CN111647412A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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Abstract
The invention discloses a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element, and belongs to the technical field of liquid crystal display. The liquid crystal aligning agent comprises a polymer A obtained by reacting a tetracarboxylic dianhydride component a with a diamine component B, wherein the diamine component B comprises a diamine compound B-1 represented by the general formula (1). The invention also discloses a liquid crystal orientation film and a liquid crystal display element prepared from the liquid crystal orientation agent. The liquid crystal orientation agent is stable in placement at room temperature, the prepared liquid crystal orientation film has excellent thermal stability, and the prepared liquid crystal display element has excellent weather resistance, so that a high-quality liquid crystal display device is prepared.
Description
Technical Field
The invention relates to the technical field of liquid crystal display, in particular to a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element.
Background
Liquid crystal elements are widely used in televisions, mobile devices, various monitors, and the like. Liquid crystal display is realized by controlling the alignment state of liquid crystal molecules, and in general, a liquid crystal alignment film is provided in a liquid crystal display element to control the initial alignment state of the liquid crystal molecules. The liquid crystal alignment film is mainly made of a polyimide material having excellent resistance to high temperatures.
The polyimide or its precursor is dissolved in an organic solvent to prepare a liquid crystal aligning agent. Since the liquid crystal aligning agent is usually stored at a low temperature due to gelation or viscosity change caused by solubility of polyimide or the material itself at room temperature, the liquid crystal aligning agent is usually stored at a low temperature and used at room temperature, and the liquid crystal aligning agent is usually used in factories to prepare liquid crystal alignment films because of inexhaustibility of the liquid crystal aligning agent on the day, which requires that the liquid crystal aligning agent is stable when stored at room temperature.
The liquid crystal alignment film is formed on the surface of the substrate that holds the liquid crystal, which is in contact with the liquid crystal, and serves to align the liquid crystal in a constant direction between the substrates, as a component of the liquid crystal display element. On the basis of this, it is sometimes required to control the pretilt angle of the liquid crystal. The ability to control the orientation of liquid crystals in such a liquid crystal alignment film is achieved by the treatment of a polyimide film constituting the liquid crystal alignment film. Such treatments are currently known as: rubbing the alignment film, oblique deposition of silicon oxide, and light irradiation of the photosensitive alignment film.
In recent years, liquid crystal display devices have been widely used for large screens, liquid crystal televisions, cellular phones, tablet personal computers, and the like, and further, as liquid crystal display devices, more stable performance and good weather resistance are required, and further, a liquid crystal alignment film is required to have better alignment properties and weather resistance, and to have good alignment properties for liquid crystal molecules even under high temperature conditions.
Disclosure of Invention
In view of the above problems of the prior art, the present applicant provides a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display device. The liquid crystal aligning agent solves the problem of unstable placement of the liquid crystal aligning agent caused by side chain aligning groups, and a liquid crystal aligning film prepared from the liquid crystal aligning agent has excellent thermal stability, and a prepared liquid crystal display element has the characteristic of good weather resistance.
The technical scheme of the invention is as follows:
one of the purposes of the invention is to provide a liquid crystal aligning agent, which comprises a polymer A and a solvent B; the polymer A is obtained by reacting a tetracarboxylic dianhydride component a and a diamine component b; the diamine component b includes a diamine compound b-1 represented by the general formula (1);
in the general formula (1), X represents a single bond, -O-, [ sic ],
-S-、
-O-CH2-、
One of (1);
y represents-CH2-O-or-O-CH2-; and Y is-O-CH2When X is not
AC1、AC2Each independently represents substituted or unsubstituted: a benzene ring or a cyclohexane ring;
m represents 0, 1,2 or 3, n represents 0, 1,2,3,4 or 5;
R1is a hydrogen atom or C1-10Linear or branched alkyl.
In a preferred embodiment, the diamine compound b-1 is a mixture of one or more of the formulas I-1 to I-8;
the polymer A is one or the mixture of polyamide acid and polyimide; the preparation method of the polymer A comprises the following steps: firstly, dissolving a mixture containing a tetracarboxylic dianhydride component a and a diamine component b in a solvent (one or more of N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide and gamma-butyrolactone), and carrying out polymerization reaction for 1-24 hours at 0-100 ℃ to obtain a polyamic acid solution; or distilling off the solvent in the polyamic acid solution under reduced pressure to obtain a polyamic acid solid, or pouring the polyamic acid solution into a large amount of a poor solvent and drying the precipitate to obtain a polyamic acid solid; the mass ratio of the mixture to the solvent is 1: 3-50.
