CN1495156A - Aromatic diamine derivative, its preparation method and LCD component regiospecific film material containing it - Google Patents
Aromatic diamine derivative, its preparation method and LCD component regiospecific film material containing it Download PDFInfo
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- CN1495156A CN1495156A CNA03157162XA CN03157162A CN1495156A CN 1495156 A CN1495156 A CN 1495156A CN A03157162X A CNA03157162X A CN A03157162XA CN 03157162 A CN03157162 A CN 03157162A CN 1495156 A CN1495156 A CN 1495156A
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Abstract
The present invention discloses a novel aromatic diamine derivative. The diamine derivative can be used in the tetracarboxylic acid and diamine polymerization reaction to form novel polyamic acid. The polyamic acid is undergone the processes of baking and closed circulation treatment to form polyimide. It can be used as regiospecific membrane material of liquid crystal display component, and has the good regiospecific property and stability, and has the effect of raising pre-defined inclined regiospecific angle (pre-inclined angle).
Description
Technical field
The present invention is about a kind of new aromatic branched chain type structure diamine monomer derivative, and contains the alignment film material of the liquid-crystal display of this diamine monomer derivative, and this material has the effect that the liquid crystal molecule that can allow in substrate has stable high dip angle relatively.
Background technology
Attracting advantages such as liquid-crystal display is the indicating meter that utilizes liquid crystal photoelectricity to change, and it has, and volume is little, in light weight, low power consumption and display quality are good have become the flat-panel screens main flow in recent years.
In LCD device, typical Liquid crystal module is twisted nematic (TN) field effect mode Liquid crystal module, and its use has positive dielectric anisotropy nematic liquid crystal.Generally speaking, liquid crystal molecule is inserted between a pair of substrate that contains electrode, and the alignment direction of this two substrates is vertical mutually, via the arrangement mode of control electric field may command liquid crystal molecule.With regard to this type liquid crystal display assembly, it is considerable allowing the long axis direction of liquid crystal molecule and substrate surface that the orientation at even angle of inclination can be arranged, and can make Liquid Crystal Molecules Alignment become the material of even tilt angle (pre-tilt angle) orientation to be called alignment film.
Industry member has two kinds of typical alignment film preparation methods at present.
First method is by steam deposition inorganic substance to be made mineral membrane, forms film as evaporation that silicon-dioxide is tilted in substrate, and by orientation, though method can obtain uniform orientation thus, this method is not more had an industrial efficiency to liquid crystal molecule in the evaporation direction.
Second method then is coated on organic membrane on the substrate surface, utilizes the soft cloth of cotton, nylon or polyester to be rubbed, and makes this organic membrane surface be directed, to such an extent as to allow liquid crystal molecule at frictional direction by orientation.Utilize this method, also obtain even orientation quite easily, because this method is simpler and easy, so be widely used in technical scale most.The polymkeric substance that can form organic film is polyvinyl alcohol, polyoxyethylene, polymeric amide or polyimide for example, and wherein polyimide is owing to have character such as chemical stability and heat-resistant quality, the most normal being utilized as alignment film material.
Because of the product application difference, alignment film material can be divided into twisted-nematic (TN) type that is applied to, supertwist is used to row (STN) type and thin film transistor (TFT) type liquid-crystal display.Alignment film is coated with the character with good except that need possess regiospecific, and tilt angle also is a critical nature.On document, there are many methods can control tilt angle at present, for example, it is alignment film material that European patent EP 60485-A discloses with siloxanes (siloxane) copolymerized macromolecule material, it utilizes the amount of siloxanes to control the angle of tilt angle, but the material that it disclosed is only applicable to wide viewing angle super-twist nematic and film transistor type liquid-crystal display.Japanese Patent 05313169-A becomes the degree of polyimide to control alignment film with the polyamic acid solution endless loop, but only applicable to high tilt angle.The polyamic acid that Japanese Patent 07287235-A adding terminal has the polymeric amide of straight chain type alkyl structure and has aliphatic tetracarboxylic acid structure can increase the pre-dumping angle, but it is only applicable to super-twist nematic liquid crystal display in alignment film.
