstrates fabulous drive characteristic and viewing angle characteristic, and can show meticulous coloured image satisfactorily.
Comparative example 1
Repeat the method for description among the above embodiment 1.In this comparative example, in order to compare, simple function group monomer and bifunctional monomer's blending ratio changed 1: 2 into from 15: 1.
Observe liquid crystal layer in the resulting display panels in the mode identical with embodiment 1, determining the formation of the resin bed on the interface between corresponding substrate and the liquid crystal layer, yet described resin bed is not the sort of film clearly that embodiment 1 forms.Can determine that further before the ultraviolet ray irradiation, independent liquid crystal molecule is approximated to parallel orientation with the surface of substrate.Yet, even after the ultraviolet ray irradiation, described orientation does not still change, liquid crystal molecule is keeping the horizontal alignment state.Because it is vertical orientated that liquid crystal molecule does not take place, even thereby can not show needed image by driving display panels.
Comparative example 2
Repeat the method for description among the above embodiment 1.In this comparative example, in order to compare, simple function group monomer and bifunctional monomer's blending ratio changed 60: 1 into from 15: 1:.
Observe liquid crystal layer in the resulting display panels in the mode identical with embodiment 1, determining the formation of the resin bed on the interface between corresponding substrate and the liquid crystal layer, yet described resin bed is not the sort of film clearly that embodiment 1 forms.Can determine that further before the ultraviolet ray irradiation, independent liquid crystal molecule is approximated to parallel orientation with the surface of substrate.Yet, even after the ultraviolet ray irradiation, described orientation does not still change, liquid crystal molecule is keeping the horizontal alignment state.Because it is vertical orientated that liquid crystal molecule does not take place, even thereby can not show needed image by driving display panels.
Embodiment 4
Repeat the method for description among the above embodiment 1.In the present embodiment, replaced 1,6 hexanediol diacrylate with a kind of bifunctional monomer (trade name " KAYARAD R-684 " is produced by Nihon Kayaku company), its available following molecular formula is represented:
Simple function group monomer and bifunctional monomer's blending ratio still is 15: 1.
Observe liquid crystal layer in the resulting display panels in the mode identical, with the formation of the resin bed of determining the interface upper film form (about 40nm) between corresponding substrate and liquid crystal layer with embodiment 1.Can determine that further before the ultraviolet ray irradiation, liquid crystal molecule single in the liquid crystal layer is approximated to parallel orientation with the surface of substrate, but after the ultraviolet ray irradiation, liquid crystal molecule is approximated to vertical orientation with the surface of substrate.In addition, described display panels also demonstrates fabulous drive characteristic and viewing angle characteristic, and can show meticulous coloured image satisfactorily.
Embodiment 5
Repeat the method for description among the above embodiment 1.In the present embodiment, replaced 1,6 hexanediol diacrylate with a kind of bifunctional monomer (trade name " KAYARAD R-268 " is produced by Nihon Kayaku company), its available following molecular formula is represented:
CH
2＝CHCOO-(C
2H
4O)
4-COCH＝CH
2
Simple function group monomer and bifunctional monomer's blending ratio still is 15: 1.
Observe liquid crystal layer in the resulting display panels in the mode identical, with the formation of the resin bed of determining the interface upper film form (about 40nm) between corresponding substrate and liquid crystal layer with embodiment 1.Can determine that further before the ultraviolet ray irradiation, liquid crystal molecule single in the liquid crystal layer is approximated to parallel orientation with the surface of substrate, but after the ultraviolet ray irradiation, liquid crystal molecule is approximated to vertical orientation with the surface of substrate.In addition, described display panels also demonstrates fabulous drive characteristic and viewing angle characteristic, and can show meticulous coloured image satisfactorily.
Embodiment 6
Repeat the method for description among the above embodiment 1.In the present embodiment, replaced 1,6 hexanediol diacrylate with a kind of bifunctional monomer (trade name " KAYARAD R-526 " is produced by Nihon Kayaku company), its available following molecular formula is represented:
Simple function group monomer and bifunctional monomer's blending ratio still is 15: 1.
Observe liquid crystal layer in the resulting display panels in the mode identical, with the formation of the resin bed of determining the interface upper film form (about 40nm) between corresponding substrate and liquid crystal layer with embodiment 1.Can determine that further before the ultraviolet ray irradiation, liquid crystal molecule single in the liquid crystal layer is approximated to parallel orientation with the surface of substrate, but after the ultraviolet ray irradiation, liquid crystal molecule is approximated to vertical orientation with the surface of substrate.In addition, described display panels also demonstrates fabulous drive characteristic and viewing angle characteristic, and can show meticulous coloured image satisfactorily.
Embodiment 7
Repeat the method for description among the above embodiment 1.In the present embodiment, with a kind of trifunctional monomer (trade name " KAYARAD SR-502 ", produce by Nihon Kayaku company) replaced bifunctional monomer's (1,6 hexanediol diacrylate), its available following molecular formula is represented with as a kind of polyfunctional monomer:
The blending ratio of simple function group monomer and trifunctional monomer still is 15: 1.