The polyamic acid is heated in the presence of a dehydrating agent, a solvent (the same as solvent B), and a catalyst to obtain polyimide (the amic acid functional group in the polyamic acid is converted into an imide group by imidization). Wherein the weight ratio of the polyamic acid to the imidization solvent is 1: 5-30; the imidization rate of the amic acid is 30-100%; the temperature of the imidization reaction is 0-100 ℃, and the reaction time is 1-120 hours; the dehydrating agent can be selected from acid anhydride compounds, such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride; the molar ratio of the polyamic acid to the dehydrating agent is 1: 1-10; the catalyst can be selected from pyridine, trimethylamine or triethylamine; the molar ratio of the dehydrating agent to the catalyst is 1: 0.1-5.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the imidization ratio of the amic acid is 55 to 100%.
Further, the temperature of the imidization reaction is 20-60 ℃, and the reaction time is 2-30 hours.
The solvent in the preparation method of the polymer A can also be used together with a proper amount of poor solvent, wherein the poor solvent does not cause the precipitation of polyamic acid. Poor solvents may be used alone or in admixture, including but not limited to (1) alcohols: methanol, ethanol, isopropanol, cyclohexanol, or ethylene glycol; (2) ketones: acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclobutanone; (3) esters: methyl acetate, ethyl acetate or butyl acetate; (4) ethers: ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ethyl ether, ethylene glycol dimethyl ether or tetrahydrofuran; (5) halogenated hydrocarbon: dichloromethane, chlorobenzene or 1, 2-dichloroethane. Wherein the poor solvent accounts for 0-80%, preferably 0-50% of the total weight of the solvent.
The solvent B is one or more of N-methyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylacetamide, N-dimethylformamide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ethyl ether, ethylene glycol dimethyl ether and diethylene glycol monomethyl ether ethyl ester. The weight ratio of the polymer A to the solvent B is 1: 5-80.
The tetracarboxylic dianhydride component a is one or more of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentyl acetic dianhydride, pyromellitic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and 3,3 ', 4, 4' -biphenyl sulfone tetracarboxylic dianhydride.
The diamine component b also comprises a diamine compound b-2, wherein the diamine compound b-2 is p-phenylenediamine, m-phenylenediamine, 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, p-aminophenylethylamine, 4 '-diaminodiphenylmethane, 4' -diaminodiphenylethane, 4 '-diaminodiphenylether, 1, 4-bis (4-aminophenoxy) benzene, 4' -diaminobenzophenone, 1, 2-bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, n, N '-bis (4-aminophenyl) piperazine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2, 4-diaminododecyloxybenzene, 2, 4-diaminooctadecyloxybenzene, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, 4- (4-heptylcyclohexyl) phenyl-3, 5-diaminobenzoate, 2' -dimethyl-4, 4 '-diaminobiphenyl, 4' -diaminobenzamide, 1- (4- (4-pentylcyclohexylcyclohexyl) phenoxy) -2, 4-diaminobenzene, 1- (4- (4-heptylcyclohexyl) phenoxy) -2, one or more of 4-diaminobenzene and 3, 5-diaminobenzoic acid; in the diamine component b, the mole percentage of b-1 is 0.5-99.5%. The molar ratio of the tetracarboxylic dianhydride component a to the diamine component b is 100:20-200, and the further preferable molar ratio is 100: 80-120.
Preferably, in the general formula (1), the substitution position of the two amino groups is 2, 4-position or 3, 5-position with respect to the X position.
The liquid crystal aligning agent according to the present invention includes an additive C within a range that does not affect the efficacy of the present invention. The additive C is an epoxy compound or a silane compound with functional groups. The additive C has the function of improving the adhesive force between the liquid crystal orientation film and the substrate, and can be used singly or mixed with a plurality of additives.