In addition, about 1～3 ° usually at the inclination angle of rubbed polyimide resin gained is difficult to obtain high tilt angle.Be head it off, Japanese unexamined reason patent 142099/1987 proposes a kind of liquid crystal orienting film, and it comprises the reaction product of long-chain alkanamine and polyimide resin, because importing chain alkyl, so can increase tilt angle, but because of the import volume of chain alkyl limited, so the enhancement of tilt angle is limited; In United States Patent (USP) 5773559/1998, once proposed to introduce again to contain the diamine monomer of cholesterol (cholesterol) structure to the polyimide alignment film resin, though the control of its tilt angle is good, but it contains the diamine monomer of cholesterol structure, some can't be stablized in acid for a long time, some then is that preparation process is loaded down with trivial details, and synthetic cost is too expensive.
For solving the aforesaid drawbacks, this case inventor finds that through broad research a kind of novelty contains cholesterol structure aromatic diamine monomer derivative, it can be applicable in the alignment film, its synthesis step is simple, has good regiospecific, and has stable high dip angle characteristic and stable chemically reactive.
Summary of the invention
One object of the present invention system provides a kind of novel aromatic diamine monomer derivative.
Another object of the present invention system provides the method for this aromatic diamine monomer derivative of preparation.
Another object of the present invention system provides a kind of liquid-crystal display alignment film material that contains this aromatic diamine monomer derivative.
The present invention relates to a kind of aromatic diamine derivative, it has the structure suc as formula (I):
Formula (I)
Wherein,
R
1Be H or C
1-C
5Alkyl; And
R
2For being selected from the steroid derivatives group that comprises following group:
Described R
1Be H or methyl, and R
2For
Described diamine derivative is 4-[(17-(1,5-dimethyl hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-ten tetrahydrochysenes-1H-encircles penta [a] phenanthrene-3-yl) the oxygen base]-1, the 3-phenylenediamine.
The invention still further relates to the method for a kind of preparation suc as formula (I) compound, it comprises the following steps:
(a) exist down in alkali and organic solvent, the dinitrobenzene thing of formula (II)
Formula (II)
With steroid compound HOR
2React, obtain the compound of formula (III);
Formula (III)
And
(b) formula (III) compound is carried out hydrogenation, obtains formula (I) compound,
Formula (I)
R wherein
1And R
2Definition the same, X is F, Cl or Br.
Alkali wherein is selected from carbonate, Trimethylamine, triethylamine and the diisopropyl ethyl amine that comprises IA and IIA family metal, and composition thereof.
Organic solvent system wherein is selected from ethylene dichloride, methylene dichloride, chloroform, acetone, butanone, N-N-methyl 2-pyrrolidone N-, N,N-dimethylacetamide or N, dinethylformamide or its mixture.
The invention further relates to a kind of polyimide resin that is used for liquid crystal display assembly as alignment film material, this polyimide resin is to obtain through polyreaction by tetracarboxylic acid or its dicarboxylic anhydride derivative and diamines, and wherein this diamines comprises the above-mentioned formula of being selected from of at least 5 moles of % (I) diamine derivative.
Described diamines comprises at least 20 moles of above-mentioned formulas of % (I) diamine derivative.
Described diamines can also comprise 4-[(17-(1,5-dimethyl hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-ten tetrahydrochysenes-1H-encircles penta [a] phenanthrene-3-yl) the oxygen base]-1, the 3-phenylenediamine.
Embodiment
Disclosed aromatic diamine monomer derivative, its structure is suc as formula shown in (I):
Formula (I)
Wherein:
R
1Be H or C
1-C
5Alkyl;
R
2For being selected from the steroid derivatives group that comprises following group:
According to preferred embodiment of the present invention, formula (I) compound can be 4-[(17-(1,5-dimethyl hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-ten tetrahydrochysenes-1H-encircles penta [a] phenanthrene-3-yl) the oxygen base]-1, the 3-phenylenediamine.