Observe liquid crystal layer in the resulting display panels in the mode identical, with the formation of the resin bed of determining the interface upper film form (about 40nm) between corresponding substrate and liquid crystal layer with embodiment 1.Can determine that further before the ultraviolet ray irradiation, liquid crystal molecule single in the liquid crystal layer is approximated to parallel orientation with the surface of substrate, but after the ultraviolet ray irradiation, liquid crystal molecule is approximated to vertical orientation with the surface of substrate.In addition, described display panels also demonstrates fabulous drive characteristic and viewing angle characteristic, and can show meticulous coloured image satisfactorily.
Embodiment 8
Repeat the method for description among the above embodiment 1.In the present embodiment, with a kind of four-functional group monomer (trade name " KAYARAD SR-295 ", produce by Nihon Kayaku company) replaced bifunctional monomer's (1,6 hexanediol diacrylate), its available following molecular formula is represented with as a kind of polyfunctional monomer:
The blending ratio of simple function group monomer and four-functional group monomer still is 15: 1.
Observe liquid crystal layer in the resulting display panels in the mode identical, with the formation of the resin bed of determining the interface upper film form (about 40nm) between corresponding substrate and liquid crystal layer with embodiment 1.Can determine that further before the ultraviolet ray irradiation, liquid crystal molecule single in the liquid crystal layer is approximated to parallel orientation with the surface of substrate, but after the ultraviolet ray irradiation, liquid crystal molecule is approximated to vertical orientation with the surface of substrate.In addition, described display panels also demonstrates fabulous drive characteristic and viewing angle characteristic, and can show meticulous coloured image satisfactorily.
Embodiment 9
Repeat the method for description among the above embodiment 1.In the present embodiment, replace and use bifunctional monomer (1 separately, the 6-hexanediyl ester) as a kind of method of polyfunctional monomer, adopt trifunctional monomer (trade name " KAYARAD the SR-502 ") potpourri described in above-mentioned bifunctional monomer and the embodiment 7, its blending ratio is 1: 1.The blending ratio of described simple function group monomer and polyfunctional monomer (being the potpourri of described bifunctional monomer and trifunctional monomer) still remained 15: 1.
Observe liquid crystal layer in the resulting display panels in the mode identical, with the formation of the resin bed of determining the interface upper film form (about 40nm) between corresponding substrate and liquid crystal layer with embodiment 1.Can determine that further before the ultraviolet ray irradiation, liquid crystal molecule single in the liquid crystal layer is approximated to parallel orientation with the surface of substrate, but after the ultraviolet ray irradiation, liquid crystal molecule is approximated to vertical orientation with the surface of substrate.In addition, described display panels also demonstrates fabulous drive characteristic and viewing angle characteristic, and can show meticulous coloured image satisfactorily.
In the present embodiment, according to above embodiment 1 described method production such as Figure 26 A and the illustrated display panels of 26B.
Prepare a glass substrate 11, enclose the edge zone to form a kind of seal form 31 with what encapsulant (trade name XN-21F, by Mitsui Kagaku company produce) was coated on one surface with one deck ITO electrode 15.Have the isolated material that sprays a kind of preparing spherical SiO 2 on the surface of glass substrate 12 of ITO electrode 19 at another piece, its diameter is 4 μ m (being produced by Sekisui FineChemical company) and is soaked by ethanol.The substrate 12 that will have the substrate 11 of encapsulant then and have an isolated material is bonded together, its bonding mode be encapsulant and isolated material in inside, in vacuum, two substrates are compressed, and bake in 130 ℃.Bake and carry out 90 minutes.Obtain a hollow panel thus, it has two glass substrates that are bonded together 11 and 12 cavitys that are used to inject liquid crystal that reach between the two.
A simple function group monomer (SR-335) and a bifunctional monomer (HDDA) are mixed with 15: 1 ratio.The monomer mixture of gained is mixed with consumption that accounts for 3 weight % and the nematic crystal with negative dielectric anisotropic (MLC2002).In addition, also a kind of Photoepolymerizationinitiater initiater (Irgacure 184) is sneaked into the potpourri of liquid crystal and monomer with the consumption of the 1 weight % that accounts for the monomer total amount.
The potpourri of gained is injected hollow panel by the opening in the encapsulant.Described opening is sealed with epoxy resin.Then, to the liquid crystal panel of the potpourri that comprised the liquid crystal that is sealed in wherein and monomer, adopt ultraviolet ray (wavelength: 300 to the 450nm) irradiation 3 minutes of 10mw.Described ultraviolet irradiation at room temperature carries out.
By observation to liquid crystal layer 13 in the display panels that obtains, the resin bed 36 (about 30nm) that confirms form of film is shown in Figure 26 B, by the polymerization of above-mentioned two kinds of monomers, be formed at the interface of interface between interface, encapsulant 31 and the liquid crystal layer 13 between corresponding substrate 11 (12) and the liquid crystal layer 13 and isolated material 32 and liquid crystal layer 13.