The epoxy compound includes, but is not limited to, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, N ' -tetracyclooxypropyl-m-xylylenediamine, N ' -tetracyclooxypropyl-4, 4 ' -diaminodiphenylmethane, or 3- (N, N-diglycidyl) aminopropyltrimethoxysilane. Wherein the weight ratio of the polymer A to the epoxy compound is 100: 0.1-15.
Further, the weight ratio of the polymer A to the epoxy compound is 100: 1-3.
The silane compound having a functional group includes, but is not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, or N-bis (oxyethylene) -3-aminopropyltriethoxysilane. Wherein the weight ratio of the polymer A to the silane compound with the functional group is 100: 0-2.
Further, the weight ratio of the polymer A to the silane compound having a functional group is 100:0.02 to 0.2.
The liquid crystal aligning agent can be prepared by mixing the polymer A and the additive C in the solvent B at 20-100 ℃ under stirring.
The second object of the present invention is to provide a liquid crystal alignment film prepared from the liquid crystal alignment agent.
It is a further object of the present invention to provide a liquid crystal display device comprising the liquid crystal alignment film.
The preparation method of the liquid crystal display element comprises the following steps: preparing two substrates, wherein each substrate is provided with a layer of liquid crystal orientation film, and filling liquid crystal between the two substrates to prepare a liquid crystal box.
The liquid crystal display element produced by using the liquid crystal aligning agent of the present invention is suitable for various liquid crystal display elements such as Twisted Nematic (TN), Super Twisted Nematic (STN), Vertical Alignment (VA), in-plane switching (IPS), or Fringe Field Switching (FFS). Among the above liquid crystal display elements, a VA-type liquid crystal display element is preferable.
The beneficial technical effects of the invention are as follows:
(1) the liquid crystal aligning agent is prepared by polymerizing a diamine monomer containing a formula I and a tetracarboxylic dianhydride monomer; because the side chain of the diamine monomer contains stable flexible electron-donating group-CH2-O-or-O-CH2The problem of unstable placement of the liquid crystal aligning agent caused by side chain aligning groups is solved, the viscosity change is not large after long-time placement, and if the liquid crystal aligning agent does not use the diamine compound b-1, the liquid crystal aligning agent is unstable after long-time placement at room temperature, the viscosity change is large, and gel is easy to separate out;
(2) the liquid crystal alignment film prepared from the liquid crystal alignment agent has excellent thermal stability;
(3) the liquid crystal display element prepared by the liquid crystal aligning agent has good weather resistance, and the pre-tilt angle change is small after the liquid crystal display element is lightened for 1000 hours under the conditions of 85 ℃ and 85% of humidity.
Detailed Description
The present invention will be described in detail with reference to examples.
In the following specific examples, the liquid crystal aligning agent will be described only for a VA-type liquid crystal display device, but the present invention is not limited thereto.
Example for Synthesis of (mono) diamine Compound b-1
Example 1
The compound (b-1-1) represented by the formula I-1 can be synthesized according to the following scheme 1:
synthesis scheme 1
(1) Synthesis of Compound b-1-1a
Into a 1000mL three-necked round-bottomed flask were charged biphenol (37.2g, 200 mmol), 5CCMeO (53.2g, 200 mmol), and PPh3(52.4g, 240 mmol) and 500g THF were stirred at 25 deg.C until completely dissolved, DIAD (48.5g, 240 mmol) was added dropwise over 0.5h, incubated for 6 hours, desolventized to a residual amount of 210g, then cooled to-20 deg.C, the solution was filtered, and the resulting solid crystallized, filtered, and dried to give solid b-1-1 a.
(2) Synthesis of Compound b-1-1b
2, 4-dinitrochlorobenzene (33.4g, 165 mmol), b-1-1a (65.2g, 150 mmol) and 500g of toluene are put into a 1000mL three-neck round-bottom flask, and then the mixture is stirred, heated to reflux and insulated for 6 hours, then the solution is filtered by cooling, the filtrate is dried, 150g of toluene and 300g of ethanol are added into the obtained solid, and the solid is stirred, crystallized for half an hour, filtered and dried to obtain the solid b-1-1 b.
