CN101050367A - Method for preparing orientation agent of polyimide liquid crystal - Google Patents
Method for preparing orientation agent of polyimide liquid crystal Download PDFInfo
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- CN101050367A CN101050367A CN 200710049059 CN200710049059A CN101050367A CN 101050367 A CN101050367 A CN 101050367A CN 200710049059 CN200710049059 CN 200710049059 CN 200710049059 A CN200710049059 A CN 200710049059A CN 101050367 A CN101050367 A CN 101050367A
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Abstract
This invention discloses a method for preparing polyamic acid liquid crystal aligning agent. The method comprises: dissolving diamine 1-10 parts into organic solvent 50-100 parts at room temperature under nitrogen protection, adding tetracarboxylic dianhydride 10 parts into the reaction kettle, reacting for 0.1-1 h, adding organic diamine 1-10 parts, reacting for 2-24 h to obtain polyamic acid solution, and adding a mixture of organic solvent 50-400 parts and organic leveling agent 50-500 parts to obtain polyamic acid liquid crystal aligning agent (solid content = 1`-5%). The liquid crystal molecules have a pre-tilt angle of 4-20 deg. The liquid crystal aligning agent can be used for twisted and super-twisted nematic liquid crystal display.
Description
Technical field:
The present invention relates to a kind of preparation method of orientation agent of polyimide liquid crystal, belong to the preparation field of various liquid-crystal displays in the electronic industry.
Background technology:
Liquid-crystal display will obtain good display effect, necessarily requires liquid crystal molecule to have good stable orientations, so liquid crystal aligning agent has become a key subject in liquid-crystal display (LCD) research and development.At present the industrial production liquid crystal aligning agent is polyimide (PI), and this mainly has comprehensive premium propertiess such as high temperature resistant, resist chemical, stable, the easy film forming of orientation, cost of manufacture be low owing to polyimide.
Usually, polyimide cannot not be molten insoluble.Therefore often adopt its presoma, i.e. polyamic acid in use.At first polyamic acid is coated on glass (the being generally ITO) substrate, heating makes its imidization generate polyimide then.The present business-like orientation agent of polyimide liquid crystal overwhelming majority provides with its presoma polyamic acid form.The orientations of liquid crystal molecule mainly is that the substrate surface that has scribbled PI by rubbing is realized, just so-called rubbing manipulation (rubbing method) (write in vain by Ding Mengxian, what day, the polyimide type material. Beijing: Chemical Industry Press, 1998:142.).
The liquid-crystal display of the no display defect of desire preparation just must make liquid crystal molecule produce certain tilt angle, to avoid liquid crystal molecule antidip rotation.The fast development of LCD technology also improves constantly the performance requriements of alignment films, and TN-LCD requires the tilt angle of liquid crystal molecule greater than 1 °, and STN-LCD more requires to be not less than 4 °; And TFT-LCD more requires under the prerequisite of certain alignment capability, and the solidification value of alignment films, voltage retention etc. are had higher requirement.
Whether the selection of tilt angle is appropriate, will directly have influence on the homogeneity of liquid-crystal display and the electro-optical properties of device.EP0282254 discloses diamine monomer and the polyamic acid liquid crystal orientation agent prepared therefrom that a kind of side chain has long alkyl substituent, and the oriented layer that is prepared by this alignment agent can obtain 20～30 ° tilt angle after friction treatment; People such as Lee have reported a kind of organic diamine synthetic polyamic acid liquid crystal orientation agent by tetramethylene tetracarboxylic dianhydride and belt length alkyl group side chain, and tilt angle can reach 13.3 ° of (Lee K.-W., Pack S.-H.., Lien A., et al.Macromolecules, 1996,29:8894-8899).EP0682283 discloses the high tilt angle polyamic acid liquid crystal orientation agent of a class, has the side chain that contains phenyl or xenyl on its main chain, and this side chain contains the substituted radical with electrophilic characteristic, as-CF
3,-CN ,-COCH
3,-NO
2,-F ,-Cl etc., tilt angle can reach 27-39 °.Chinese patent 02102545.2 also discloses the fluorine-containing polyamic acid liquid crystal orientation agent of a kind of side chain, and tilt angle can reach 9 °, and stability better.Many STN type visual angle of liquid crystal display are narrow and small in order to solve, response speed waits problem slowly, and Chinese patent 01141073.6 is reduced to tilt angle about 4 ° from 6～7 ° by selecting different monomers and monomer ratio for use, has improved these problems dexterously.But required bulky side chain diamine monomer all exists and is difficult to acquisition, production cost than problems such as height in the above-mentioned patent, and therefore, such diamine monomer of use of big consumption must improve the production cost of liquid crystal aligning agent.
