CN1196768C - Liquid crystal aligning agent and liquid crystal display device - Google Patents
Liquid crystal aligning agent and liquid crystal display device Download PDFInfo
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- CN1196768C CN1196768C CNB951150189A CN95115018A CN1196768C CN 1196768 C CN1196768 C CN 1196768C CN B951150189 A CNB951150189 A CN B951150189A CN 95115018 A CN95115018 A CN 95115018A CN 1196768 C CN1196768 C CN 1196768C
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Abstract
The present invention relates to a liquid crystal orientation agent which comprises polyamine acid with aliphatic and/or alicyclic hydrocarbon groups, polyimide with aliphatic and/or alicyclic hydrocarbon groups and a liquid crystal display device adopting the liquid crystal orientation agent. The liquid crystal orientation agent generates a liquid crystal orientation film with good liquid crystal orientation characteristics, a tilt angle can be changed by a little radiation, and the orientation agent is suitable for domain-divided orientation type liquid crystal displays with wide view angles.
Description
The present invention relates to a kind of liquid crystal aligning agent that is used for subregion alignment-type liquid crystal indicating meter, the invention particularly relates to a kind of like this liquid crystal aligning agent, when this liquid crystal aligning agent forms liquid crystal orientation film, its liquid crystal aligning excellent performance, and by irradiation liquid crystal orientation film exposed and can change the tilt angle of liquid crystal.
This liquid-crystal display of known a kind of like this liquid-crystal display (being called " TN-STN indicating meter " later on) has a sandwich structure, the liquid crystal that clamping has positive dielectric anisotropy between two substrates that are made of transparency electrode and liquid crystal orientation film of being formed by polyimide etc. wherein, also have a TN (twisted nematic) or STN (super-twist nematic) liquid crystal cell between two substrates, wherein the main shaft of liquid crystal molecule can distortion continuously in 90 to 270 ° of scopes.Yet there is such problem in the TN-STN indicating meter, and promptly owing to utilize the lifting of the anisotropic liquid crystal molecule of specific refractory power to make demonstration open and close, the visual angle of demonstration is especially narrow for the demonstration of shadow tone.
In other words, for example the common white mode that when not applying voltage, shows white TN-STN indicating meter situation under, when from forward observation, the L of its voltage-transmission characteristics such as Fig. 1
1Shown in, and transmissivity descends when the voltage that applies increases.Yet, when at the normal direction of observation of liquid crystal ascent direction at an angle when diagonal lines is observed, the L among its voltage-transmission characteristics such as Fig. 1
2Shown in, and this rational curve zone of having a transmissivity to increase with the voltage that applies.The counter-rotating of tone occurs in the confuse right and wrong of the feasible image in this zone.In addition, when from the reverse side of normal direction of observation at an angle when diagonal lines is observed, the L of its voltage-transmission characteristics such as Fig. 1
3Shown in, and black white contrast obviously descends.In order to address this problem, such report had been arranged already: in such a way by making up two substrate and subregion alignment-type liquid crystal (SID ' 92Digest of showing high and low tilt angle that scribble liquid crystal orientation film, 798 pages), make the zone have the zone of high tilt angle and to have a low tilt angle between last substrate and subtegulum toward each other.
When with have respectively high tilt angle and low tilt angle go up (or down) zone and down (or on) when the zone was combined, liquid crystal turned to the differently-oriented directivity with high tilt angle zone.Utilize this phenomenon, have the differently-oriented directivity of the zone of high tilt angle and zone that subtegulum has low tilt angle counter-rotating liquid crystal at last substrate, with obtain one in each pixel coverage along normal direction and rightabout viewing angle.Thereby, viewing angle characteristic (L
4) be uniformly, this auspicious making when when positive and negative both sides are observed, obtaining not have the sharply good demonstration of decline of black and white color inversion and contrast gradient.Fig. 2 represents the example of the structure of such liquid-crystal display.Because by selecting a suitable tilt angle to determine differently-oriented directivity arbitrarily, this structure is not limited to this example.Fig. 3 represents the example with the structure of a conventional liquid-crystal display of making comparisons.
As the method that forms the liquid crystal orientation film with high and low tilt angle on same substrate, Fig. 4 represents a kind of currently known methods as an example.