(3) Synthesis of Compound b-1-1
The obtained compound b-1-1b (60.1g, 100 mmol), 5% palladium on carbon (2.62g, 70% water content, 30% solid content) and 500g of tetrahydrofuran were charged into a 1L autoclave, the autoclave was sealed, and after replacement with hydrogen gas for 3 to 5 times, the pressure of hydrogen gas was increased to 0.5 to 1.0MPa, and the reaction was carried out at 40 to 45 ℃ with stirring. After the reaction is finished, the catalyst is removed through a film, then the solvent is removed, the obtained solid is added with 100g of ethanol and stirred for 30 minutes, and after filtration and drying, the solid compound b-1-1 is obtained with the yield of 90%.
The compound b-1-1 has high resolution mass spectrum, ESI source, positive ion mode and molecular formula C36H48N2O2Theoretical value 540.37, test value 541.2. Elemental analysis (C)36H48N2O2) Theoretical value C: 79.96, H: 8.95, N: 5.18, O: 5.92; found value C: 80.01, H: 8.89, N: 5.25, O: 5.85.
examples 2 to 4
The compounds shown in the formula I-2(b-1-2), the formula I-3(b-1-3) and the formula I-4(b-1-4) can be synthesized into corresponding phenol compounds by using corresponding parent compounds according to a synthesis route 1 and then etherified with 2, 4' -dinitrochlorobenzene to obtain corresponding nitro compounds; obtaining nitro compounds of structural formulas I-2 to I-4, and then carrying out reduction of the nitro groups through catalytic hydrogenation to obtain corresponding diamino compounds, wherein the high resolution mass spectrum data and the element analysis results of the compounds represented by the formulas I-2 to I-4 are shown in the following table 1:
TABLE 1
Example 5
The compound represented by formula I-5(b-1-5) can be synthesized according to the following scheme 2:
synthesis scheme 2
(1) Synthesis of Compound (b-1-5a)
Into a 1000mL three-necked round-bottomed flask were charged pentylcyclohexylphenol (49.2g, 200 mmol), 4-hydroxybiphenylcarbinol (40.1g, 200 mmol), and PPh3(52.4g, 240 mmol) and 500g THF were stirred at 25 deg.C until completely dissolved, DIAD (48.5g, 240 mmol) was added dropwise over 0.5h, incubated for 6 h, desolventized to a residual of 210g, followed byThen cooling to-20 ℃, filtering the solution, crystallizing, filtering and drying the obtained solid to obtain solid b-1-5 a.
(2) Synthesis of Compound (b-1-5b)
Putting b-1-5a (65.2g, 150 mmol), potassium carbonate (27.6g, 200 mmol) and 500g of toluene into a 1000mL three-neck round-bottom flask, stirring and heating to 80 ℃, slowly dropwise adding a mixed solution of 2, 4-dinitrochlorobenzene (38.0g, 165 mmol) and 100g of toluene into the system, dropping for about 0.5 hour, heating to reflux, continuing to perform heat preservation reaction for 6 hours, cooling to room temperature, filtering, removing the filtrate, adding 100g of ethyl acetate, stirring for 0.5 hour at room temperature, filtering and drying to obtain a solid b-1-5 b.
(3) Synthesis of Compound (b-1-5)
The obtained compound b-1-5b (62.3g, 100 mmol), 5% palladium on carbon (2.7g, solid content: 30%) and 400g of tetrahydrofuran were charged into a 1L autoclave, the autoclave was sealed, and after replacement with hydrogen gas for 3-5 times, the pressure of hydrogen gas was increased to 0.5-1.0MPa, and the reaction was carried out at 40-45 ℃ with stirring. After the reaction is finished, the catalyst is removed through a film, then the solvent is removed, 100g of ethanol is added into the obtained solid, the obtained solid is stirred for 30 minutes, and after filtration and drying, the solid compound b-1-5 is obtained with the yield of 95%.
