CN1967354A - Optical directional material improving optical directional performance of liquid crystal and its preparing method - Google Patents
Optical directional material improving optical directional performance of liquid crystal and its preparing method Download PDFInfo
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- CN1967354A CN1967354A CN 200610144030 CN200610144030A CN1967354A CN 1967354 A CN1967354 A CN 1967354A CN 200610144030 CN200610144030 CN 200610144030 CN 200610144030 A CN200610144030 A CN 200610144030A CN 1967354 A CN1967354 A CN 1967354A
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Abstract
The invention discloses a material to improve the LCD-oriented directional optical properties fabrication methods, which belongs to photosensitive materials technology. The photosensitive materials are mixed of epoxy resin-based materials and polymer-oriented materials. Those two containing materials corporations are cinnamoyl cyclization reaction, thereby induced liquid crystal alignment. The material for the preparation methods is to replace the benzene ring cinnamic acid and slightly excessive thionyl chloride and so on the benzene ring completely replace the cinnamon chloride solution Solutions to increase with the acid absorbent polar aprotic solvents, phenol or two polyphenol solution drop wise, be used doped photosensitive materials, photosensitive materials to be epoxy-based polymers for optical orientation of mixed-orientation was obtained material. This invention can improve LCD-directional capability of a single polymer-oriented material, and also achieve proper optical directional effects by choosing the type of photosensitive materials and the ratio of them.
Description
Technical field
The invention belongs to the photochromics technical field, particularly the optical directional material and the preparation method that use of LCD oriented layer.
Background technology
High-molecular optical sensitive materials and correlation technique are one of current polymer material science priority fields of studies, can be widely used in a lot of aspects of electronics and optoelectronics industry.One of important application that it is potential is as the liquid crystal material for optical orientating layer.High-quality LCD requires liquid crystal that stable and uniform initial arrangement is arranged.Have the thin layer of inducing liquid crystal to align effect and be called liquid crystal alignment layer (alignment layers).In order to obtain evenly arranging along face, the past has been reported the plurality of liquid crystals orientation arrangement method in the literature, for example:
The inclination vapour deposition method: this method is the liquid crystal aligning method that Zhan Ning was developed in 1972, mainly be with directing agent such as monox oxide or metals such as Au, Pt such as (SiO), from direction evaporation that substrate face is tilted on substrate face, the corrugated surface and the liquid crystal molecule that form on the substrate face are interacted, thereby form specific molecules align.This method comprises evaporation, a secondary evaporation and rotates three kinds of evaporations that its shortcoming is that preparation process is too complicated.
Rubbing method: rubbing method is present most widely used industrial method in LCD is made.Friction realizes by substrate being pressed onto the Velveting surface of evenly moving, the method for the round roller friction of also useful bag Velveting.This method can produce by the visible little groove of electron microscope at substrate surface.Have on little flute surfaces at such one, liquid crystal molecule is parallel or favour the groove direction and arrange.But rubbing method has a lot of important disadvantages.At first, friction can produce dust, thereby reduces the quality of LCD; The second, friction can produce static, destroys thin film transistor (TFT) etc.; The 3rd, friction can only be implemented at planar surface, then can not use rubbing method for curved surface; In addition, friction can not produce the liquid crystal arrangement of style.
Active oriented film: compare with traditional liquid crystal orientating membrane, the oriented film that another kind is known as " instruction level " can make liquid crystal its ordered state generation reversibility under the drive of the instruction molecule that photoreceiving surface drives change.This class instruction level can be called " active oriented film ".Different with traditional oriented film, the photolytic activity oriented film is by the photochromism material preparation.A kind of typical photochromic primitive is an azobenzene molecule, makes its structure by the trans cis that changes to by illumination, arranges thereby cause instruction aspect liquid crystal molecule to be arranged to change to along face by vertical plane.But this technology is also immature at present.