The aromatic diamine monomer derivative of formula of the present invention (I) generally can be synthesized into by the following step:
X＝F，Br，Cl
Therefore, the present invention discloses the method that preparation has the aromatic diamine monomer derivative of formula (I) in addition.This method comprises the following steps:
(a) exist down in alkali and organic solvent, the dinitrobenzene thing of formula (II)
Formula (II)
With steroid compound HOR
2React, obtain formula (III) compound;
Formula (III)
And
(b) formula (III) compound is carried out hydrogenation, obtain formula (I) compound
Formula (I)
Above-mentioned steps Chinese style (I) is to formula (III) compound, wherein R
1And R
2Have foregoing definition, X is F, Cl or Br.
In the synthetic method of above-mentioned diamine monomer derivative, main system will have the dinitrobenzene of formula (II), carry out substitution reaction under alkali and organic solvent exist, and carry out reduction reaction (hydrogenation) more subsequently and make the diamine monomer derivative of formula (I).The alkali that is added has the effect as catalyzer, and it can increase the speed of building-up reactions and reduce temperature of reaction.Be applicable to the alkali in this synthetic method, can be selected from the basic cpd that includes but not limited to that IA and IIA family metal form, be preferably the carbonate of IA and IIA family metal; And tertiary amine, for example Trimethylamine, triethylamine, diisopropyl ethyl amine etc.Be applicable to the organic solvent in this synthetic method, can be selected from and include but not limited to alkyl halide, as methylene dichloride, ethylene dichloride, chloroform etc.; Ketone is as acetone, butanone etc.; The N-N-methyl 2-pyrrolidone N-; N,N-dimethylacetamide and N, dinethylformamide.
In above-mentioned reduction reaction (hydrogenation), can utilize the known hydrogenation mode of skill personage to carry out.For example utilize metal catalysts such as Pt, Pd, Raney-Ni, under suitable pressure and temperature, carry out reduction reaction with hydrogen; Or for example utilize SnCl
2Or reductive agent such as Fe carries out reduction reaction with concentrated hydrochloric acid, or utilizes LiAlH
4Reductive agent carries out reduction reaction in aprotic solvent.
The present invention provides a kind of alignment film material of liquid crystal aligning in addition, it comprises the polyimide resin of the diamine monomer derivative that contains formula of the present invention (I), this resin can be by known method in any this skill, with tetracarboxylic acid or its dicarboxylic anhydride derivative of commonly using, obtain through polyreaction with the diamine monomer derivative of diamine monomer of commonly using and formula of the present invention (I).This type of polyimide resin can be dissolved in organic polar solvent, as N-N-methyl 2-pyrrolidone N-, N, in N-N,N-DIMETHYLACETAMIDE or γ-butyl lactone, to obtain polyimide resin solution, it is coated on the glass or plastic film transparency carrier with transparency electrode then, then under 120 to 350 ℃ of temperature, solvent is evaporated through thermal treatment, to form polyimide resin film, after rubbing is handled, obtain liquid crystal orienting film, it can make liquid crystal molecule have to stablize high tilt angle.