Summary of the invention:
The objective of the invention is to provide a kind of preparation method of polyamic acid liquid crystal orientation agent, be characterized under a small amount of band bulky side chain organic diamine participates in the situation of reaction, also obtaining that tilt angle is big, the tilt angle good thermal stability, can satisfy the orientation agent of polyimide liquid crystal of TN-LCD and STN-LCD needs at the deficiencies in the prior art.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specifying.
The preparation method of orientation agent of polyimide liquid crystal, its recipe ingredient is:
10 parts of organic tetracarboxylic dianhydrides
1～10 part of specific diamines
1～10 part of organic diamine
100～500 parts of organic solvents
50～500 parts of organic leveling agent
And by following processing step and processing parameter preparation
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, successively 1～10 part of specific diamines is dissolved in 50～100 parts of organic solvents, add 10 parts of organic tetracarboxylic dianhydrides again in reactor, reacted 0.1～1 hour; In this mixture solution, add 1～10 part of organic diamine then, continue reaction and obtained polyamic acid solution in 2～24 hours; Mix with 50～400 parts of organic solvents and 50～500 parts of organic leveling agent and to add that to obtain solid content in this polyamic acid solution be 1～5% polyamic acid liquid crystal orientation agent;
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 60～120 ℃ of preliminary drying 10～60min of temperature then, handle 1～3h in 200～250 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains 5～20um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
The chemical structural formula of this polyimide is as follows:
Wherein, n=20～400, x=0～1, D
1For organic tetracarboxylic dianhydride removes rest parts behind four carboxyls, D
2For organic diamine is removed rest parts behind two amidos, B
1, B
2Be respectively phenyl ring or hexanaphthene, R is-CF
3Or-OCF
3
Organic tetracarboxylic dianhydride is equal benzene tertacarbonic acid's dianhydride, biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride or 1,2,4, any among the 5-hexanaphthene tetracarboxylic dianhydride.
Specific diamines is 4-(4-(trifluoromethyl) benzoyl) cyclohexyl-3; 5-diamines yl benzoic acid ester, 4-(4-(trifluoromethoxy) benzoyl) cyclohexyl-3; 5-diamines yl benzoic acid ester, 4-(4-(trifluoromethyl) benzoyl) phenyl-3; 5-diamines yl benzoic acid ester or 4-(4-(trifluoromethoxy) benzoyl) phenyl-3, any in the 5-diamines yl benzoic acid ester.
Organic diamine is Ursol D, mphenylenediamine, 4,4 '-two amido ditanes, 4,4 '-two amido benzophenone, 4,4 '-diamines yl diphenyl ether, 3,4 '-diamines yl diphenyl ether or 3, any in 3 '-diamines yl diphenyl ether.
Organic solvent is N-Methyl pyrrolidone, N, N '-dimethyl formamide, N, any in N '-N,N-DIMETHYLACETAMIDE or the dimethyl sulfoxide (DMSO).
The organic leveling agent is any in methyl acetate, ethyl acetate, butylacetate, ethylene glycol ethyl ethers diether, phenmethyl phenol, butyl glycol ether, butyl glycol ether acetic ester or the ethyl cellosolve acetate.