Light directional technology: the nineties, people such as Schadt have reported so-called linear polarization photopolymerization reaction (LinearlyPolarized Photo-polymerization, LPP) technology makes the anisotropic polymeric membrane of the molecule crosslinked formation of cinnamate with the linear polarization rayed.At the strand of substrate surface random arrangement, when polarized ultraviolet shines, cause the generation of anisotropic reactive, formed polymeric membrane works the effect of aligning to liquid crystal.The light directional technology aligns liquid crystal molecule by non-contacting surface treatment method, can overcome the shortcoming that rubbing method brings, and realizes big plane, curved surface and the liquid crystal arrangement of style is arranged.The light directional technology is mainly realized by the light oriented polymeric material at present, polymeric material kind and the quantity used are very abundant, that has reported comprises multiclass light oriented polymeric material such as polyimide, polysiloxane, polyurethane, epoxy resin, polyvinyl alcohol (PVA), but mostly be the single polymers material, if will satisfy requirement of actual application, existing material is in the uniform and stable property of directional crystal, and directional properties aspects such as demonstration contrast still need bigger improvement.
Summary of the invention
The objective of the invention is to propose a class and can improve optical directional material of optical directional performance of liquid crystal and preparation method thereof for overcoming the weak point of existing optical directional material.The present invention obtains optical directional material by doping photochromics in epoxy resin-matrix light stereospecific polymer, can improve the liquid crystal light capacity of orientation of single polymers optical directional material, also can obtain required light directional effect by kind and the ratio of selecting photochromics.
The optical directional material that improves optical directional performance of liquid crystal that the present invention proposes; mix by photochromics and epoxy resin-matrix light oriented polymeric material; the photosensitive group of two kinds of materials is cinnamoyl (this photosensitive group under the linear polarized uv irradiation anisotropic [2+2] cycloaddition reaction can take place, thereby induces liquid crystal to align).
The proportioning of described two kinds of compositions is:
Cinnamoyl in the light oriented polymeric material: cinnamoyl in the photochromics=1: (0～0.3), even the content of cinnamoyl is 1 in the light oriented polymeric material, then in the photochromics content of cinnamoyl greater than 0 in smaller or equal to the light oriented polymeric material in 30% scope of cinnamoyl;
The molecular structural formula of described photochromics is:
Wherein:
R represents the substituting group on the phenyl ring, and substituent R can be hydrogen atom, halogen, C
1-C
8Alkyl, C
1-C
8Alkoxy preferablely is selected from hydrogen atom, to normal octane oxygen base;
Substituent R can be positioned at ortho position, a position or the contraposition of phenyl ring; M looks substituting group number difference and can be 1 to 3 integer;
Above-mentioned halogen is meant fluorine, chlorine, bromine and iodine atom.
Above-mentioned alkyl can be (but being not limited to) methyl, ethyl, propyl group, isopropyl, butyl, amyl group, hexyl.
Above-mentioned alkoxy can be (but being not limited to) methoxyl, ethoxy, propoxyl group, butoxy, octyloxy.
X is for can be but be not limited to following group
And
According to the difference of X functionality, n can round numbers 2 or 3.
The above-mentioned preparation method who improves the optical directional material of optical directional performance of liquid crystal that the present invention proposes may further comprise the steps:
1) synthetic photochromics:
(a) the preparation phenyl ring replaces cinnamoyl chloride (being the cinnamoyl chloride that different substituents is arranged on the phenyl ring): by phenyl ring substituted cinnamic acid (being the cinnamic acid that different substituents is arranged on the phenyl ring) and excessive slightly (general than the amount of phenyl ring substituted cinnamic acid excessive 5%) thionyl chloride (SOCl
2), phosphorus trichloride (PCl
3) or phosphorus pentachloride (PCl
5) obtained in 4-10 hour 40～70 ℃ of following reactions;
The structure of described phenyl ring substituted cinnamic acid is as follows:
The structure that described phenyl ring replaces cinnamoyl chloride is as follows:
Wherein m looks the integer that substituting group number difference is got 1-3;
R represents the substituting group on the phenyl ring, and substituent R can be hydrogen atom, halogen, C
1-C
8Alkyl, C
1-C
8Alkoxy;
Substituent R can be positioned at ortho position, a position or the contraposition of phenyl ring; M looks substituting group number difference and can be 1 to 3 integer;
Above-mentioned halogen is meant fluorine, chlorine, bromine and iodine atom;
Above-mentioned alkyl can be (but being not limited to) methyl, ethyl, propyl group, isopropyl, butyl, amyl group, hexyl.