Can be applicable to the tetracarboxylic acid of commonly using of the present invention and form part, be not particularly limited usually, for example the aromatic tetracarboxylic acid, it can be selected from but be not limited to 1,2,4, the 5-benzene tertacarbonic acid, 3,3 ', 4,4 '-phenylbenzene tetracarboxylic acid, 2,3,3 ', 4-phenylbenzene tetracarboxylic acid, two (3,4-dicarboxyl phenyl) ether, 3,3 ' 4,4 '-benzophenone tetracarboxylic acid, two (3,4-dicarboxyl phenyl) sulfoxide, two (3,4-dicarboxyl phenyl) methane, 2, two (3, the 4-dicarboxyl phenyl) propane of 2-, 1,1,1,3,3,3-hexafluoro-2, two (3, the 4-dicarboxyl phenyl) propane of 2-, two (3,4-dicarboxyl phenyl) dimethylsilane, two (3,4-dicarboxyl phenyl) diphenyl silane, 2,3,4,5 pyridine tetracarboxylic acids and 2,6-two (3,4-dicarboxyl phenyl) pyridine, and comprise above-mentioned deutero-dicarboxylic anhydride and dicarboxylic acid two acetyl halide compounds; Aliphatics ring-type tetracarboxylic acid is as tetramethylene tetracarboxylic acid, pentamethylene tetracarboxylic acid, hexanaphthene tetracarboxylic acid, 1,3,5-tricarboxylic basic ring amyl group acetic acid and 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene Succinic anhydried, and comprise its deutero-dicarboxylic anhydride and dicarboxylic acid two acetyl halide compounds; The aliphatics tetracarboxylic acid, as BTCA, and dicarboxylic anhydride and dicarboxylic acid two acetyl halide compounds.These tetracarboxylic acids are formed part can be by the mixture use of two or more tetracarboxylic acids alone or in combination.
Can be applicable to the diamines of commonly using of the present invention and form part, use the primary diamine of synthesizing polyamides acid usually.This type of diamines is formed part can be selected from aromatic diamine, for example include but not limited to the diamines ditan, the diamines diphenyl ether, 2,2-diamines phenyl-propane, two (3,5-diethyl-4-aminocarbonyl phenyl) methane, the diamines sulfobenzide, two amido benzophenone, two amido naphthalenes, 1, two (the 4-amido phenoxy group) benzene of 4-, 1, two (the 4-amido phenoxy group) benzene of 3-, 4, two (the 4-amido phenoxy group) sulfobenzides of 4-, 2,2-two (4,4-amido Phenoxyphenyl) propane, 2, two (4-aminocarbonyl phenyl) HFC-236fa and 2 of 2-, two (4, the 4-amido Phenoxyphenyl) HFC-236fa of 2-; The aliphatics cyclic diamine is as two (4-amido cyclohexyl) methane, two (4-amido-3-methylcyclohexyl) methane; And aliphatie diamine, as butanediamine and hexanediamine.Above-mentioned diamines is formed part and can be used separately, or makes up the mixture use of two or more diamines.
The diamines composition part that is used among the present invention must comprise at least a diamine monomer derivative that is selected from formula of the present invention (I), its consumption ratio in employed diamine monomer total amount, is generally at least 5 moles of %, be preferably at least 20 moles of %, be more preferred from least 50 moles of %.
Aspect the polyimide polyreaction, product degree of polymerization is preferably specific viscosity (reducedviscosity) 0.05 to 3.0dl/g, and the specific viscosity value of solution is 30 ℃ of temperature, and N-N-methyl 2-pyrrolidone N-concentration is measured when being 0.5g/dl.
For the reaction of tetracarboxylic acid or its dicarboxylic anhydride derivative and diamines and polymerization process and without particular limitation, can utilize in this skill method known to carry out.General employed method is that diamines is dissolved in organic polar solvent, as the N-N-methyl 2-pyrrolidone N-, N, N-N,N-DIMETHYLACETAMIDE or N in the dinethylformamide, add tetracarboxylic acid or its dicarboxylic anhydride derivative then and carry out polyreaction in this solution and obtain polyamic acid solution.The temperature range of this reaction is that preferable temperature of reaction is-5 ℃ to 100 ℃ between-20 ℃ to 150 ℃; Polyreaction forms the required time of polyamic acid usually between 3 minutes to 24 hours, and the preferable time was between 10 minutes to 6 hours.