The orientation agent of polyimide liquid crystal that adopts method for preparing to obtain.
Orientation agent of polyimide liquid crystal is used for twisted nematic liquid crystal display, super twisted nematic liquid crystal display.
The performance test of orientation agent of polyimide liquid crystal
(1) sign of orientation agent of polyimide liquid crystal orientation characteristic
Ready-made liquid crystal cell is placed under the orthogonal polarizing microscope, and specimen rotating holder makes the liquid crystal cell frictional direction parallel with the polarization direction of the polarizer, observes to have or not light leakage phenomena; Specimen rotating holder is observed transmitted light intensity whether considerable change is taken place.If the liquid crystal cell frictional direction does not have light leak when being parallel to the polarizer, and transmitted light intensity changes greatly during specimen rotating holder, and it is good then to be judged as orientation characteristic.
(2) test of liquid crystal molecule tilt angle
The tilt angle of liquid crystal is 4～20 ° in the liquid crystal cell.For each liquid crystal cell, its tilt angle is tested in our 3～4 different positions of picked at random, asks its mean value then, as the tilt angle of this liquid crystal cell.Testing tool is PAT-20 type tilt angle tester (Changchun joins sincere Instr Ltd. system), and test error is ± 0.1 °.
(3) sign of liquid crystal molecule tilt angle thermostability
The good thermal stability of the tilt angle of liquid crystal in the liquid crystal cell.Place 140 ℃ baking oven to keep 5hr liquid crystal cell, take out its orientation effect of test and tilt angle then.All do not have considerable change as orientation effect and tilt angle, then be judged as the good thermal stability of tilt angle.
The present invention has the following advantages:
(1) by regulating organic diamine and reaching the purpose that improves tilt angle with the reaction sequence of the specific diamines of big side group.Satisfying under the prerequisite of using required tilt angle size, this method will significantly reduce the usage ratio of specific diamines, and the production cost of alignment agent is significantly reduced.
(2) liquid crystal cell is at 140 ℃ down behind the baking 5h, and considerable change does not all take place for the orientation effect of liquid crystal molecule and tilt angle, and liquid crystal molecule tilt angle good thermal stability is described, can satisfy that liquid-crystal display is at high temperature worked for a long time and the service requirements of not losing efficacy.
Embodiment:
Below by embodiment the present invention is carried out concrete description.Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; but can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 7 parts of 4-(4-(trifluoromethyl) benzoyl) cyclohexyl-3,5-diamines yl benzoic acid ester is dissolved in 50 parts of N-Methyl pyrrolidone, adds 10 parts of equal benzene tertacarbonic acid's dianhydrides again in reactor, reacts 1 hour successively; In this mixture solution, add 3 parts of mphenylenediamines then, continue reaction and obtained polyamic acid solution in 24 hours; Mix with 230 parts of N-Methyl pyrrolidone and 100 parts of ethylene glycol ethyl ethers diether and to add that to obtain solid content in this polyamic acid solution be 3% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 60 ℃ of preliminary drying 30min of temperature then, handle 3h in 250 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 10um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 2:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 6 parts of 4-(4-(trifluoromethyl) benzoyl) cyclohexyl-3,5-diamines yl benzoic acid ester is dissolved in 60 parts of N successively, in N '-N,N-DIMETHYLACETAMIDE, add 10 part 3 again, 3 ', 4,4 '-triphen diether tetracarboxylic dianhydride reacted 1 hour in reactor; Add 4 part 4 then in this mixture solution, 4 '-two amido benzophenone continue reaction and obtained polyamic acid solution in 24 hours; With 40 parts of N, N '-N,N-DIMETHYLACETAMIDE and 80 parts of butyl glycol ethers mix and add that to obtain solid content in this polyamic acid solution