The compound b-1-5 has high resolution mass spectrum, ESI source, positive ion mode and molecular formula C37H42N2O3Theoretical value 562.57, test value 563.33. Elemental analysis (C)37H42N2O3) Theoretical value C: 78.97, H: 7.52, N: 4.98, O: 8.53; found value C: 78.92, H: 7.55, N: 4.88, O: 8.65.
examples 6 to 8
Compounds of formula I-6(b-1-6), formula I-7(b-1-7), formula I-8(b-1-7) can be prepared by the synthetic route 2 and the corresponding hydroxy compound with the corresponding parent compound, then esterification with 2, 4-dinitrobenzoyl chloride to obtain the corresponding nitro compound, reduction of the nitro group by catalytic hydrogenation to obtain the corresponding diamino compound, and the results of high resolution mass spectrometry data field elemental analysis of compounds b-1-6, b-1-7 are shown in Table 2 below:
TABLE 2
Synthesis example of (di) Polymer A
Synthesis example A-1
In a 2000mL three-necked round-bottomed flask, under a nitrogen atmosphere, were charged compound b-1-1(27.02g, 50 mmol), p-phenylenediamine (10.81g, 100 mmol) (hereinafter referred to as b-2-1), 4,4 '-diaminodiphenyl ether (10.01g, 50 mmol) (hereinafter referred to as b-2-2),4, 4' -diaminodiphenylmethane (9.91g, 50 mmol) (hereinafter referred to as b-2-3) and 600g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and the resulting suspension was stirred until a yellow solution was obtained; then 49.02g (250 mmol) of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (hereinafter referred to as a-1) and 100g of NMP were added to the system; the reaction releases heat, the mixture is stirred for 4 hours at room temperature, the reaction solution is dripped into 7L of deionized water, solid is separated out, the mixture is filtered, a filter cake is dried in a vacuum oven at 80 ℃ and 0.09MPa for 24 hours, and the polymer A-1-1 is obtained.
Synthesis examples A-1-2 to A-1-20 and comparative Synthesis examples A-2-1 to A-2-7
Synthesis examples A-1-2 to A-1-20 and comparative Synthesis examples A-2-1 to A-2-7 were prepared by the same method as in Synthesis example A-1-1, except that: the types and amounts of monomers used were varied, and the results are shown in tables 3 and 4 below, in tables 3 and 4:
a-1: 1,2,3, 4-cyclobutanetetracarboxylic dianhydride
a-2: 2,3, 5-tricarboxylic cyclopentyl acetic dianhydride
a-3: pyromellitic dianhydride
a-4: 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride
b-1-1：
b-1-2：
b-1-5：
b-1-8：
b-2-1: p-phenylenediamine
b-2-2: 4, 4' -diaminodiphenyl ether
b-2-3: 4, 4' -diaminodiphenylmethane
b-2-4: 3, 5-diaminobenzoic acid
b-2-5: 2, 4-diaminododecyloxybenzene
b-2-6: 1- (4- (4-heptylcyclohexyl) phenoxy) -2, 4-diaminobenzene
b-2-7: 1- (4- (4-pentylcyclohexylcyclohexyl) phenoxy) -2, 4-diaminobenzene
b-2-8: 4, 4' -diaminodiphenylethane
b-2-9：
TABLE 3
TABLE 4
(III) application examples and comparative examples
Application example 1
a. Liquid crystal aligning agent
100 parts by weight of polymer (A-1-1), 900 parts by weight of NMP (hereinafter referred to as B-1) and 800 parts by weight of ethylene glycol monobutyl ether (hereinafter referred to as B-2) were put into a three-necked round-bottomed flask under nitrogen atmosphere, the system was stirred at room temperature for 30 minutes, and then the solution was filtered through a 0.3 μm filter to obtain a liquid crystal aligning agent of practical example 1.
b. Liquid crystal alignment film and liquid crystal display element
Coating the liquid crystal aligning agent of application example 1 on a first glass substrate having an ITO electrode by spin coating to form a precoat layer; the polyimide coating with a film thickness of 80nm was obtained by precuring (hot plate, 80 ℃, 10 minutes), main curing (circulating oven, 230 ℃, 60 minutes).
A rubbing treatment was performed on the film surface by a rayon cloth rubbing device having a roller diameter of 120mm under conditions of a Gurlen rotation speed of 700rpm, a substrate advancing speed of 40mm/sec and an insertion amount of 0.3mm to obtain a substrate comprising a liquid crystal alignment film, two substrates were prepared in the rubbing orientation state with spacers of 4 μm interposed therebetween on the inner side of the film surface in the opposite rubbing direction, the two glass substrates were combined, the peripheral portions were bonded with a sealant to prepare an empty cell, a VA-type liquid crystal was injected into the empty cell by a reduced pressure injection method, and the liquid crystal injection port was sealed to obtain a VA-type liquid crystal display cell having parallel opposite directions.