Above-mentioned alkoxy can be (but being not limited to) methoxyl, ethoxy, propoxyl group, butoxy, octyloxy.
(b) (a) step is synthetic phenyl ring replacement cinnamoyl chloride is dissolved in the aprotic polar solvent that is added with acid absorbent fully, in ice-water bath, drip to diphenol or polyphenol solution, (wherein cinnamoyl chloride was excessive in slightly to guarantee that phenolic hydroxyl group reacts completely in 4-10 hour to be warming up to 70 ℃ of reactions then, solvent load dissolves reactant fully and gets final product, the acid absorbent consumption is 3-6 a times of acyl chlorides consumption, the acid that generates with abundant absorption reaction), obtain the photochromics that is used to mix, its structure is as follows:
Wherein n gets 2 or 3 according to phenols functionality difference;
(the synthetic photochromics of said method can prove by infrared spectrum, nmr analysis and obtain pure substance, can be used for liquid crystal light orientation).
The diphenol that adopts in the present invention (b) step can adopt but is not limited to p-dihydroxy-benzene, bisphenol-A, '-biphenyl diphenol; The polyphenol that adopts can adopt but be not limited to phloroglucin.
The aprotic polar solvent that adopts in the present invention (b) step can adopt but is not limited to tetrahydrofuran (THF), N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) and N,N-dimethylacetamide (DMAC).
Acid absorbent in the present invention (b) step for catching free hydrionic weak base, can adopt but is not limited to pyridine (Py), triethylamine (TEA), N-ethylmorpholine (NEM) and xylidin (NDMA).
2) synthetic epoxy resin base light stereospecific polymer
Epoxy resin-matrix light stereospecific polymer that the present invention selects for use and synthetic method thereof are public technology (Chinese patent: " LCD directional material and method for making thereof ", publication number: CN 1504537A).
Above-mentioned epoxy resin-matrix light stereospecific polymer, structure is as follows:
Wherein N is the integer greater than 1;
R
1, R
2All can be hydrogen atom, halogen, C
1-C
8Alkyl, C
1-C
8Alkoxy, R
1, R
2All can be positioned at ortho position, a position and the contraposition of phenyl ring; X, y look all desirable 1 to 3 the integer of substituting group number difference on the phenyl ring.
Y is selected from following group:
3) with the described photochromics of step 1) to step 2) promptly improve after mixing and the mixing optical directional material of optical directional performance of liquid crystal of described epoxy resin-matrix light stereospecific polymer, wherein,
Cinnamoyl group content with epoxy resin-matrix light stereospecific polymer is a benchmark; the cinnamoyl content range of the photochromics that mixes is in greater than 0 30% scope smaller or equal to polymkeric substance cinnamoyl group content; preferable doping ratio is the 10%-20% of cinnamoyl group content scope (the photo-crosslinking mechanism of cinnamoyl is mainly [2+2] cycloaddition reaction, so doping ratio calculates with the cinnamoyl group content).
The epoxy resin-matrix optical directional material of doping photochromics of the present invention can be prepared into liquid crystal light oriented film and be used for LCD.The preparation of liquid crystal light oriented film can be by known method, for example, optical directional material of the present invention can be dissolved with aprotic solvent, be made into the homogeneous solution of massfraction at 1%-3%, by the surperficial rotary plating of desk-top sol evenning machine at base material, and carry out photo-crosslinking with polarized ultraviolet (for example centre wavelength is 365nm) irradiation 1-60min, and obtain anisotropic light orientating layer, be assembled into liquid crystal cell and pour into liquid crystal test liquid crystal aligning effect.
Characteristics of the present invention and technique effect:
The present invention has broken through the tradition of former use single polymers directional crystal, synthesizes the multiple photochromics that contains cinnamoyl, and it is doped in the single epoxy resin-matrix light stereospecific polymer.Experimental result shows, the present invention is on the basis that guarantees directed homogeneity and stability, make the liquid crystal cell contrast increase substantially, contrast can be improved 280% in the most preferred embodiment, can improve the liquid crystal aligning effect of existing polymkeric substance well, also can obtain required light directional effect by kind and the ratio of selecting photochromics.