As mentioned above, might form resin bed 36, directly contact with liquid crystal layer, thereby might play stabilization near the orientation of the liquid crystal molecule of encapsulant 31 with regard to the side of described encapsulant 31 in the side of encapsulant 31.Therefore the gap between encapsulant 31 and the display pixel (not illustrating among the figure) might be reduced to less than 0.5mm.Except the side of encapsulant 31, also might form resin bed 36, thereby also make and to control the orientation of the liquid crystal molecule on isolated material 32 surfaces in the side of isolated material 32.
In addition, although these elements are applied to other display panels of the present invention equally, but in the display panels of present embodiment, still can obtain many attractive advantages, its advantage comes from has saved the step that forms alignment films (for example alignment film of polyimide) by print process (for example photo-offset printing or letterpress), and the conventional just display panels of described step is necessary.
At first, be not accompanied by the pattern that prints and bring owing to do not use printing process, the surface of resin bed no longer to have, for example the orientation to liquid crystal has dysgenic sieve shape.
Further, owing to do not use printing process, then no longer produce the end of the printed patterns that is positioned at substrate surface or the step of boundary.Thus, the undesired orientation that can avoid the formation owing to step to cause, and liquid crystal molecule will obtain gratifying orientation in whole screen scope.
Further, owing to do not use printing process, then no longer need those heavy operation stepss, as aligning film material is dissolved in the organic solvent, the viscosity of adjusting resulting solution is very difficult.In addition, from protection environment and the starting point of avoiding being retained in the defective that causes the resin bed, with an organic solvent not more favourable because of organic solvent.
In addition, use conventional printing process to be difficult to dwindle the thickness of alignment films technically.In contrast, according to the present invention, because it has used a kind of method of innovation, described method is to make the monomer in the liquid crystal layer form resin bed to the migration of substrate one side and by polymerization, thereby it makes and might form the very little resin bed of thickness that is kept.Specifically, the invention enables easily to form the film that homogeneous thickness is not more than 40nm, under the preferred situation, its thickness is not more than 30nm, and this is to use conventional printing process institute irrealizable.Because formed resin bed can keep so little thickness, thereby make and to apply highly reinforcing voltage to liquid crystal layer, thereby can drive described display panels with lower threshold voltage.Specifically, the threshold voltage that is used to change liquid crystal aligning can reduce about 0.5V.
In the present embodiment, according to above embodiment 1 and 10 described method productions such as the illustrated display panels of Figure 27.In this liquid crystal panel, also encapsulant and isolated material are arranged in preposition according to above embodiment 10 described methods, but, do not express in the drawings for for the purpose of simplifying narration.
Prepare a glass substrate (TFT substrate) 11, enclose the edge zone to form a kind of seal form 31 with what encapsulant (trade name XN-21F, by Mitsui Kagaku company produce) was coated on one surface with one deck ITO electrode (common electrode) 15.Have at another piece on the surface of glass substrate (CF substrate) 12 of ITO electrode (reverse electrode) 19 and spray a kind of preparing spherical SiO 2, its diameter is 4 μ m (being produced by Sekisui Fine Chemical company) and is soaked by ethanol.Further, be used to be electrically connected reverse electrode 19 on common electrode 15 and the CF substrate 12 forming transfer electrode 33 on the precalculated position of TFT substrate 11, and therefore apply a predetermined voltage to reverse electrode 19.Described transfer electrode 33 is by the silver paste of deposition one deck predetermined thickness, makes pattern immediately and obtains.
Then, the CF substrate 12 that will have the substrate 11 of encapsulant and transfer electrode and have an isolated material is bonded together, its bonding mode be encapsulant and isolated material in inside, in vacuum, two substrates are compressed, and bake in 130 ℃.Bake and carry out 90 minutes.Obtain a hollow panel thus, it has two substrates that are bonded together 11 and 12 cavitys that are used to inject liquid crystal that reach between the two.
A simple function group monomer (SR-335) and a bifunctional monomer (HDDA) are mixed with 15: 1 ratio.The monomer mixture of gained is mixed with consumption that accounts for 3 weight % and the nematic crystal with negative dielectric anisotropic (MLC2002).In addition, also a kind of Photoepolymerizationinitiater initiater (Irgacure 184) is sneaked into the potpourri of liquid crystal and monomer with the consumption of the 1 weight % that accounts for the monomer total amount.
The potpourri of gained is injected hollow panel by the opening in the encapsulant.Described opening is sealed with epoxy resin.Then, to the liquid crystal panel of the potpourri that comprised the liquid crystal that is sealed in wherein and monomer, adopt ultraviolet ray (wavelength: 300 to the 450nm) irradiation 3 minutes of 10mw.Described ultraviolet irradiation at room temperature carries out.
By observation to liquid crystal layer 13 in the display panels that obtains, the resin bed 36 (about 30nm) of confirmation form of film as shown in figure 27, by the polymerization of above-mentioned two kinds of monomers, be formed at interface between corresponding substrate 11 (12) and the liquid crystal layer 13 and the interface between transfer electrode 33 and the liquid crystal layer 13.In addition, although not explanation has confirmed also to have formed the similar film resin layer with uniform thickness on the interface of the interface of encapsulant and liquid crystal layer and isolated material and liquid crystal layer.
