CN100476548C - Method for preparing liquid crystal vertical oriented membrane - Google Patents
Method for preparing liquid crystal vertical oriented membrane Download PDFInfo
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- CN100476548C CN100476548C CNB200410010638XA CN200410010638A CN100476548C CN 100476548 C CN100476548 C CN 100476548C CN B200410010638X A CNB200410010638X A CN B200410010638XA CN 200410010638 A CN200410010638 A CN 200410010638A CN 100476548 C CN100476548 C CN 100476548C
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- liquid crystal
- tropism
- cinnamate
- crystal vertical
- hexafluoro bisphenol
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Abstract
This invention is a method of producing the liquid crystal vertical tropism membrane. This invention chooses the monomer with cinnamonic acid structure at both ends of the molecule, and the hexafluorodiphene A dicinnamonic acid ester containing fluoroform radicle. At the normal temperature, dissolve the hexafluorodiphene A dicinnamonic acid ester in the solvent of quadplex hydroxy furan to confect into solution. Smear the solution on the basal board reelingly to form membrane. Shine the monomer membrane material of the hexafluorodiphene A dicinnamonic acid ester with the ultraviolet radiation, and make the both ends of the monomer molecule take place [2+2] cycloaddition reaction, then produce a tropism membrane that can induce the liquid crystal vertical tropism array. This invention avoids heat treatment at high temperature in the confecting process, which consumedly simplified the traditional technics of confecting the liquid crystal vertical tropism membrane. Compared with the traditional method of confecting the liquid crystal vertical tropism membrane, this invention has a simpler technics, and is a new method of confecting the liquid crystal vertical tropism membrane.
Description
Technical field
The invention belongs to the photoelectron material technical field, relate to the preparation of liquid crystal device alignment films, specifically a kind of method for preparing the liquid crystal vertical-tropism film.
Background technology
LCD enjoys people's favor in field of information display with its flat board, portable, low-power consumption, electromagnetic-radiation-free, to the undamaged characteristics of eyesight.The drawbacks limit that yet the visual angle is narrow partially, response speed is slow the application of LCD.Though the ferroelectric liquid crystals response speed is far longer than nematic liquid crystal, also do not find a kind of stable orientations method that can practicability so far.Show that at twisted nematic liquid crystal (TN-LCD), supertwist nematic liquid crystal show that (STN-LCD), thin film transistor (TFT) twisted nematic liquid crystal show that (TFT-TN-LCD), homeotropic alignment liquid crystal show in (VA-LCD) pattern, the response speed of VA-LCD is the fastest, contrast is also very high, is applied.For overcoming the problem of narrow viewing angle, multidomain homeotropic alignment (MVA) display mode is proposed again in recent years, not only response speed is fast, and has solved the narrow partially shortcoming of visual angle of liquid crystal display, so the research of liquid crystal homeotropic alignment becomes current focus.
The preparation method of vertical alignment layer comprises inclination evaporation SiO method, LB embrane method, macromolecule spin-coating method etc.The non-friction orientation process of the general employing of the preparation process of vertical alignment layer, oriented material mostly is polyimide or the polyamic acid that has alkyl chain, and preparation process needs high-temperature heat treatment to desolvate and imidization curing to remove.The heat treatment process of high temperature has limited the selection of substrate, and can cause certain injury for established driving circuit on the substrate.
The various countries researchist just is being devoted to the exploratory development of light control orientation material at present.Photopolymerisable characteristics are that the required energy of activation of polyreaction is low, are easy to cold polymerization.People have proposed the thought of the photo orientated arrangement liquid crystal of polymeric membrane for this reason.Traditional photo orientated method is that the molecule that contains photosensitive group is inserted in the macromolecular main chain as side chain, makes polymkeric substance generation directional light crosslinked under the polarized ultraviolet irradiation, and polymer surfaces produces the tension force anisotropy, thereby induces liquid crystal aligning.For the selection of prepolymer, people have carried out deep discussion to cinnamic acid, cumarin, azo quasi-molecule, light-sensitive polyamic acid etc.But these material molecules are all very big, and ubiquity steric hindrance height, low, the unfavorable problem of orientation effect of photo-crosslinking efficient.The Chinese patent communique discloses " a kind of both-end has the photo orientated membrane preparation method of carbon carbon double bond monomer " (CN1367404A) and the patented claim of " a kind of photo orientated membrane preparation method of both-end photosensitive monomer " (CN 1367403A, open day on September 4th, 2002).These two patented claims, used small molecule monomer two ends all have the photosensitivity group, provide approach for solving the photo-crosslinking efficiency.