Embodiment
Following examples are used for that the invention will be further described, but not in order to limit the scope of the invention.Modification that any those of ordinary skill in the art can reach easily and change are included within this case instructions disclosure and the claims.
Embodiment 1
The preparation method of optical directional material in the present embodiment may further comprise the steps:
1) photochromics is synthetic:
(a) preparation of cinnamoyl chloride: be equipped with in the there-necked flask of reflux condensing tube and gas absorber and add 14.8g (0.100mol) cinnamic acid, stir down and add 7.5mL (12.3g gradually with tap funnel, 0.105mol) thionyl chloride, be to react 4-10hr under 40-70 ℃ the condition with water-bath control temperature, obtain the white solid cinnamoyl chloride.
(b) the two cinnamates of bisphenol-A is synthetic: be equipped with in the there-necked flask of reflux condenser one and add 1.140g (5mmol) bisphenol-A, 2mL anhydrous pyridine and 10mL anhydrous tetrahydro furan, in ice-water bath, slowly drip the anhydrous tetrahydrofuran solution of 1.689g (10.2mmol) cinnamoyl chloride, be warming up to 70 ℃ of reaction 4-10hr after treating all to dropwise.Reaction product precipitates with deionized water, filters, and washing, oven dry obtains the two cinnamates of bisphenol-A.
2) epoxy resin-matrix light stereospecific polymer is synthetic:
Preparation method's referenced patent CN 1504537A of polymer B P-AN-CA, molecular structural formula is as follows:
3) the two cinnamates of bisphenol-A are mixed with 5% ratio with BP-AN-CA, obtain the optical directional material that improves optical directional performance of liquid crystal of the present invention.
Adopt present embodiment to improve the experiment of liquid crystal aligning effect:
The optical directional material that obtains with step 3) is mixed with the tetrahydrofuran solution of 2% (polymer quality mark), coat the ito glass surface with desk-top sol evenning machine and form transparent homogeneous film, through 60 ℃/3 hours thermal treatments remove desolvate after, place under the polarized ultraviolet irradiation 1 to 10 minute, and be assembled into liquid crystal cell then.Liquid crystal cell is placed the power detector below, rotation liquid crystal cell angle is measured its penetrating light intensity, and getting the maximum transmission intensity cycle with the method is pi/2, the light stereospecific polymer of hence one can see that doping photochromics is behind polarized ultraviolet irradiation, and the liquid crystal cell of assembling possesses good liquid crystal aligning effect.Guaranteeing that the contrast of this liquid crystal cell uses the liquid crystal cell contrast of single polymers BP-AN-CA to improve 30% on the inhomogeneity basis of directional crystal.
Embodiment 2
Optical directional material and preparation method in the present embodiment may further comprise the steps:
1) with embodiment 1
2) with embodiment 1
3) the two cinnamates of bisphenol-A are mixed with 10% ratio with BP-AN-CA, obtain the material that improves liquid crystal light directional effect of the present invention.
The liquid crystal aligning effect of present embodiment:
The material that step 3) obtains has good liquid crystal aligning effect, and the contrast of liquid crystal cell uses the contrast of single polymers BP-AN-CA liquid crystal cell to improve 90% on the basis that guarantees directional crystal homogeneity and stability.
Embodiment 3
The preparation method of optical directional material in the present embodiment may further comprise the steps:
1) with embodiment 1
2) with embodiment 1
3) the two cinnamates of bisphenol-A are mixed with 20% ratio with BP-AN-CA, obtain the material that improves liquid crystal light directional effect of the present invention.
The liquid crystal aligning effect of present embodiment:
The material that step 3) obtains has good liquid crystal aligning effect, and the contrast of liquid crystal cell uses the contrast of single polymers BP-AN-CA liquid crystal cell to improve 30% on the basis that guarantees directional crystal homogeneity and stability.