As mentioned above, might form resin bed 36 in the bottom and the side of transfer electrode 33, bottom with regard to described transfer electrode 33 directly contacts with liquid crystal layer with the side, thereby might play stabilization near the orientation of the liquid crystal molecule the transfer electrode 33.Conventional method needs a heavy operation, is promptly forming alignment films on the substrate, optionally removes wherein a part of and form transfer electrode on exposed electrodes.Yet, in the present embodiment, do not need this step, thereby it helps to simplify production stage and lowers production cost very much.In addition, when optionally removing alignment films according to conventional methods, will produce bad orientation inevitably.Yet present embodiment has but been got rid of the generation of above-mentioned bad orientation problem.
Except above advantage, present embodiment also provides resulting advantage among the above embodiment 10, in other words, promptly form the advantage that resin bed brings by the interface between the interface between encapsulant and the liquid crystal layer and isolated material and liquid crystal layer, and by the advantage of not using printing process and being brought.
In addition, the display panels of described present embodiment also demonstrates fabulous drive characteristic and viewing angle characteristic, and can show meticulous coloured image satisfactorily.
In these embodiments, according to above embodiment 1 and 10 described method productions such as the illustrated display panels of Figure 28 to 30 with weir structure and/or narrow slit structure.In these liquid crystal panels, also encapsulant and isolated material are arranged in preposition according to above embodiment 10 described methods, obtained confers similar advantages, but in order to simplify narration, not in addition graphic extension.
In addition, although not explanation, in any in these display panels, resin bed can as description before, form with the two-layer structure with reference to figure 25B.The resin bed of described two-layer structure comprises, for example
Resin 1... resin of forming first resin bed, its one side at liquid crystal layer forms, and wherein, for instance, is combined for example a kind of (methyl) acrylate resin with a straight chained alkyl by a branched alkyl; And
Resin 2... resin of forming second resin bed, its one side at substrate forms, and wherein combines a straight chained alkyl or formed a skeleton, for example a kind of (methyl) acrylate resin;
Foregoing had description at preamble.
These mixed with resin obtain resin compound after together.Then, for instance, liquid crystal (for example showing as the nematic crystal of negative dielectric anisotropic) and resin compound mix with 98: 2 ratio (weight ratio), and to wherein adding a kind of polymerization initiator, its consumption accounts for 5 weight % of resin.Herein, being suitable for of described resin 1 and resin 2, obtain vertical orientated blending ratio usually in 1: 1 to 30: 1 scope, and described scope also can upwards expand to 50: 1.
In embodiment shown in Figure 28 12, liquid crystal layer 13 is sealed between TFT substrate 11 with ITO electrode 15 and the CF substrate 12 with ITO electrode 19.Further fold the resin bed 16 that last layer has a narrow slit structure on TFT substrate 11, described narrow slit structure is owing to a step on the ITO electrode 15 produces.Resin bed 16 forms by the polymerization that is dispersed in the monomer in the liquid crystal.On the other hand, ITO electrode 19 and resin bed 17 form on CF substrate 12 successively.Formed a kind of pattern of projection on the surface of resin bed 17, it comes from the weir structure 25 that forms in advance on ITO electrode 19.
In having the display panels of above structure, when being in the state that does not apply voltage, the liquid crystal molecule 3 in the liquid crystal layer 13 is vertical orientated.This is because the resin bed 16 (17) that contacts with liquid crystal layer 13 has participated in the orientation process of liquid crystal.Then, display panels is applied voltage, and the electric field that is applied tilts, liquid crystal molecule 3 will run-off the straight on both direction thus, thereby causes the differentiation that is orientated.Described orientation differentiation helps to improve response speed very much.
In embodiment shown in Figure 29 13, also liquid crystal layer 13 is sealed between TFT substrate 11 with ITO electrode 15 and CF substrate 12 with ITO electrode 19.Further folding the resin bed 16 that ITO electrode 15 and one deck have narrow slit structure 26 on the TFT substrate 11.As mentioned above, resin bed 16 forms by the polymerization that is dispersed in the monomer in the liquid crystal.On the other hand, ITO electrode 19 and resin bed 17 form on CF substrate 12 successively.Yet different with the situation of the display panels (embodiment 12) of Figure 28 is on the surface of resin bed 17, not have to form the pattern of the protrusion that is produced by the weir structure.
Need be briefly described if be used to put on record, when using the potpourri of liquid crystal and the resin that is used to form the resin bed with above-mentioned two-layer structure, described display panels can adopt mode as described below to make so.