But photo orientated method usually is used for preparing the alignment films that is arranged in parallel of liquid crystal molecule, seldom is used for preparing the liquid crystal vertical-tropism film.
Summary of the invention
The present invention carries out photopolymerization with fluorine-containing photosensitive monomer molecule, and purpose provides a kind of method for preparing the liquid crystal vertical-tropism film.
The present invention adopts the two cinnamate monomer membrane materials of UV-irradiation hexafluoro bisphenol-a, makes the monomer molecule two ends that [2+2] cycloaddition reaction take place under light action, the alignment films that generation can induce liquid crystal vertical-tropism to arrange.
In order to obtain vertical orientated liquid crystal orientation film, the present invention has selected the molecule two ends to have the cinnamic acid structure, has contained the monomer of the two cinnamates of hexafluoro bisphenol-a of trifluoromethyl, and its molecular structural formula is:
At normal temperatures the two cinnamates of hexafluoro bisphenol-a are dissolved in the tetrahydrofuran solvent wiring solution-forming.Solution is spun on film forming on the substrate, uses the film on the UV-irradiation substrate immediately, make the monomer molecule both-end that [2+2] cycloaddition polyreaction take place, the gained polymeric membrane can directly be induced the liquid crystal molecule homeotropic alignment.
In order more to be expressly understood the present invention in detail, process of the present invention is described in detail below.
One, the two cinnamate monomers of hexafluoro bisphenol-a is synthetic
Synthetic chemical reaction process is as follows:
The two cinnamates of the hexafluoro bisphenol-a that generates recrystallization in 1: 1 ethanol and ethyl acetate mixture can obtain being higher than 99% pure product.
Two, the two cinnamate monomer solutions of preparation hexafluoro bisphenol-a
The two cinnamate monomers of excessive hexafluoro bisphenol-a are placed tetrahydrofuran solvent, through sonic oscillation it is dissolved to greatest extent, centrifugal treating is taken out settled solution then, and obtaining concentration is the two cinnamate monomer solutions of hexafluoro bisphenol-a of 5～10wt%.
Three, film
The two cinnamate monomer solutions of above-mentioned hexafluoro bisphenol-a are spin-coated on glass substrate or CaF
2On substrate that can be wetted, twice of spin coating.Substrate surface forms uniform monomer film.
Four, illumination
The two cinnamate monomer films of hexafluoro bisphenol-a were directly used UV-irradiation 10～20 minutes, monomer generation photo-crosslinking and solidifying.Ultraviolet source adopts mercury xenon lamp, and the optical power density of 297nm place monitoring is 1.2～10mw/cm
2
Can on substrate, make the vertical alignment layer of liquid crystal in order to last method.
Being the performance of check alignment films, is that inboard, 10 μ m polyimide film bars are that chock insulator matter is to changing into liquid crystal cell, the injection liquid crystal with the alignment films with two substrates after the illumination.At first whether check is vertical orientated, liquid crystal cell is placed under the polarizing microscope observe.Under the cross-polarized light condition, the rotation liquid crystal cell, the visual field is always dark attitude, and this is the inevitable phenomenon that liquid crystal vertical-tropism is arranged; Observe under awl light polarizing microscope then, can see black cross image as shown in Figure 1, this is the optical signature of liquid crystal vertical-tropism.Check the thermal stability of alignment films again,, make the variation that liquid crystal cell is observed the liquid crystal molecule inclination angle, need to prove on the molecule inclination angle term under the making alive condition not to claim tilt angle at first with alignment films thermal treatment.As shown in Figure 2, temperature from 60 ℃ until being increased to 120 ℃, the tilt angle of liquid crystal molecule changes hardly, illustrates that the thermal stability of alignment films is fine.
The present invention has avoided high-temperature heat treatment in preparation process, has simplified the technology of traditional preparation process liquid crystal vertical-tropism film greatly.Compare with traditional method for preparing the liquid crystal vertical-tropism film, technology is simple, is the new method of preparation liquid crystal vertical-tropism film.