Alignment film material of the present invention has suitable molecular weight distribution and intensity in order to make polyamic acid, and the mol ratio of its tetracarboxylic acid or its dicarboxylic anhydride derivative and diamines is between the 0.8-1.2.When the mol ratio of tetracarboxylic acid or its dicarboxylic anhydride derivative and diamines more near 1 the time, molecular weight is big more and viscosity is high more.When the mol ratio of tetracarboxylic acid or its dicarboxylic anhydride derivative and diamines less than 1 the time, can add an amount of end and add cap functional group (end cap functional group), remedy the part of difference, be not equal to the oxidative phenomena that was caused at 1 o'clock to reduce because of mol ratio.The terminal closed official who is suitable for can be selected from anhydride phthalic acid, maleic anhydride, aniline and hexamethylene alkanamine etc. by base system.
In addition the polymerization degree and the reduction reaction times, can in reaction, add catalyzer in order to increase polyreaction of the present invention.The catalyzer that is suitable for can be selected from but be not limited to triethylamine, diethylamide, n-butylamine and pyridine etc.These catalyzer also have the function of adjusting the pH value of solution value.
Obtain polyamic acid after polyreaction is finished, its polymerization degree is 10 to 5,000, and the preferable polymerization degree is 16 to 250, and weight average molecular weight is 5,000 to 2,500,000, and better suited weight average molecular weight is 8,000 to 125,000.
Solid content when polyreaction forms polyamic acid, promptly polymer phase should be between 10% to 30% for solvent weight percent.So when using,, solid content should be downgraded between 4% to 10% for regulating viscosity with the control thickness.
For improving the tackyness of polyamic acid resin alignment film material, can in resin, add trace mineral supplement, as silane coupling agent (silane coupling agent) to base material.Silane coupling agent commonly used is such as but not limited to 3-amine propyl trimethoxy silicane, 3-amine propyl-triethoxysilicane, 2-amine propyl trimethoxy silicane, 2-amine propyl group three ethoxy alkyl silanes, and composition thereof.
Alignment film material of the present invention is in order to cooperate processibility, with solid content with organic solvent diluting to 4% to 10% of weight percent to regulate viscosity, be convenient to follow-up alignment film procedure for processing.Its organic solvent that is suitable for system be selected from the N-N-methyl 2-pyrrolidone N-,-cresols, gamma-butyrolactone, N,N-dimethylacetamide and N, dinethylformamide, and composition thereof.Perhaps, the solvent that does not even have dissolving polyamide resin ability, only otherwise cause polyamide resin in solution system, to produce bad solubleness, also can be added in the above-mentioned solvent, this kind solvent is such as but not limited to ethylene glycol monomethyl ether (Ethylene glycol monoethyl ether), ethylene glycol monobutyl ether (Ethylene glycol monobuthyl ether), Diethylene Glycol single-butyl ether (Diethyleneglycol monobuthyl ether), TC (Diethylene glycolmonoethyl ether) diethylene glycol monobutyl ether (Butyl carbitol), acetic acid ethyl carbitol ester (Ethyl carbitol acetate) or ethylene glycol, or its mixture.Preferable below 90 of percentage that should be controlled at whole solvent systems weight of the amount of this kind solvent.
For the polyamic acid resin in the solution is converted into polyimide resin, normally used method becomes polyimide resin for the dehydration endless loop that heating makes, the temperature of heating can be according to circumstances between from 100 ℃ to 350 ℃, better suited cyclisation temperature is between 120 ℃ to 320 ℃, and the cyclisation time is between 3 minutes to 6 hours.
Person provided by the present invention is a kind of alignment film material that makes Liquid Crystal Molecules Alignment become high tilt angle, and it can evenly be coated alignment film material on the substrate via commercial coating machine such as scraper coating, rotary coating or roller coating etc.In this method, lie on the transparent substrate that has transparent electrode material on glass or the plastic plate, coating thickness is 200 to 3000 polyimide resin film, then polyimide resin film is obtained liquid crystal orienting film after rubbing is handled.