Clean described TFT substrate 11 and CF substrate 12, after sealant is coated in the marginal portion of these substrates, bond them together.Then, the potpourri with liquid crystal and resin injects from the position (inlet) that a sealing is broken under vacuum state.After potpourri injects, use a kind of resin of available visible-light curing that inlet is sealed.Then, adopt the whole liquid crystal panel of ultraviolet ray irradiation.Use a kind of high-pressure mercury-vapor lamp as irradiation source.When ultraviolet ray passed glass, described glass can cut off the short part of wavelength in the ultraviolet ray.Therefore, the absorption edge of scalable polymerization initiator makes it and passes glass substrate and the light reaction that enters.Specifically, the absorption edge with polymerization initiator is adjusted to wavelength one side greater than 300nm.Those become horizontal alignment or randomly-oriented liquid crystal molecule immediately after injection is finished, after the ultraviolet ray irradiation, taken place vertical orientated at once on whole surface.
In having the display panels of above structure, when being in the state that does not apply voltage, the liquid crystal molecule 3 in the liquid crystal layer 13 is vertical orientated.This is because the resin bed 16 (17) that contacts with liquid crystal layer 13 has participated in the orientation process of liquid crystal.Then, display panels is applied voltage, and the electric field that is applied tilts, liquid crystal molecule 3 will run-off the straight on both direction thus, thereby causes the differentiation that is orientated.Described orientation differentiation helps to improve response speed very much.
In embodiment shown in Figure 30 14, also liquid crystal layer 13 is sealed between TFT substrate 11 with ITO electrode 15 and CF substrate 12 with ITO electrode 19.Further stacked ITO electrode 15 and one deck have the resin bed 16 of narrow slit structure 26 on TFT substrate 11.As mentioned above, resin bed 16 forms by the polymerization that is dispersed in the monomer in the liquid crystal.On the other hand, ITO electrode 19 and resin bed 17 form on CF substrate 12 successively.In addition, on the surface of resin bed 17, also exist a narrow slit structure 26, it comes from a step on the ITO electrode 19.
In having the display panels of above structure, when being in the state that does not apply voltage, the liquid crystal molecule 3 in the liquid crystal layer 13 is vertical orientated.This is because the resin bed 16 (17) that contacts with liquid crystal layer 13 has participated in the orientation process of liquid crystal.Then, display panels is applied voltage, and the electric field that is applied tilts, liquid crystal molecule 3 will run-off the straight on both direction thus, thereby causes the differentiation that is orientated.Described orientation differentiation helps to improve response speed very much.
Although not explanation herein, what recommend is, the display panels of the present invention that comprises the display panels of present embodiment all can be clipped between a pair of circularly polarizing plate (or circular polarizing coating) and make sandwich structure.This makes might improve brightness widely.Known to the inventor, to compare with the sandwich structure of making by crossed nicols simply, its brightness has strengthened about 40%.
In the present embodiment, according to above embodiment 1 and 10 described method productions such as the illustrated display panels of Figure 31.In this liquid crystal panel, also encapsulant and isolated material are arranged in preposition according to above embodiment 10 described methods, but in order to simplify narration, not in addition graphic extension.About being arranged in the color filter 18 on the TFT substrate 11, described liquid crystal indicator 10 is different from the liquid crystal indicator of the invention described above according to Figure 20.
If be further described, then described liquid crystal indicator 10 is by a pair of glass substrate, i.e. TFT substrate 11 and opposing substrates 12, and the liquid crystal layer 13 that is fixed between these substrates is formed.The liquid crystal of forming liquid crystal layer 13 is a kind of nematic crystal.
As shown in the figure, on TFT substrate 11, made TFT unit is made up of a gate electrode 41 and a source electrode 42.Described TFT unit is general any TFT unit on the TFT substrate so far.On TFT substrate 11, also formed a color filter 18.Further form pixel electrode 15 at described color filter 18.Form the resin bed 16 of appointment of the present invention, so that cover pixel electrode 15.Resin bed 17 according to the present invention is stacked on the opposing substrates 12. Polaroid 21 and 22 is adhered to the outside of TFT substrate 11 and opposing substrates 12.
Present embodiment adopts a kind of composition, had not wherein both had color filter (CF) and also do not have black matrix" (BM) on opposing substrates 12, and described opposing substrates 12 is arranged in the position in the face of TFT substrate 11.Therefore, the whole surface energy of TFT substrate obtains ultraviolet irradiation equably.The ultraviolet ray of irradiation can not decay on CF or BM; In other words, shade can be do not formed, uniform image can be shown.The thickness of the CF on the CF substrate, BM and bus is enough to cut off the ultraviolet ray irradiation.Therefore, in other words, present embodiment has been avoided because of near the bus on the TFT substrate, near the CF and near the inconvenience brought of the cut-out of the ultraviolet ray BM irradiation.
Claims (24)
1. liquid crystal indicator, this device comprises a pair of opposing substrates, the orientation key-course that on described a pair of substrate, forms, be arranged in liquid crystal layer and an electrode that is used for applying electric field between the described a pair of substrate to described liquid crystal layer, wherein said orientation key-course is formed at least one substrate in the described a pair of substrate, and comprise a plurality of first elongated orientation area and a plurality of second elongated orientation area, the described first elongated orientation area is used to make liquid crystal molecule to be orientated by the direction perpendicular to substrate surface almost, the described second elongated orientation area is used to make liquid crystal molecule to be orientated by the direction that almost is parallel to substrate surface, described first orientation area and described second orientation area are alternately arranged, and the part liquid crystal that is positioned at described first orientation area is orientated continuously with the part liquid crystal that is positioned at described second orientation area.