Description of drawings
Fig. 1 is observed black cross image under awl light polarizing microscope;
The change curve of Fig. 2 liquid crystal pretilt angle under the different heat treatment temperature, horizontal ordinate are the heat treatment temperature of vertical alignment layer, and unit is a Celsius temperature, and ordinate is the tilt angle of liquid crystal molecule, and unit is degree.
Embodiment
1) the two cinnamate monomers of hexafluoro bisphenol-a is synthetic
Get hexafluoro replacement bisphenol-A (U.S. Aldrich Co.) 3.31g and be dissolved in the 40mL anhydrous tetrahydro furan (the safe chemical company in sky, Tianjin, import packing), and be placed in the 100mL there-necked flask.Get triethylamine (chemical plant, Dongxing, Shenyang City) 2.76mL again, directly join in the there-necked flask.
Get cinnamoyl chloride (U.S. Aldrich Co.) 4.1g and be dissolved in the 10mL anhydrous tetrahydro furan, place the tap funnel of 50mL then.
Under the frozen water cooling, the solution of cinnamoyl chloride slowly is added drop-wise in the there-necked flask, open automatic stirrer simultaneously and stir, there are a large amount of white insolubless to generate.After being added dropwise to complete, continue to stir 30 minutes.
Leach insolubles, get colourless transparent solution.
In a large amount of cold water of colourless transparent solution impouring, separate out whiteness, be the two cinnamate monomers of hexafluoro bisphenol-a, productive rate is 85%.
Recrystallization obtains being higher than 99% pure product in 1: 1 ethanol and ethyl acetate mixture.
2) the two cinnamate monomer solutions of preparation hexafluoro bisphenol-a
The two cinnamate monomers of excessive hexafluoro bisphenol-a are placed tetrahydrofuran solvent, through sonic oscillation it is dissolved to greatest extent, centrifugal treating is taken out settled solution then, and obtaining concentration is the two cinnamate monomer solutions of hexafluoro bisphenol-a of 5wt%.
3) film
The two cinnamate monomer solutions of the hexafluoro bisphenol-a that obtains are spun on the glass substrate twice of spin coating.Spin speed and time are made as: V=1500rpm, t=10 second;
4) illumination
Light source adopts the 300W mercury xenon lamp, and the optical power density at 297nm wavelength place is 1.2mw/cm
2
The substrate of will filming is used the 300W mercury xenon lamp immediately, and vertical irradiation is 10 minutes under the 297nm ultraviolet light, and the alignment films after the curing is insoluble to solvent, illustrates to form polymeric membrane.
Detect the orientation effect of the two cinnamates of hexafluoro bisphenol-a with following method.
With two substrates after the illumination is inboard with the alignment films, and 10 μ m polyimide film bars are that chock insulator matter is made liquid crystal cell.TEB30A nematic liquid crystal (Shijiazhuang strength gram company product) injects liquid crystal cell for 62 ℃ at cleaning point.Naturally reduce to room temperature, obtain the liquid crystal cell test sample.
Under orthogonal polarizing microscope, observe, the rotation liquid crystal cell, the visual field is always dark attitude.Under awl light polarizing microscope, observe the black cross image of seeing as shown in Figure 1, show that the two cinnamate alignment films of prepared hexafluoro bisphenol-a can induce liquid crystal homeotropic alignment equably.
To under different temperatures, heat half an hour respectively with the substrate of alignment films, naturally cool to room temperature again, make the liquid crystal cell after series of temperature is handled.Inject liquid crystal respectively, the variation of observation liquid crystal pretilt angle.As shown in Figure 2, heating is until 120 ℃, and the tilt angle of liquid crystal illustrates that still near 90 ° the liquid crystal vertical-tropism film of the present invention's preparation has good thermal stability.
Claims (5)
1, a kind of method for preparing the liquid crystal vertical-tropism film, comprise the two cinnamate monomers of synthetic hexafluoro bisphenol-a, the preparation monomer solution, monomer solution is spin-coated on film forming on the substrate, four processes of UV-irradiation film, it is characterized in that monomer is the fluorine-containing photosensitive two cinnamate molecules of hexafluoro bisphenol-a of both-end, molecular structural formula is:
The two cinnamate monomers of hexafluoro bisphenol-a are dissolved in the tetrahydrofuran solvent, are made into monomer solution; Monomer solution is spin-coated on film forming on the substrate, uses the film on the UV-irradiation substrate immediately, makes the two cinnamate molecule generation polymerizations of hexafluoro bisphenol-a, forms the vertical alignment layer of liquid crystal.