Embodiment 4
The preparation method of optical directional material may further comprise the steps in the present embodiment:
1) photochromics is synthetic:
(a) preparation of ethyl cinnamoyl chloride between: be equipped with in the there-necked flask of reflux condensing tube and gas absorber and add ethyl-cinnamic acid between 17.6g (0.100mol), stir down and add 7.5mL (12.3g gradually with tap funnel, 0.105mol) thionyl chloride, be to react 4-10hr under 40-70 ℃ the condition with water-bath control temperature, obtain an ethyl cinnamoyl chloride.
(b) '-biphenyl diphenol two between ethyl-cinnamic acid ester synthetic: be equipped with in the there-necked flask of reflux condenser one and add 0.930g (5mmol) '-biphenyl diphenol, 2mL anhydrous pyridine and 10mL anhydrous tetrahydro furan, in ice-water bath, slowly drip the anhydrous tetrahydrofuran solution of ethyl cinnamoyl chloride between 1.979g (10.2mmol), be warming up to 70 ℃ of reaction 4-10hr after treating all to dropwise.Reaction product precipitates with deionized water, filter, washing, oven dry,, obtain '-biphenyl diphenol two between the ethyl-cinnamic acid ester.
2) epoxy resin-matrix light stereospecific polymer is synthetic:
Preparation method's referenced patent CN 1504537A of polymkeric substance DP-EAN-ECA, molecular structural formula is as follows:
3) the two cinnamates of ethyl mix with 5% ratio with DP-EAN-ECA between general, obtain the optical directional material that improves optical directional performance of liquid crystal of the present invention
The liquid crystal aligning effect of present embodiment:
The material that step 3) obtains has good liquid crystal aligning effect, and the contrast of liquid crystal cell uses the contrast of single polymers DP-EAN-ECA liquid crystal cell to improve 40% on the basis that guarantees directional crystal homogeneity and stability.
Embodiment 5
The preparation method of optical directional material in the present embodiment may further comprise the steps:
1) with embodiment 4
2) with embodiment 4
3) the two cinnamates of ethyl mix with 10% ratio with DP-EAN-ECA between general, obtain the optical directional material that improves optical directional performance of liquid crystal of the present invention.
The liquid crystal aligning effect of present embodiment:
The material that step 3) obtains has good liquid crystal aligning effect, and the contrast of liquid crystal cell uses the contrast of single polymers DP-EAN-ECA liquid crystal cell to improve 120% on the basis that guarantees directional crystal homogeneity and stability.
Embodiment 6
The preparation method of optical directional material in the present embodiment may further comprise the steps:
1) with embodiment 4
2) with embodiment 4
3) the two cinnamates of ethyl mix with 20% ratio with DP-EAN-ECA between general, obtain the optical directional material that improves optical directional performance of liquid crystal of the present invention.
The liquid crystal aligning effect of present embodiment:
The material that step 3) obtains has good liquid crystal aligning effect, and the contrast of liquid crystal cell uses the contrast of single polymers DP-EAN-ECA liquid crystal cell to improve 40% on the basis that guarantees directional crystal homogeneity and stability.
Embodiment 7
The preparation method of optical directional material in the present embodiment may further comprise the steps:
1) photochromics is synthetic:
(a) to the preparation of normal octane oxygen base cinnamoyl chloride: with 7.5mL (12.3g, 0.105mo1) thionyl chloride dropwise adds 27.6g (0.100mol) in the normal octane oxygen base cinnamic acid, be to react 4-10hr under 40-70 ℃ the condition with water-bath control temperature, obtain normal octane oxygen base cinnamoyl chloride.
(b) p-dihydroxy-benzene biconjugate normal octane oxygen base cinnamate is synthetic: to 0.550g (5mmol) p-dihydroxy-benzene, drip the anhydrous tetrahydrofuran solution of 3.006g (10.2mmol) to normal octane oxygen base cinnamoyl chloride in 2mL anhydrous pyridine and the 10mL anhydrous tetrahydro furan.Be warming up to 70 ℃ of reaction 4-10hr after treating all to dropwise.Reaction product precipitates with deionized water, filters, and washing, oven dry obtains p-dihydroxy-benzene biconjugate normal octane oxygen base cinnamate.