For determining that the novel alignment film material of the present invention can produce the alignment film at the high pre-hectare of angle of tool, now with the making of liquid crystal cell and the test of tilt angle, detects the high tilt angle characteristic of alignment film material of the present invention.The making of liquid crystal cell system coats alignment film material of the present invention with its surface after two indium sb oxides (ITO) glass is cleaned, and its coating process can be scraper coating, rotary coating or roller coating, through roasting, high bake in advance, forms the polyimide alignment film; After cooling is carried out rubbing with bristle, it is assembled into liquid crystal cell, pour into liquid crystal after, utilize tilt angle test machine (Tilt Angle Tester, TBA) test tilt angle.
The present invention will further be described in detail via the following example, only this narration only is in order to illustrate the present invention, but not the scope of the invention is imposed any restrictions, modification and change that any personage who is familiar with this skill can reach easily are included in the scope of this case specification sheets disclosure and appended claim.
Embodiment
Synthesizing of aromatic diamine compound
Example 1
4-[(17-(1,5-dimethyl hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-ten tetrahydrochysenes-1H-encircles penta [a] phenanthrene-3-yl) the oxygen base]-1,3-phenylenediamine (hereinafter to be referred as " CH-1 ") synthetic
In 500 of prolong milliliters of two-neck bottles, add 1,2-ethylene dichloride (200 milliliters) on the frame, add 2 again, 4-dinitrofluorobenzene (18.62 grams, 0.100 mole), cholesterol (cholesterol, 39.44 gram, 0.102 mole) and triethylamine (11.13 grams, 0.110 mole).After stirring 6 hours under the room temperature, add distilled water (300 milliliters), with ethyl acetate extraction (400 milliliters * 3), with the organic layer collected with anhydrous sodium sulfate drying, after filtration and after concentrating, utilize ethanol to carry out recrystallize, obtain 17-(1,5-dimethyl hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-ten tetrahydrochysenes-1H-ring penta [a] phenanthrene-3-base (2, the 4-dinitrophenyl) ether (16.00 grams, 0.029 mole), productive rate is 29%.Fusing point: 175.8 ~ 177.0 ℃.SPECTRAL DATA: IR (KBr) 3121,3088,2918,2853,1611,1530,1470,1350,1287,1159,1097,1075cm
-1 1H NMR (CDCl
3, 400MHz) δ 8.69 (d, J=2.7Hz, 1H), 8.37 (dd, J=2.5, J=9.3Hz, 1H), 7.18 (d, J=9.4Hz, 1H), 5.44 (d, J=4.9Hz, 1H), 4.41 (septet, J=5.2Hz, 1H), 2.60 ~ 2.40 (m, 2H), 2.10 ~ 1.70 (m, 6H), 1.65 ~ 0.80 (m, 32H), 0.69 (s, 3H).
13C?NMR(CDCl
3，100.6MHz)δ155.8，139.5，138.7，128.6，123.6，121.8，115.1，80.5，56.6，56.0，50.0，42.2，39.6，39.4，37.9，36.8，36.6，36.1，35.7，31.8，31.7，28.1，27.9，27.7，24.2，23.7，22.7，22.4，21.0，19.3，18.6，11.7。
With the 17-(1,5-dimethyl hexyl)-10 of gained, 13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-ten tetrahydrochysenes-1H-ring penta [a] phenanthrene-3-base (2, the 4-dinitrophenyl) ether (10.00 grams, 0.018 mole), ethanol (300 milliliters) and 10%Pd/C (0.50 gram) insert in 1 liter of reaction flask, react on and feed hydrogen normal pressure under after 6 hours, after filtration with the concentrated crude product that obtains.Utilize ethanol to carry out recrystallize crude product, obtain compound 4-[(17-(1,5-dimethyl hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-ten tetrahydrochysenes-1H-encircles penta [a] phenanthrene-3-yl) the oxygen base]-1,3-phenylenediamine (6.98 grams, 0.014 mole), productive rate is 78%.Fusing point: 158.6 ~ 163.3 ℃.SPECTRAL DATA: IR (KBr) 3434,3347,2932,2864,1614,1510,1457,1366,1215,1036 cm
-1 1H NMR (CDCl
3, 400MHz) δ 6.54 (d, J=8.3Hz, 1H), 5.91 (d, J=2.6Hz, 1H), 5.70 (dd, J=8.3, J=2.6Hz, 1H), 5.28 (d, J=4.5Hz, 1H), 4.39 (d, J=9.8Hz, 3H), 3.63 (septet, J=5.2Hz, 1H), 2.35 ~ 2.20 (m, 2H), 2.00 ~ 1.70 (m, 5H), 1.60 ~ 0.80 (m, 34H), 0.64 (s, 3H).