On a substrate, at first form a liquid crystal orientation film A.On film A, form the liquid crystal orientation film B (for example, the tilt angle of film A is 7 °, and the tilt angle of film B is 1 °) that another layer tilt angle is different from liquid crystal orientation film A.In addition, on film B, form the positive resist of one deck alkali-developable, and by a predetermined pattern expose and develops with removal resist with exposure area liquid crystal aligning agent.
Then, remove zone and the zone of liquid crystal orientation film B, i.e. according to the low tilt angle of pattern exposure and unexposed zone the regional and high tilt angle zone of unexposed area to form liquid crystal orientation film A of resist.
There are some problems like this in above-mentioned formation method of patterning, and is very strict such as liquid crystal orientation film is required, complicate fabrication process, and the electrical property variation of liquid-crystal display.Thereby the someone proposes a kind of method that replaces this method, promptly utilizes the method (seeing EP613037A) of being controlled tilt angle by the change of shining the liquid crystal orientation film that the direct exposure of the liquid crystal orientation film that forms is caused on substrate.
Yet, when using conventional liquid crystal aligning agent, can not change tilt angle with the irradiation exposure in some cases, even and when tilt angle changes, still need a large amount of irradiation energies to obtain the difference of needed tilt angle.Therefore, conventional liquid crystal aligning agent can not satisfy the needs of above-mentioned application.
Thereby an object of the present invention is to provide a kind of like this liquid crystal aligning agent, this liquid crystal aligning agent is the liquid crystal aligning excellent property when its formation liquid crystal orientation film, and can cause the change of tilt angle when the radiation with little quantity of radiant energy exposes liquid crystal orientation film with short cycle.
Can clearly see other purpose of the present invention and advantage from the following description.
According to the present invention, can reach these purposes and advantage by the liquid crystal aligning agent that is used for a subregion alignment-type liquid crystal indicating meter, this liquid crystal aligning agent comprises a kind of like this polymkeric substance, this polymkeric substance comprises at least one from by the structural unit of selecting the structural unit (being called " specific structure unit I " later on) of following structural formula (1) representative and the group by the structural unit (being called " specific structure unit II " later on) of following structural formula (2) representative, and with before the irradiation exposure relatively after with the irradiation exposure when the liquid crystal aligning agent formation film, this liquid crystal aligning agent has the ability that changes liquid crystal pretilt angle
R wherein
1And R
2Be respectively tetravalence and divalent organic group, and one of them organic group is aliphatic series or alicyclic alkyl, or a group that comprises aliphatic series or alicyclic alkyl,
R wherein
3And R
4Be respectively tetravalence and divalent organic group, and one of them organic group is aliphatic series or alicyclic alkyl, or a group that comprises aliphatic series or alicyclic alkyl.
Fig. 1 represents the voltage transmission characteristics of a conventional TN-STN indicating meter;
Fig. 2 represents an example that is formed with the liquid crystal display device structure of the liquid crystal orientation film with high and low tilt angle on same substrate;
Fig. 3 represents another example of the liquid crystal display device structure of a liquid crystal orientation film that is formed with same pretilt angle on same substrate;
Fig. 4 is the diagrammatic sketch that an explanation is used to make the method for liquid crystal orientation film, and this method adopts two kinds of liquid crystal aligning agent that show different tilt angles to form height and low tilt angle on identical substrate;
Fig. 5 is the diagrammatic sketch that an explanation is used to make the method for the subregion alignment-type liquid crystal indicating meter that has used liquid crystal aligning agent of the present invention;
Fig. 6 is a sectional view that is used to measure the liquid-crystal display of tilt angle;
Fig. 7 is a sectional view that is used to measure the liquid-crystal display that is orientated characteristic; With
Fig. 8 is that an explanation adopts liquid crystal orientation film to form the step of liquid-crystal display in an embodiment of the present invention.