be 5% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 110 ℃ of preliminary drying 60min of temperature then, handle 3h in 230 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 5um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 3:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 5 parts of 4-(4-(trifluoromethoxy) benzoyl) cyclohexyl-3,5-diamines yl benzoic acid ester is dissolved in 80 parts of N-Methyl pyrrolidone successively, add 10 part 3 again, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride reacted 1 hour in reactor; Add 5 part 4 then in this mixture solution, 4 '-two amido benzophenone continue reaction and obtained polyamic acid solution in 12 hours; Mix with 220 parts of N-Methyl pyrrolidone and 80 parts of ethylene glycol ethyl ethers ether acetic acid fat and to add that to obtain solid content in this polyamic acid solution be 3% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 120 ℃ of preliminary drying 60min of temperature then, handle 1.5h in 230 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 5um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 4:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 4 parts of 4-(4-(trifluoromethoxy) benzoyl) cyclohexyl-3,5-diamines yl benzoic acid ester is dissolved in 90 parts of N successively, in N '-N,N-DIMETHYLACETAMIDE, adds 10 parts of equal benzene tertacarbonic acid's dianhydrides again in reactor, reacts 0.5 hour; In this mixture solution, add 6 parts of Ursol D then, continue reaction and obtained polyamic acid solution in 8 hours; With 220 parts of N, N '-N,N-DIMETHYLACETAMIDE and 70 parts of ethyl acetate are mixed and are added that to obtain solid content in this polyamic acid solution be 2.5% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 80 ℃ of preliminary drying 10min of temperature then, handle 1h in 200 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 10um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 5:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 8 parts of 4-(4-(trifluoromethyl) benzoyl) phenyl-3,5-diamines yl benzoic acid ester is dissolved in 100 parts of N successively, in N '-dimethyl formamide, add 10 part 1,2 again, 3,4-tetramethylene tetracarboxylic dianhydride reacted 0.8 hour in reactor; Add 2 part 4 then in this mixture solution, 4 '-diamines yl diphenyl ether continues reaction and obtained polyamic acid solution in 20 hours; With 320 parts of N, N '-dimethyl formamide and 60 parts of ethylene glycol ethyl ethers ether acetic acid fat mix and add that to obtain solid content in this polyamic acid solution be 2% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 90 ℃ of preliminary drying 20min of temperature then, handle 2h in 200 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 15um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 6:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 3 parts of 4-(4-(trifluoromethyl) benzoyl) phenyl-3,5-diamines yl benzoic acid ester is dissolved in 80 parts of N successively, in N '-dimethyl formamide, add 10 part 1,2 again, 3,4-tetramethylene tetracarboxylic dianhydride reacted 0.2 hour in reactor; Add 7 part 4 then in this mixture solution, 4 '-diamines yl diphenyl ether continues reaction and obtained polyamic acid solution in 8 hours; With 332 parts of N, N '-dimethyl formamide and 268 parts of butylacetates mix and add that to obtain solid content in this polyamic acid solution be 1% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 60 ℃ of preliminary drying 10min of temperature then, handle 2.5h in 250 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 15um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 7:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 4 parts of 4-(4-(trifluoromethoxy) benzoyl) cyclohexyl-3,5-diamines yl benzoic acid ester is dissolved in 80 parts of N-Methyl pyrrolidone, adds 10 parts of equal benzene tertacarbonic acid's dianhydrides again in reactor, reacts 0.5 hour successively; Add 6 part 4 then in this mixture solution, 4 '-two amido ditanes continue reaction and obtained polyamic acid solution in 2 hours; Mix with 222 parts of N-Methyl pyrrolidone and 478 parts of ethylene glycol ethyl ethers ether acetic acid fat and to add that to obtain solid content