2) epoxy resin-matrix light stereospecific polymer is synthetic:
Preparation method's referenced patent CN 1504537A of polymer P P-OAN-OCA, molecular structural formula is as follows:
3) p-dihydroxy-benzene biconjugate normal octane oxygen base cinnamate is mixed with 5% ratio with polymer P P-OAN-OCA, obtain the optical directional material that improves optical directional performance of liquid crystal of the present invention.
The liquid crystal aligning effect of present embodiment:
The material that step 3) obtains has good liquid crystal aligning effect, and the contrast of liquid crystal cell uses the contrast of single polymers PP-OAN-OCA liquid crystal cell to improve 85% on the basis that guarantees directional crystal homogeneity and stability.
Embodiment 8
The preparation method of optical directional material in the present embodiment may further comprise the steps:
1) with embodiment 7
2) with embodiment 7
3) p-dihydroxy-benzene biconjugate normal octane oxygen base cinnamate is mixed with 10% ratio with polymer P P-OAN-OCA, obtain the optical directional material that improves optical directional performance of liquid crystal of the present invention.
The liquid crystal aligning effect of present embodiment:
The material that step 3) obtains has good liquid crystal aligning effect, and the contrast of liquid crystal cell uses the contrast of single polymers PP-OAN-OCA liquid crystal cell to improve 280% on the basis that guarantees directional crystal homogeneity and stability.
Embodiment 9
The preparation method of optical directional material in the present embodiment may further comprise the steps:
1) with embodiment 7
2) with embodiment 7
3) p-dihydroxy-benzene biconjugate normal octane oxygen base cinnamate is mixed with 20% ratio with polymer P P-OAN-OCA, obtain the optical directional material that improves optical directional performance of liquid crystal of the present invention.
The liquid crystal aligning effect of present embodiment:
The material that step 3) obtains has good liquid crystal aligning effect, and the contrast of liquid crystal cell uses the contrast of single polymers PP-OAN-OCA liquid crystal cell to improve 85% on the basis that guarantees directional crystal homogeneity and stability.
Embodiment 10
The preparation of optical directional material may further comprise the steps in the present embodiment:
1) photochromics is synthetic:
(a) to the preparation of chloro-cinnamic acid: be equipped with in the there-necked flask of reflux condensing tube and gas absorber one and add 18.3g (0.100mol) to chloro-cinnamic acid, stir down and add 7.5mL (12.3g gradually with tap funnel, 0.105mol) thionyl chloride, be to react 4-10hr under 40-70 ℃ the condition with water-bath control temperature, obtain the chloro cinnamoyl chloride.
(b) bisphenol-A biconjugate chloro-cinnamic acid ester is synthetic: be equipped with in the there-necked flask of reflux condenser one and add 1.140g (5mmol) bisphenol-A, 2mL anhydrous pyridine and 10mL anhydrous tetrahydro furan, in ice-water bath, slowly drip the anhydrous tetrahydrofuran solution of 2.050g (10.2mmol), be warming up to 70 ℃ of reaction 4-10hr after treating all to dropwise the chloro cinnamoyl chloride.Reaction product precipitates with deionized water, filters, and washing, oven dry obtains bisphenol-A biconjugate chloro-cinnamic acid ester.
2) epoxy resin-matrix light stereospecific polymer is synthetic:
Preparation method's referenced patent CN 1504537A of polymer B P-AN-XCA, molecular structural formula is as follows:
3) bisphenol-A biconjugate chloro-cinnamic acid ester is mixed with 5% ratio with polymer B P-AN-XCA, obtain the optical directional material that improves optical directional performance of liquid crystal of the present invention.
The liquid crystal aligning effect of present embodiment:
The optical directional material that step 3) obtains has good liquid crystal aligning effect.Guaranteeing that the contrast of this liquid crystal cell uses the contrast of single polymers BP-AN-XCA liquid crystal cell to improve 60% on the inhomogeneity basis of directional crystal.