13C?NMR(CDCl
3，100MHz)δ143.9，140.7，140.5，135.7，121.5，118.7，102.7，101.6，79.4，56.4，55.8，49.8，42.1，36.9，36.6，35.9，35.4，31.6，28.5，28.0，27.6，24.1，23.4，22.9，22.6，20.9，19.4，18.8，11.9。
Polyimide synthesizes the preparation with alignment film
Example 2
18.5 gram (0.045 mole) 2, two [4-(the 4-amine phenoxy group) phenyl] propane (this paper is designated hereinafter simply as BAPP) of 2-, 2.47 gram (0.005 mole) Compound C H-1 and 10.9 gram (0.05 moles) 1,2,4,5-phthalic acid (this paper is designated hereinafter simply as PMDA), 127 the gram NMP under room temperature the reaction 25 hours, add again 478 the gram NMP with its dilution after, obtain polyamic acid solution, its specific viscosity is 1.00dl/g.This solution rotates under 3500rpm to be coated on the glass baseplate with transparency electrode, heat under 250 ℃ and handled 60 minutes, form polyimide resin film, after cooling is carried out rubbing with bristle, utilize 50 microns interval dose, it is assembled into the direction liquid crystal cell that is parallel to each other, pour into liquid crystal (model: ZLI-2293, make by Merck company) after, this assembly rotates between quadrature Ni Keer Ling Jing (crossed nicols), light and half-light can gratifyingly be analysed identification clearly, and (Tilt Angle Tester, TBA) obtaining tilt angle numerical value is 5.2 to utilize the tilt angle measuring machine.
Comparative example 1
20.5 the gram (0.05 mole) BAPP with 10.9 the gram (0.05 mole) PMDA 126 the gram NMP in, under room temperature the reaction 15 hours, add again 470 the gram NMP with its dilution after, the acquisition polyamic acid solution, its specific viscosity is 1.22dl/g.This solution rotates under 3500rpm to be coated on the glass baseplate with transparency electrode, heat under 250 ℃ and handled 60 minutes, form polyimide resin film, after cooling is carried out rubbing with bristle, utilize 50 microns interval dose, it is assembled into the direction liquid crystal cell that is parallel to each other, pour into liquid crystal (model: ZLI-2293, make by Merck company) after, it is 2.6 that this assembly utilizes the tilt angle measuring machine to obtain tilt angle numerical value.
Comparative example 2
20.5 gram (0.05 mole) BAPP, 5.4 gram (0.025 mole) PMDA and 7.4 gram (0.025 mole) BPDA (3,3 ', 4,4 '-phenylbenzene dicarboxylic anhydride), 133 the gram NMP in, under room temperature the reaction 20 hours, add again 500 the gram NMP with its dilution after, obtain polyamic acid solution, its specific viscosity is 1.15dl/g.This solution rotates under 3500rpm to be coated on the glass baseplate with transparency electrode, heat under 250 ℃ and handled 60 minutes, form polyimide resin film, after cooling is carried out rubbing with bristle, utilize 50 microns interval dose, it is assembled into the direction liquid crystal cell that is parallel to each other, pour into liquid crystal (model: ZLI-2293, make by Merck company) after, it is 3.0 that this assembly utilizes the tilt angle measuring machine to obtain tilt angle numerical value.