in this polyamic acid solution be 2.5% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 80 ℃ of preliminary drying 30min of temperature then, handle 2h in 210 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 20um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 8:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 5 parts of 4-(4-(trifluoromethoxy) benzoyl) phenyl-3,5-diamines yl benzoic acid ester is dissolved in 60 parts of N successively, in N '-dimethyl formamide, add 10 part 3 again, 3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride reacted 0.4 hour in reactor; Add 5 part 3 then in this mixture solution, 4 '-diamines yl diphenyl ether continues reaction and obtained polyamic acid solution in 18 hours; With 220 parts of N, N '-dimethyl formamide and 500 parts of butyl glycol ethers mix and add that to obtain solid content in this polyamic acid solution be 2.5% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 80 ℃ of preliminary drying 30min of temperature then, handle 3h in 240 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 20um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 9:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 5 parts of 4-(4-(trifluoromethoxy) benzoyl) phenyl-3,5-diamines yl benzoic acid ester is dissolved in 60 parts of N successively, in N '-dimethyl formamide, add 10 part 1,2 again, 4,5-hexanaphthene tetracarboxylic dianhydride reacted 1 hour in reactor; Add 5 part 3 then in this mixture solution, 3 '-diamines yl diphenyl ether continues reaction and obtained polyamic acid solution in 24 hours; With 402 parts of N, N '-dimethyl formamide and 218 parts of butyl glycol ethers mix and add that to obtain solid content in this polyamic acid solution be 1% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 60 ℃ of preliminary drying 40min of temperature then, handle 1h in 200 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 8um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 10:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 10 parts of 4-(4-(trifluoromethoxy) benzoyl) cyclohexyl-3,5-diamines yl benzoic acid ester is dissolved in 90 parts of N-Methyl pyrrolidone successively, add 10 part 1,2 again, 4,5-hexanaphthene tetracarboxylic dianhydride reacted 1 hour in reactor; Add 1 part 3 then in this mixture solution, 3 '-diamines yl diphenyl ether continues reaction and obtained polyamic acid solution in 24 hours; Mix with 45 parts of N-Methyl pyrrolidone and 95 parts of butyl glycol ether acetate fat and to add that to obtain solid content in this polyamic acid solution be 4% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 100 ℃ of preliminary drying 50min of temperature then, handle 1h in 250 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 8um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 11:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 2 parts of 4-(4-(trifluoromethoxy) benzoyl) phenyl-3,5-diamines yl benzoic acid ester is dissolved in 60 parts of N successively, in N '-dimethyl formamide, add 10 part 1,2 again, 3,4-tetramethylene tetracarboxylic dianhydride reacted 0.1 hour in reactor; Add 8 part 4 then in this mixture solution, 4 '-two amido benzophenone continue reaction and obtained polyamic acid solution in 2 hours; With 239 parts of N, N '-dimethyl formamide and 81 parts of methyl acetates mix and add that to obtain solid content in this polyamic acid solution be 1.5% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 100 ℃ of preliminary drying 20min of temperature then, handle 3h in 230 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 10um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 12:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 1 part of 4-(4-(trifluoromethyl) benzoyl) cyclohexyl-3,5-diamines yl benzoic acid ester is dissolved in 80 parts of N-Methyl pyrrolidone, adds 10 parts of equal benzene tertacarbonic acid's dianhydrides again in reactor, reacts 0.2 hour successively; Add 10 part 4 then in this mixture solution, 4 '-two amido ditanes continue reaction and obtained polyamic acid solution in 2 hours; Mix with 335 parts of N-Methyl pyrrolidone and 65 parts of phenmethyl phenol and to add that to obtain solid content in this polyamic acid solution be 1% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 120 ℃ of preliminary drying 20min of temperature then, handle 1.5h in 200 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 5um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 13:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 3 parts of 4-(4-(trifluoromethoxy) benzoyl) cyclohexyl-3,5-diamines yl benzoic acid ester is dissolved in 70 parts of dimethyl sulfoxide (DMSO) successively, add 10 part 1,2 again, 3,4-tetramethylene tetracarboxylic dianhydride reacted 0.1 hour in reactor; In this mixture solution, add 7 parts of Ursol D then, continue reaction and obtained polyamic acid solution in 4 hours; Mix with 382 parts of dimethyl sulfoxide (DMSO) and 228 parts of phenmethyl phenol and to add that to obtain solid content in this polyamic acid solution be 3% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 80 ℃ of preliminary drying 40min of temperature then, handle 3h in 250 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 20um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 14:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 4 parts of 4-(4-(trifluoromethoxy) benzoyl) phenyl-3,5-diamines yl benzoic acid ester is dissolved in 80 parts of N successively, in N '-dimethyl formamide, adds 10 parts of equal benzene tertacarbonic acid's dianhydrides again in reactor, reacts 0.5 hour; Add 6 part 3 then in this mixture solution, 4 '-diamines yl diphenyl ether continues reaction and obtained polyamic acid solution in 12 hours; With 50 parts of N, N '-dimethyl formamide and 50 parts of butyl glycol ether acetate fat mix and add that to obtain solid content in this polyamic acid solution be 5% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 70 ℃ of preliminary drying 50min of temperature then, handle 2h in 220 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 15um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
Embodiment 15:
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, with 2 parts of 4-(4-(trifluoromethoxy) benzoyl) cyclohexyl-3,5-diamines yl benzoic acid ester is dissolved in 95 parts of N-Methyl pyrrolidone, adds 10 parts of biphenyl tetracarboxylic dianhydrides again in reactor, reacts 0.2 hour successively; Add 8 part 4 then in this mixture solution, 4 '-two amido benzophenone continue reaction and obtained polyamic acid solution in 8 hours; Mix with 395 parts of N-Methyl pyrrolidone and 290 parts of phenmethyl phenol and to add that to obtain solid content in this polyamic acid solution be 2% polyamic acid liquid crystal orientation agent.
(2) preparation of liquid crystal cell
To evenly be spun on by the polyamic acid liquid crystal orientation agent solution that above-mentioned preparation method makes on the clean ito glass, successively this ito glass substrate is placed on 90 ℃ of preliminary drying 10min of temperature then, handle 1.5h in 240 ℃ of imidizations of temperature again, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains the 10um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell.
The The performance test results of embodiment is detailed to be shown in Table 1.
The orientation effect of table 1 polyamic acid liquid crystal orientation agent, tilt angle and thermostability thereof
| Embodiment | Orientation characteristic | Tilt angle (°) | Thermostability |
| Embodiment 1 | Well | 12 | Well |
| Embodiment 2 | Well | 14.6 | Well |
| Embodiment 3 | Well | 9.1 | Well |
| Embodiment 4 | Well | 6 | Well |
| Embodiment 5 | Well | 10.7 | Well |
| Embodiment 6 | Well | 4.3 | Well |
| Embodiment 7 | Well | 4.1 | Well |
| Embodiment 8 | Well | 5.2 | Well |
| Embodiment 9 | Well | 7.2 | Well |
| Embodiment 10 | Well | 19.3 | Well |
| Embodiment 11 | Well | 4.7 | Well |
| Embodiment 12 | Well | 4.5 | Well |
| Embodiment 13 | Well | 4.9 | Well |
| Embodiment 14 | Well | 6.8 | Well |
| Embodiment 15 | Well | 5.2 | Well |
Claims (8)
1. the preparation method of an orientation agent of polyimide liquid crystal is characterized in that this method may further comprise the steps, and wherein said raw material umber is parts by weight:
10 parts of organic tetracarboxylic dianhydrides
1～10 part of specific diamines
1～10 part of organic diamine
100～500 parts of organic solvents