2. approximate orientation uniformly takes place in liquid crystal indicator as claimed in claim 1, the liquid crystal of wherein said liquid crystal layer body part, and satisfies θ
h＜θ
b＜θ
vRelation, wherein said θ
vBe the tilt angle of described liquid crystal molecule in described first orientation area, θ
hBe the tilt angle of described liquid crystal molecule in described second orientation area, and θ
bIt is the pitch angle in the body part of described liquid crystal layer.
3. liquid crystal indicator as claimed in claim 1, the width of wherein said first orientation area and described second orientation area all is not more than 10 μ m.
4. liquid crystal indicator as claimed in claim 1, wherein said orientation key-course comprises one deck vertical alignment layer, and described first orientation area and described second orientation area are by vertical alignment layer is carried out the zone that different disposal obtains.
5. liquid crystal indicator, described liquid crystal indicator has panel construction, this panel construction comprises a pair of substrate that is arranged relative to each other and is sealed in liquid crystal between the described a pair of substrate, wherein, one resin bed is inserted in liquid crystal panel that described liquid crystal and described and described liquid crystal contact forms interface between the element, described resin bed is by curable adjuvant is solidified to form, described curable adjuvant comprises a kind of monomer and a kind of multi-functional monomer of simple function group, and the functional group that is contained in the vertical orientated expression on the monomer in the described curable additives derives out from the surface of described resin bed.
6. liquid crystal indicator as claimed in claim 5, the functional group of wherein said vertical orientated expression is a kind of alkyl or alkoxy and/or halogen atom.
7. as claim 5 or 6 described liquid crystal indicators, wherein said liquid crystal panel form element be selected from by described substrate, be used for sealing described liquid crystal encapsulant, be used to keep the isolated material of constant clearance between the described substrate and at least one element of the group that the electrode that forms is formed on described substrate.
8. as each described liquid crystal indicator of claim 5 to 7, wherein said curable additives comprises described simple function group monomer, and the mole dosage of described simple function group monomer is approximately equal to or greater than the mole dosage of described polyfunctional monomer.
9. as each described liquid crystal indicator of claim 5 to 8, wherein said simple function group monomer and the described polyfunctional monomer molar weight ratio ranges in described curable additives is from 1: 1 to 50: 1.
10. as each described liquid crystal indicator of claim 5 to 9, wherein said simple function group monomer and/or described polyfunctional monomer are (methyl) acrylic acid simple function group monomer, bifunctional monomer, trifunctional monomer or four-functional group monomer.
11. liquid crystal indicator as claimed in claim 10, wherein said (methyl) acrylic acid simple function group monomer is represented with following general formula (I):
R wherein
1Be a hydrogen atom or a low-grade alkyl group; A is one can make when being used for liquid crystal panel liquid crystal molecule that vertical orientated functional group takes place, or comprises a unit of this functional group.
12. as claim 10 or 11 described liquid crystal indicators, wherein said (methyl) acrylic acid the bifunctional monomer represent with following general formula (III):
R wherein
1And R
2Can be identical or different, it is hydrogen atom or low alkyl group; B is an energy is determined skeleton in the curable additives that obtains unit.
13. as each described liquid crystal indicator of claim 10 to 12, wherein said (methyl) acrylic acid the bifunctional monomer represent with following general formula (III-1):
R wherein
1And R
2Can be identical or different, it is hydrogen atom or low alkyl group; R
1And R
2Can be identical or different, it is the light alkene group; R is a kind of straight chain or branched chain aliphatic alkyl, a kind of replacement or unsubstituted aromatic hydrocarbyl or replacement or unsubstituted alicyclic alkyl; M and n are the integers of independently of one another and from 0 to 4.
14. as each described liquid crystal indicator of claim 10 to 12, wherein said (methyl) acrylic acid the bifunctional monomer represent with following general formula (III-2):
R wherein
1And R
2Can be identical or different, it is hydrogen atom or low alkyl group; R
1It is a light alkene group; N is one from 0 to 12 a integer.
15. as each described liquid crystal indicator of claim 10 to 12, wherein said (methyl) acrylic acid the bifunctional monomer represent with following general formula (III-3):
R wherein
1And R
2Can be identical or different, it is hydrogen atom or low alkyl group; R, R ' and R " can be identical or different, it is straight chain or branched chain aliphatic alkyl, replacement or unsubstituted aromatic hydrocarbyl or replacement or unsubstituted alicyclic alkyl; M and n are independent of each other 0 or 1.