Embodiment 11
The preparation method of optical directional material in the present embodiment may further comprise the steps:
1) with embodiment 10
2) with embodiment 10
3) bisphenol-A biconjugate chloro-cinnamic acid ester is mixed with 10% ratio with polymer B P-AN-XCA, obtain the optical directional material that improves optical directional performance of liquid crystal of the present invention.
The liquid crystal aligning effect of present embodiment:
The material that step 3) obtains has good liquid crystal aligning effect, and the contrast of liquid crystal cell uses the contrast of single polymers BP-AN-XCA liquid crystal cell to improve 150% on the basis that guarantees directional crystal homogeneity and stability.
Embodiment 12
The preparation method of optical directional material in the present embodiment may further comprise the steps:
1) with embodiment 10
2) with embodiment 10
3) bisphenol-A biconjugate chloro-cinnamic acid ester is mixed with 20% ratio with polymer B P-AN-XCA, obtain the optical directional material that improves optical directional performance of liquid crystal of the present invention
The liquid crystal aligning effect of present embodiment:
The material that step 3) obtains has good liquid crystal aligning effect, and the contrast of liquid crystal cell uses the contrast of single polymers BP-AN-XCA liquid crystal cell to improve 60% on the basis that guarantees directional crystal homogeneity and stability.
Claims (10)
1, a kind of optical directional material that improves optical directional performance of liquid crystal, it is characterized in that, this material is mixed by photochromics and epoxy resin-matrix light oriented polymeric material, and the photosensitive group of described two kinds of materials is the cinnamoyl cycloaddition reaction, thereby induces liquid crystal to align;
The proportioning of described two kinds of material compositions is:
Cinnamoyl in the light oriented polymeric material: cinnamoyl in the photochromics=1: (0～0.3);
The molecular structural formula of described photochromics is:
Wherein:
R represents the substituting group on the phenyl ring, and m is 1 to 3 integer;
X is following group
And
N round numbers 2 or 3.
2, optical directional material as claimed in claim 1 is characterized in that, described substituent R adopts hydrogen atom, halogen, C
1-C
8Alkyl or C
1-C
8Alkoxy a kind of; Substituent R is positioned at ortho position, a position or the contraposition of phenyl ring.
3, optical directional material as claimed in claim 2 is characterized in that, described halogen adopts a kind of of fluorine, chlorine, bromine or iodine atom; Described alkyl adopts a kind of of methyl, ethyl, propyl group, isopropyl, butyl, amyl group or hexyl; Described alkoxy adopts a kind of of methoxyl, ethoxy, propoxyl group, butoxy or octyloxy.
4, a kind of preparation method who improves the optical directional material of optical directional performance of liquid crystal according to claim 1 may further comprise the steps:
1) synthetic photochromics:
(a) the preparation phenyl ring replaces cinnamoyl chloride: by phenyl ring substituted cinnamic acid and excessive slightly thionyl chloride SOCl
2, phosphorus trichloride PCl
3Or phosphorus pentachloride PCl
5Reaction obtained in 4-10 hour under 40～70 ℃;
The structure of described phenyl ring substituted cinnamic acid is as follows:
The structure that described phenyl ring replaces cinnamoyl chloride is as follows:
Wherein
R represents the substituting group on the phenyl ring, and m gets the integer of 1-3;
(b) (a) step is synthetic phenyl ring replacement cinnamoyl chloride is dissolved in the aprotic polar solvent that is added with acid absorbent fully, in ice-water bath, drip to diphenol or polyphenol solution, be warming up to 70 ℃ of reactions 4-10 hour then, obtain the photochromics that is used to mix, its structure is as follows:
Wherein n gets 2 or 3 according to phenols functionality difference;
2) synthetic epoxy resin base light stereospecific polymer
Described epoxy resin-matrix light stereospecific polymer, structure is as follows:
Wherein N is the integer greater than 1;
R
1, R
2All represent the substituting group on the phenyl ring, x, y all get 1 to 3 integer;
Y is selected from following group:
3) with the described photochromics of step 1) to step 2) promptly improve after mixing and the mixing optical directional material of optical directional performance of liquid crystal of described epoxy resin-matrix light stereospecific polymer, wherein,
Cinnamoyl group content with epoxy resin-matrix light stereospecific polymer is a benchmark, and the cinnamoyl content range of the photochromics of doping is in greater than 0 30% scope smaller or equal to polymkeric substance cinnamoyl group content.