The liquid crystal aligning agent and the liquid crystal display device of application example 1 were evaluated, and the results are shown in table 5.
Application example 2 to application example 33
Application examples 2 to 33 of a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element can be prepared by the same procedure as in application example 1 except that: the kinds and amounts of the polymer (A), the solvent (B) and the additive (C) used were changed, and the orientation process was also changed, as shown in Table 5. The liquid crystal display elements of application example 2 to application example 33 were evaluated and the results are shown in table 5.
Comparative application example 1 to comparative application example 10
Application comparative examples 1 to 7 of a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element can be prepared by the same procedure as in application example 1 except that: the kinds and amounts of the polymer (A), the solvent (B) and the additive (C) used were changed, and the orientation process was also changed, as shown in Table 6. The liquid crystal display elements of comparative example 1 to comparative example 10 were evaluated and the results are shown in table 6.
Evaluation method
The liquid crystal aligning agent standing stability evaluation can be carried out by standing the liquid crystal aligning agent solution at 20 ℃ for 3 days, and the standing stability is good as no gel is generated and the viscosity change is smaller.
The test method is as follows:
restoring the liquid crystal orientation agent to 20 ℃, taking 2mL of sample to test the viscosity of the sample and recording the viscosity as eta 1;
standing the sample at 20 ℃ for 3 days, observing whether gel particles are generated, and if no gel particles are generated, sampling and measuring the viscosity and recording the viscosity as eta 2;
viscosity change Δ η (%) ═ (η 1- η 2)/η 1 × 100%
The evaluation criteria are as follows:
x: gel particles appear, and the liquid crystal aligning agent has poor placing stability;
gel-free particles:
v: the delta eta is less than or equal to 5 percent, which shows that the liquid crystal orientation agent has excellent placement stability;
o: the liquid crystal orientation agent has good standing stability when the delta eta is more than 5% and less than 8%;
x: the delta eta is more than 8 percent, which indicates that the liquid crystal orientation agent has poor placement stability;
the thermal stability of the liquid crystal alignment film can be evaluated by the voltage holding ratio of the liquid crystal display device (hereinafter abbreviated as VHR), and the method for detecting the voltage holding ratio is as follows.
The conditions for testing VHR were: after applying 5V voltage for 60ms, the voltage was released, and VHR (denoted as VHR) was measured 167ms after the release of the voltage1). Then, the liquid crystal display element was left at 60 ℃ for 12 hours, and VHR (described as VHR) at this time was measured by the same method2). Then, the change value of VHR (denoted as Δ VHR (%)) is calculated by the formula (V), and a lower Δ VHR (%) means thatThe better the thermal stability.
Evaluation criteria of Δ VHR (%) are as follows:
very good delta VHR (%)% is less than or equal to 5%, and the thermal stability is excellent;
5 percent to delta VHR (percent) is less than or equal to 10 percent, and the thermal stability is good;
delta is more than 10 percent and less than or equal to 20 percent of delta VHR (%), and the thermal stability is general;
x: 20% < delta VHR (%), and the thermal stability is poor.
The weather resistance test conditions of the liquid crystal display element are as follows: continuously lighting the liquid crystal display element in a constant-temperature constant-humidity oven at 85 ℃ and 85% humidity for 1000 hours; the pretilt angle of the liquid crystal display element before the constant temperature and humidity oven is taken as PTA1, and the pretilt angle of the liquid crystal display element after the constant temperature and humidity oven is lightened for 1000 hours is taken as PTA 2; the pretilt angle change is designated Δ PTA.
ΔPTA(％)＝(PTA1-PTA2)/PTA1*100％
The evaluation criteria are as follows:
very good: delta PTA is less than or equal to 0.55 percent, which shows that the liquid crystal display element has excellent weather resistance;
o: the liquid crystal display element has good weather resistance when the ratio of 0.55 percent to Delta PTA is less than or equal to 1.10 percent;
x: DELTA PTA > 1.10% indicating poor weatherability of the liquid crystal display element.