16. as each described liquid crystal indicator of claim 10 to 15, wherein said (methyl) acrylic acid trifunctional monomer is represented with following general formula (IV):
R wherein
1, R
2And R
3Can be identical or different, it is hydrogen atom or low alkyl group; R
1, R
2And R
3Can be identical or different, it is the light alkene group; R is a kind of straight chain or branched chain aliphatic alkyl, a kind of replacement or unsubstituted aromatic hydrocarbyl or replacement or unsubstituted alicyclic alkyl; L, m and n are 0 to 3 integers independent of each other.
17. as each described liquid crystal indicator of claim 10 to 16, wherein said (methyl) acrylic acid trifunctional monomer is represented with following general formula (V):
R wherein
1, R
2, R
3And R
4Can be identical or different, it is hydrogen atom or low alkyl group; R
1, R
2, R
3And R
4Can be identical or different, it is the light alkene group; R is a kind of straight chain or branched chain aliphatic alkyl, a kind of replacement or unsubstituted aromatic hydrocarbyl or replacement or unsubstituted alicyclic alkyl; K, l, m and n are 0 to 2 integers independent of each other.
18. as each described liquid crystal indicator of claim 5 to 17, the thickness of wherein said resin bed is within the scope of 5nm to 40nm.
19. as each described liquid crystal indicator of claim 5 to 18, wherein said resin bed is to inject between the described substrate by the potpourri with described liquid crystal and described curable additives, forms with after-applied energy.
20. liquid crystal indicator as claimed in claim 19, the ratio of wherein said liquid crystal and described curable additives is within 10: 1 to 400: 1 scope.
21. as each described liquid crystal indicator of claim 5 to 20, wherein said liquid crystal watch reveals negative dielectric anisotropic, and makes that in the orientation that does not apply described liquid crystal molecule under the voltage condition major axis of described liquid crystal molecule is vertical with described substrate proximate.
22. as each described liquid crystal indicator of claim 5 to 21, wherein said resin bed is divided into two-layer in fact, resin with functional group of vertical orientated expression mainly is distributed in the interface zone with respect to described liquid crystal layer, and the resin bed with sieve texture mainly is distributed in the interface zone with respect to described substrate.
23. as each described liquid crystal indicator of claim 5 to 21, wherein said resin bed is made up of first resin bed and second resin bed, described first resin bed forms and has the functional group of vertical orientated expression by first resin that contacts with described liquid crystal layer, and described second resin bed is formed by second resin with described substrate contacts and have sieve texture.
24., wherein on described substrate, form a kind of weir structure and/or a kind of narrow slit structure as each described a kind of liquid crystal indicator of claim 5 to 23.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP160062/2002 | 2002-05-31 | ||
| JP2002160062A JP4037690B2 (en) | 2002-05-31 | 2002-05-31 | Liquid crystal display device and manufacturing method thereof |
| JP218495/2002 | 2002-07-26 | ||
| JP353879/2002 | 2002-12-05 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031238831A Division CN1272659C (en) | 2002-05-31 | 2003-05-30 | LCD and its mfg. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1900796A true CN1900796A (en) | 2007-01-24 |
| CN100447638C CN100447638C (en) | 2008-12-31 |
Family
ID=30429603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101018188A Expired - Lifetime CN100447638C (en) | 2002-05-31 | 2003-05-30 | Liquid crystal display device and method of producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4037690B2 (en) |
| CN (1) | CN100447638C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105022193A (en) * | 2014-04-29 | 2015-11-04 | 群创光电股份有限公司 | Display panel |
| CN106707636A (en) * | 2017-03-30 | 2017-05-24 | 京东方科技集团股份有限公司 | Display panel, display device and display panel preparation method |
| CN109891314A (en) * | 2016-12-27 | 2019-06-14 | 株式会社Lg化学 | It is used to form the method and liquid crystal color-changing device of the wiring part of liquid crystal color-changing device |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4477421B2 (en) | 2004-05-28 | 2010-06-09 | 富士通株式会社 | Liquid crystal display device and manufacturing method thereof |
| JP2006091547A (en) | 2004-09-24 | 2006-04-06 | Sharp Corp | Liquid crystal panel and liquid crystal display device |
| JP4549819B2 (en) | 2004-11-12 | 2010-09-22 | シャープ株式会社 | Liquid crystal display device and manufacturing method thereof |
| JP5165667B2 (en) * | 2009-11-17 | 2013-03-21 | 友達光電股▲ふん▼有限公司 | Liquid crystal display device and manufacturing method thereof |
| KR101297393B1 (en) * | 2010-02-26 | 2013-08-16 | (주)엔디스 | Liquid crystal display and method of manufacturing the same |
| WO2012046608A1 (en) | 2010-10-07 | 2012-04-12 | シャープ株式会社 | Liquid crystal display device |
| WO2012108317A1 (en) | 2011-02-09 | 2012-08-16 | シャープ株式会社 | Liquid crystal display device and liquid crystal display device manufacturing method |