5, preparation method as claimed in claim 4 is characterized in that, substituent R or step 2 in the described step (a)) in substituent R
1, R
2Be hydrogen atom, halogen, C
1-C
8Alkyl or C
1-C
8Alkoxy a kind of; Substituent R or R
1, R
2Ortho position, a position or contraposition in phenyl ring;
6, preparation method as claimed in claim 5 is characterized in that, described halogen is meant fluorine, chlorine, bromine and iodine atom; Described alkyl is methyl, ethyl, propyl group, isopropyl, butyl, amyl group, hexyl; Described alkoxy is methoxyl, ethoxy, propoxyl group, butoxy, octyloxy.
7, preparation method as claimed in claim 5 is characterized in that, the diphenol that adopts in described (b) step is for adopting a kind of of p-dihydroxy-benzene, bisphenol-A or '-biphenyl diphenol; Described polyphenol is a phloroglucin.
8, preparation method as claimed in claim 5, it is characterized in that, the aprotic polar solvent that adopts in described (b) step adopts tetrahydrofuran (THF), N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) or N,N-dimethylacetamide (DMAC) a kind of.
9, preparation method as claimed in claim 5 is characterized in that, the acid absorbent in described (b) step is for catching free hydrionic weak base, and employing pyridine Py, triethylamine TEA, N-ethylmorpholine NEM or xylidin NDMA's is a kind of.
10, preparation method as claimed in claim 5 is characterized in that, the cinnamoyl content of the photochromics that mixes in the described step 3) is the 10%-20% scope of the cinnamoyl group content of epoxy resin-matrix light stereospecific polymer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102190887A (en) * | 2010-03-01 | 2011-09-21 | Jsr株式会社 | Composition for organic EL luminophor orientation controlling, organic EL luminophor orientation controlling film, and organic EL element and fabricating method thereof |
| CN102241989A (en) * | 2010-05-06 | 2011-11-16 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display device and polyorganosilioxane compound |
| CN105500857A (en) * | 2015-12-18 | 2016-04-20 | 北京大学 | Light-driven composite with double-layer-film structure and preparation method of light-driven composite |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187521A (en) * | 1996-12-13 | 1998-07-15 | 三星电管株式会社 | Optical alignment composition, alignment layer formed therefrom, liquid crystal device employing alignment layer |
| KR19980078124A (en) * | 1997-04-25 | 1998-11-16 | 손욱 | Photopolymerization type liquid crystal aligning material and manufacturing method of liquid crystal aligning film using same |
| CN1231558C (en) * | 2002-11-28 | 2005-12-14 | 长兴化学工业股份有限公司 | Liquid crystal display orientation layer material and preparing method thereof |
| CN1256404C (en) * | 2004-09-16 | 2006-05-17 | 南开大学 | Light controllable orientated liquid crystal polymer containing photosensitive group of cinnyl and its synthesis |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190887A (en) * | 2010-03-01 | 2011-09-21 | Jsr株式会社 | Composition for organic EL luminophor orientation controlling, organic EL luminophor orientation controlling film, and organic EL element and fabricating method thereof |
| CN102190887B (en) * | 2010-03-01 | 2014-09-10 | Jsr株式会社 | Composition for organic EL luminophor orientation controlling, organic EL luminophor orientation controlling film, and organic EL element and fabricating method thereof |
| CN102241989A (en) * | 2010-05-06 | 2011-11-16 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display device and polyorganosilioxane compound |
| TWI492969B (en) * | 2010-05-06 | 2015-07-21 | Jsr Corp | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element and polyorgano siloxane compound |
| CN105500857A (en) * | 2015-12-18 | 2016-04-20 | 北京大学 | Light-driven composite with double-layer-film structure and preparation method of light-driven composite |
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| CN100428026C (en) | 2008-10-22 |
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