Now the result with example 2 and comparative example 1 and 2 further specifies as in the table one.
Table one
| The embodiment numbering | Diamine compounds (mole %) | Tetracarboxylic acid (mole %) | Regiospecific | Tilt angle | ||
| ????BAPP | ????CH-1 | ????PMDA | ??BPDA | |||
| Embodiment 2 | ????90 | ????10 | ????100 | Good | ????5.2 | |
| Comparative example 1 | ????100 | ????100 | Can | ????2.6 | ||
| Comparative example 2 | ????100 | ????50 | ??50 | Can | ????3.0 | |
By The above results as can be known, in alignment layer material, add aromatic diamine monomer derivative of the present invention, can obtain the effect of good regiospecific and raising tilt angle.
Claims (9)
1. aromatic diamine derivative, it has the structure suc as formula (I):
Formula (I)
Wherein,
R
1Be H or C
1-C
5Alkyl; And
R
2Comprise following steroid derivatives group for being selected from:
2. diamine derivative according to claim 1, wherein R
1Be H or methyl, and R
2For
3. diamine derivative according to claim 1 is 4-[(17-(1,5-dimethyl hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-ten tetrahydrochysenes-1H-encircles penta [a] phenanthrene-3-yl) the oxygen base]-1, the 3-phenylenediamine.
4. method for preparing formula as claimed in claim 1 (I) compound, it comprises the following steps:
(a) exist down in alkali and organic solvent, the dinitrobenzene thing of formula (II)
Formula (II)
With steroid compound HOR
2React, obtain the compound of formula (III);
Formula (III)
And
(b) formula (III) compound is carried out hydrogenation, obtains formula (I) compound,
Formula (I)
R wherein
1And R
2Have definition as claimed in claim 1, X is F, Cl or Br.
5. according to the method for claim 4, wherein alkali is selected from carbonate, Trimethylamine, triethylamine and the diisopropyl ethyl amine that comprises IA and IIA family metal, and composition thereof.
6. according to the method for claim 4, wherein organic solvent is selected from ethylene dichloride, methylene dichloride, chloroform, acetone, butanone, N-N-methyl 2-pyrrolidone N-, N,N-dimethylacetamide or N, dinethylformamide or its mixture.
7. polyimide resin that is used for liquid crystal display assembly as alignment film material, this polyimide resin is to obtain through polyreaction by tetracarboxylic acid or its dicarboxylic anhydride derivative and diamines, and wherein this diamines comprises being selected from of at least 5 moles of % formula according to claim 1 (I) diamine derivative.
8. polyimide resin according to claim 7, wherein this diamines comprises the formula according to claim 1 (I) diamine derivative of at least 20 moles of %.
9. polyimide resin according to claim 7, wherein this diamines comprises 4-[(17-(1,5-dimethyl hexyl)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-ten tetrahydrochysenes-1H-encircles penta [a] phenanthrene-3-yl) the oxygen base]-1, the 3-phenylenediamine.
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| CNB03157162XA CN100497294C (en) | 2002-09-16 | 2003-09-16 | Aromatic diamine derivative, its preparation method and LCD component alignment film material containing it |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195711B (en) * | 2006-12-06 | 2012-07-04 | 大立高分子工业股份有限公司 | Polyamic acid component and alignment film produced by the same |
| CN103074075A (en) * | 2011-10-25 | 2013-05-01 | 达兴材料股份有限公司 | Liquid crystal aligning agent |
-
2003
- 2003-09-16 CN CNB03157162XA patent/CN100497294C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195711B (en) * | 2006-12-06 | 2012-07-04 | 大立高分子工业股份有限公司 | Polyamic acid component and alignment film produced by the same |
| CN103074075A (en) * | 2011-10-25 | 2013-05-01 | 达兴材料股份有限公司 | Liquid crystal aligning agent |
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| Publication number | Publication date |
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| CN100497294C (en) | 2009-06-10 |
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