| WO2012121330A1 (en) | 2011-03-09 | 2012-09-13 | シャープ株式会社 | Liquid crystal display device |
| US9151987B2 (en) | 2011-03-09 | 2015-10-06 | Sharp Kabushiki Kaisha | Liquid crystal display device and production method for liquid crystal display device |
| US10190050B2 (en) | 2016-01-21 | 2019-01-29 | Samsung Display Co., Ltd. | Liquid crystal composition, liquid crystal display device including the same, and method of manufacturing liquid crystal display device |
| US10041001B2 (en) | 2016-01-21 | 2018-08-07 | Samsung Display Co., Ltd. | Liquid crystal composition, liquid crystal display device including the same, and method of manufacturing liquid crystal display device |
| KR20170104079A (en) | 2016-03-04 | 2017-09-14 | 삼성디스플레이 주식회사 | Liquid crystal display and method of manufacturing the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5818560A (en) * | 1994-11-29 | 1998-10-06 | Sanyo Electric Co., Ltd. | Liquid crystal display and method of preparing the same |
| JPH09146096A (en) * | 1995-11-20 | 1997-06-06 | Asahi Glass Co Ltd | Liquid crystal display device and its production |
| WO1999032924A1 (en) * | 1997-12-19 | 1999-07-01 | Hitachi, Ltd. | Liquid crystal display |
| JP4201942B2 (en) * | 1999-12-02 | 2008-12-24 | シャープ株式会社 | Liquid crystal display |
-
2002
- 2002-05-31 JP JP2002160062A patent/JP4037690B2/en not_active Expired - Lifetime
-
2003
- 2003-05-30 CN CNB2006101018188A patent/CN100447638C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105022193A (en) * | 2014-04-29 | 2015-11-04 | 群创光电股份有限公司 | Display panel |
| US10043460B2 (en) | 2014-04-29 | 2018-08-07 | Innolux Corporation | Display panel |
| CN105022193B (en) * | 2014-04-29 | 2019-02-26 | 群创光电股份有限公司 | Display panel |
| US10818248B2 (en) | 2014-04-29 | 2020-10-27 | Innolux Corporation | Display panel |
| CN109891314A (en) * | 2016-12-27 | 2019-06-14 | 株式会社Lg化学 | It is used to form the method and liquid crystal color-changing device of the wiring part of liquid crystal color-changing device |
| CN109891314B (en) * | 2016-12-27 | 2021-12-07 | 株式会社Lg化学 | Method for forming wiring portion of liquid crystal color-changing device and liquid crystal color-changing device |
| CN106707636A (en) * | 2017-03-30 | 2017-05-24 | 京东方科技集团股份有限公司 | Display panel, display device and display panel preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004004329A (en) | 2004-01-08 |
| JP4037690B2 (en) | 2008-01-23 |
| CN100447638C (en) | 2008-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1272659C (en) | LCD and its mfg. method | |
| CN1154002C (en) | Liquid crystal display device and method for producing the same | |
| CN1088524C (en) | A liquid crystal display element and a manufacturing method of the same | |
| CN1282018C (en) | Liquid crystal display device | |
| CN1156729C (en) | Liquid crystal display device and method for manufacturing the same | |
| CN1149437C (en) | Liquid crystal alignment film, method for mfg. same, liquid crystal display using the film and method, and method for mfg. for display | |
| CN1085344C (en) | Liquid crystal display device and method for producing the same | |
| CN1261800C (en) | Liquid crystal display and its producing method | |
| CN1079954C (en) | Liquid crystal display device and method of manufacturing the same | |
| CN1306323C (en) | Reflective liquid crystal display and its producing process | |
| CN1291271C (en) | Liquid crystal display device | |
| CN1225672C (en) | Substrate for liquid-crystal display, liquid-crystal display and manufacture thereof | |
| CN1213327C (en) | Resin-liquid crystal formed body, liquid crystal device, liquid crystal display comprising the same and methods of manufacturing the same | |
| CN1900796A (en) | Liquid crystal display device and method of producing the same | |
| CN1639622A (en) | A liquid crystal device, a method for producing a liquid crystal device and a method for controlling a liquid crystal device | |
| CN1564962A (en) | Liquid crystal display device and method of fabricating the same | |
| CN1707336A (en) | Liquid crystal display | |
| CN1495492A (en) | Active matrix vertical orientation mode liquid crystal display and its driving method | |
| CN1841166A (en) | Oriented film, method for forming the same, liquid crystal plate and electronic equipment | |
| CN1394294A (en) | Liquid crystal display and its manufacturing mehtod | |
| CN1904684A (en) | Liquid crystal display device having a plurality of pixel electrodes | |
| CN1668945A (en) | Polarizing plate having optically anisotropic layer formed from liquid crystal molecules | |
| CN1253302A (en) | Liquid crystal display element and its manufacturing method and evaluating method | |
| CN1234877A (en) | Liquid crystal alignment film, method of producing same, liquid crystal display made by using film, and method of producing same | |
| CN1690807A (en) | Brightness strengthening film for LCD and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160504 Address after: Darmstadt Patentee after: MERCK PATENT GmbH Address before: Osaka Patentee before: Sharp Corp. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20081231 |
|
| CX01 | Expiry of patent term |