2, the method for preparing the liquid crystal vertical-tropism film according to claim 1 is characterized in that the two cinnamate monomers of hexafluoro bisphenol-a are dissolved in the tetrahydrofuran solvent, and the mass percent concentration of the two cinnamate monomers of hexafluoro bisphenol-a is 5～10wt%.
3, the method for preparing the liquid crystal vertical-tropism film according to claim 2 is characterized in that the two cinnamate monomer films of hexafluoro bisphenol-a, directly uses the ultraviolet light vertical irradiation 10～20 minutes.
4, the method for preparing the liquid crystal vertical-tropism film according to claim 3 is characterized in that ultraviolet source adopts mercury xenon lamp, and 297nm place polarized light power density is 1.2～10mw/cm
2
5,, it is characterized in that the synthetic chemical reaction process of the two cinnamate monomers of hexafluoro bisphenol-a is as follows according to claim 1 or the 3 described methods that prepare the liquid crystal vertical-tropism film:
The two cinnamates of the hexafluoro bisphenol-a that generates are recrystallization in 1: 1 ethanol and ethyl acetate mixture.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200410010638XA CN100476548C (en) | 2004-01-10 | 2004-01-10 | Method for preparing liquid crystal vertical oriented membrane |
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| CNB200410010638XA CN100476548C (en) | 2004-01-10 | 2004-01-10 | Method for preparing liquid crystal vertical oriented membrane |
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| CN1641449A CN1641449A (en) | 2005-07-20 |
| CN100476548C true CN100476548C (en) | 2009-04-08 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8310636B2 (en) * | 2007-03-26 | 2012-11-13 | Sharp Kabushiki Kaisha | Liquid crystal display device and polymer for aligning film material |
| CN102516497B (en) * | 2008-12-19 | 2013-08-28 | 比亚迪股份有限公司 | Fluorine-containing resin, preparation method thereof, conformal coating and printed circuit board |
| CN102368129B (en) * | 2011-10-14 | 2013-06-26 | 深圳市华星光电技术有限公司 | Manufacturing method of liquid crystal display |
| CN103063582A (en) * | 2012-12-27 | 2013-04-24 | 大连海事大学 | Sensitive orientation film of liquid crystal chemical sensor for detecting organic amines, and preparation method thereof |
| CN105629585A (en) * | 2016-01-13 | 2016-06-01 | 深圳市华星光电技术有限公司 | Liquid crystal display panel structure and manufacturing method thereof |
| CN105885872B (en) * | 2016-04-07 | 2018-11-23 | 深圳市华星光电技术有限公司 | The production method of liquid crystal material, liquid crystal display panel and liquid crystal display panel |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR940004317B1 (en) * | 1991-12-23 | 1994-05-19 | 주식회사 금성사 | Liquid crystal display devices having color seal |
| CN1036026C (en) * | 1993-09-18 | 1997-10-01 | 株式会社金星社 | Method for forming an orientation film of photopolymer in a liquid crystal display |
| CN1343755A (en) * | 2001-10-26 | 2002-04-10 | 中国科学院长春应用化学研究所 | Process for preparing liquid crystal orientated film from polyimide containing photosensitive terminating agent |
| CN1367403A (en) * | 2001-12-14 | 2002-09-04 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of photo orientated film whose two ends possess photosensitive monomer |
-
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- 2004-01-10 CN CNB200410010638XA patent/CN100476548C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR940004317B1 (en) * | 1991-12-23 | 1994-05-19 | 주식회사 금성사 | Liquid crystal display devices having color seal |
| CN1036026C (en) * | 1993-09-18 | 1997-10-01 | 株式会社金星社 | Method for forming an orientation film of photopolymer in a liquid crystal display |
| CN1343755A (en) * | 2001-10-26 | 2002-04-10 | 中国科学院长春应用化学研究所 | Process for preparing liquid crystal orientated film from polyimide containing photosensitive terminating agent |
| CN1367403A (en) * | 2001-12-14 | 2002-09-04 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of photo orientated film whose two ends possess photosensitive monomer |
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