In tables 5 and 6:
b-1: n-methyl-2-pyrrolidone is added,
b-2: ethylene glycol monobutyl ether,
c-1: n, N, N ', N ' -tetracyclooxypropyl-4, 4 ' -diaminodiphenylmethane,
c-2: 3-aminopropyldiethoxymethylsilane.
TABLE 5
TABLE 6
Therefore, compared with the prior art, the liquid crystal aligning agent is formed by polymerizing a diamine monomer containing a specific branched chain structure and a tetracarboxylic dianhydride monomer; because the diamine monomer side chain contains stable flexible electron-donating group-CH2-O-or-O-CH2The orientation agent is stable at room temperature; the prepared liquid crystal alignment film has excellent thermal stability; after the liquid crystal display element is lightened for 1000 hours under the conditions of 85 ℃ and 85% of humidity, the pre-tilt angle change is small, and further, the liquid crystal display element has the characteristic of good weather resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The liquid crystal aligning agent is characterized by comprising a polymer A and a solvent B; the polymer A is obtained by reacting a tetracarboxylic dianhydride component a and a diamine component b; the diamine component b includes a diamine compound b-1 represented by the general formula (1);
in the general formula (1), X represents a single bond, -O-, [ sic ],
-S-、
-O-CH2-、
One of (1);
y represents-CH2-O-or-O-CH2-; and Y is-O-CH2When X is not
AC1、AC2Each independently represents substituted or unsubstituted: a benzene ring or a cyclohexane ring;
m represents 0, 1,2 or 3, n represents 0, 1,2,3,4 or 5;
R1is a hydrogen atom or C1-10Linear or branched alkyl.
2. The liquid crystal aligning agent according to claim 1, wherein the diamine compound b-1 is a mixture of one or more of the formulae I-1 to I-8;
3. the liquid crystal aligning agent according to claim 1, wherein the solvent B is one or more selected from the group consisting of N-methyl-2-pyrrolidone, γ -butyrolactone, N-dimethylacetamide, N-dimethylformamide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, and diethylene glycol monomethyl ether ethyl ester.
4. The liquid crystal aligning agent according to claim 1, wherein the weight ratio of the polymer A to the solvent B is 1:5 to 80.
5. The liquid crystal aligning agent according to claim 1, wherein the tetracarboxylic dianhydride component a is one or more selected from the group consisting of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid dianhydride, pyromellitic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, and 3,3 ', 4, 4' -biphenylsulfone tetracarboxylic dianhydride.
6. The liquid crystal aligning agent according to claim 1, wherein the diamine component b further comprises a diamine compound b-2, and the diamine compound b-2 is p-phenylenediamine, m-phenylenediamine, 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, p-aminoethylamine, 4 '-diaminodiphenylmethane, 4' -diaminodiphenylethane, 4 '-diaminodiphenylether, 1, 4-bis (4-aminophenoxy) benzene, 4' -diaminobenzophenone, 1, 2-bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 1, 5-diaminonaphthalene, or the like, 1, 6-bis (4-aminophenoxy) hexane, N '-bis (4-aminophenyl) piperazine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2, 4-diaminododecyloxybenzene, 2, 4-diaminooctadecyloxybenzene, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, 4- (4-heptylcyclohexyl) phenyl-3, 5-diaminobenzoate, 2' -dimethyl-4, 4 '-diaminobiphenyl, 4' -diaminobenzamide, 1- (4- (4-pentylcyclohexylcyclohexyl) phenoxy) -2, one or more of 4-diaminobenzene, 1- (4- (4-heptylcyclohexyl) phenoxy) -2, 4-diaminobenzene, 3, 5-diaminobenzoic acid; in the diamine component b, the mole percentage of b-1 is 0.5-99.5%.
7. The liquid crystal aligning agent according to claim 1, wherein the molar ratio of the tetracarboxylic dianhydride component a to the diamine component b is 100:20 to 200.
8. The liquid crystal aligning agent according to claim 1, wherein the substitution position of the two amino groups in the general formula (1) is 2, 4-position or 3, 5-position with respect to the X position.
9. A liquid crystal alignment film comprising the liquid crystal aligning agent according to any one of claims 1 to 7.
10. A liquid crystal display element comprising the liquid crystal alignment film according to claim 8.
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