50～500 parts of organic leveling agent
And by following processing step and processing parameter preparation
(1) preparation of polyamic acid liquid crystal orientation agent
Under room temperature and nitrogen protection, successively 1～10 part of specific diamines is dissolved in 50～100 parts of organic solvents, add 10 parts of organic tetracarboxylic dianhydrides again in reactor, reacted 0.1～1 hour; In this mixture solution, add 1～10 part of organic diamine then, continue reaction and obtained polyamic acid solution in 2～24 hours; Mix with 50～400 parts of organic solvents and 50～500 parts of organic leveling agent and to add that to obtain solid content in this polyamic acid solution be 1～5% polyamic acid liquid crystal orientation agent;
(2) preparation of liquid crystal cell:
The polyamic acid liquid crystal orientation agent solution that aforesaid method is made evenly is spun on the clean ito glass, successively this ito glass substrate is placed on 60～120 ℃ of preliminary drying 10～60min of temperature, handle 1～3h in 200～250 ℃ of imidizations of temperature, then with rub Kapton on this ito glass substrate of rubbing machine, and two ito glass substrates are bonded to box along the frictional direction antiparallel with the optic-solidified adhesive that contains 5～20um introns, pour into liquid crystal, seal with optic-solidified adhesive subsequently, obtain liquid crystal cell;
The chemical structural formula of this polyimide is as follows:
Wherein, n=20～400, x=0～1, D
1For organic tetracarboxylic dianhydride removes rest parts behind four carboxyls, D
2For organic diamine is removed rest parts behind two amidos, B
1, B
2Be respectively phenyl ring or hexanaphthene, R is-CF
3Or-OCF
3
2. the preparation method of orientation agent of polyimide liquid crystal according to claim 1 is characterized in that the tetracarboxylic dianhydride is equal benzene tertacarbonic acid's dianhydride, biphenyl tetracarboxylic dianhydride, 3,3,4,4 '-phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride or 1,2,4, any among the 5-hexanaphthene tetracarboxylic dianhydride.
3. the preparation method of orientation agent of polyimide liquid crystal according to claim 1; it is characterized in that specific diamines is 4-(4-(trifluoromethyl) benzoyl) cyclohexyl-3; 5-diamines yl benzoic acid ester, 4-(4-(trifluoromethoxy) benzoyl) cyclohexyl-3; 5-diamines yl benzoic acid ester, 4-(4-(trifluoromethyl) benzoyl) phenyl-3; 5-diamines yl benzoic acid ester or 4-(4-(trifluoromethoxy) benzoyl) phenyl-3, any in the 5-diamines yl benzoic acid ester.
4. the preparation method of orientation agent of polyimide liquid crystal according to claim 1, it is characterized in that organic diamine is Ursol D, mphenylenediamine, 4,4 '-two amido ditanes, 4,4 '-two amido benzophenone, 4,4 '-diamines yl diphenyl ether, 3,4 '-diamines yl diphenyl ether or 3, any in 3 '-diamines yl diphenyl ether.
5. the preparation method of orientation agent of polyimide liquid crystal according to claim 1 is characterized in that used organic solvent is N-Methyl pyrrolidone, N, N '-dimethyl formamide, N, any in N '-N,N-DIMETHYLACETAMIDE or the dimethyl sulfoxide (DMSO).
6. the preparation method of orientation agent of polyimide liquid crystal according to claim 1 is characterized in that the organic leveling agent is any in methyl acetate, ethyl acetate, butylacetate, ethylene glycol ethyl ethers diether, phenmethyl phenol, butyl glycol ether, butyl glycol ether acetic ester or the ethyl cellosolve acetate.
7. the orientation agent of polyimide liquid crystal that adopts the described method of claim 1 to prepare.
8. be used for twisted nematic liquid crystal display, super twisted nematic liquid crystal display as orientation agent of polyimide liquid crystal as described in the claim 7.
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| CN105659155B (en) * | 2013-10-23 | 2020-01-21 | 日产化学工业株式会社 | Liquid crystal aligning agent containing polyimide precursor and/or polyimide having thermally-releasable group |
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| CN108780250B (en) * | 2016-07-27 | 2022-03-08 | 株式会社Lg化学 | Transmittance variable film, method for producing same, and use thereof |
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