Can obtain to be used for the polymer (hereinafter referred to as " particular polymers I ") that mainly comprises specific structure unit I of the present invention by making tetracarboxylic dianhydride and diamine reactant. Can or obtain mainly to comprise the polymer (hereinafter referred to as " particular polymers II ") of specific structure unit II at the construction unit I that exists in the situation of catalyst chemically amination to comprise the polymer of suitable specific structure unit I by calorifics ground. In the manufacturing of particular polymers I, for the molecular weight of controlling polymer, improve the adaptability of substrate or the purpose of a tilt angle is provided, can add acid anhydrides and monoamine compound. The such particular polymers I of the final change of preparation and can be as aligning agent for liquid crystal of the present invention and without any problem as the particular polymers II of the amination polymer of particular polymers I. Be included in aliphatic series among particular polymers I and the particular polymers II and/or alicyclic alkyl and can be included at least tetracarboxylic dianhydride and diamines in one of them. Be preferably in and comprise these groups in the two or more components.
In the present invention, angle from solubility organic solvent, more preferably 40 to 100mol%, more preferably 60 to 100mol% as the ratio of the polymer of aligning agent for liquid crystal for specific structure unit I and/or specific structure unit II, and the most preferably 70 to 100mol%.
In addition in the present invention, angle from the liquid crystal aligning characteristic, after having carried out following curing, characteristic structure unit II occupies the ratio of polymer of the liquid crystal orientation film that forms liquid crystal display preferably 40 to 100mol%, more preferably 60 to 100mol%, and the most preferably 70 to 100mol%.
According to the present invention, particular polymers I in fact is called polyamic acid and in fact particular polymers II is called polyimides. Particular polymers I is represented by following structural formula (A) usually:
R wherein1And R2Be respectively tetravalence and divalent organic group, and one of them organic group is aliphatic series or alicyclic alkyl, or a group that comprises an aliphatic series or alicyclic alkyl, and n is the number of repetitive.
Particular polymers II is represented by following structural formula (B) usually:
R wherein
3And R
4Be respectively tetravalence and divalent organic group, and one of them organic group is aliphatic series or alicyclic alkyl, or a group that comprises aliphatic series or alicyclic alkyl, and n is a number of repeating units.
Particular polymers II comprises specific structure unit I sometimes.
Tetracarboxylic dianhydride's illustrative example comprises aliphatic series or alicyclic tetracarboxylic dianhydride, such as butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group second dianhydride, 3,5,6-three carboxyls norbornane-2-second dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,2,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-benzo [1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofuran (THF) methylene radical)-3-methyl-3-hexanaphthene-1,2-dicarboxylic acid dianhydride and two ring [2,2,2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride; And the aromatic tetracarboxylic acid dianhydride, such as the pyromellitic acid dianhydride, 3,3 ', 4,4 '-the sulfobenzide tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor sec.-propyl subunit two phthalic acid dianhydrides, two (phthalic acid) phenylphosphine oxide dianhydride, P-phenylene-two (triphenylbenzene dioctyl phthalate) dianhydride, m-phenylene-two (triphenylbenzene dioctyl phthalate) dianhydride, two (triphenylbenzene dioctyl phthalate)-4,4 '-phenylbenzene ether dianhydride and two (triphenylbenzene dioctyl phthalate)-4,4 '-the ditan dianhydride.Wherein preferred 1,2,3 at this, 4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group second dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1,3-diketone, 5-(2,5-dioxo tetrahydrofuran (THF) methylene radical)-3-methyl-3-hexanaphthene-1,2-dicarboxylic acid dianhydride and two rings [2,2,2]-and Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride.Particularly preferably be 1,2,3,4-tetramethylene tetracarboxylic dianhydride and 2,3,5-tricarboxylic basic ring amyl group second dianhydride.They can use separately, also can two or more be used in combination.
The illustrative example of diamine compound comprises aromatic diamine, such as 3, and the 5-diaminobenzoic acid, 4,4 '-diamino-diphenyl ethane, 4,4 '-the diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 4,4 '-the diamino-diphenyl ether, 1, the 5-diaminonaphthalene, 3,3-dimethyl-4,4 '-diamino-diphenyl, 4,4 '-the diaminobenzene formylaniline, 3,4 '-the diamino-diphenyl ether, 3,3 '-the diamino benzophenone, 3,4 '-the diamino benzophenone, 4,4 '-the diamino benzophenone, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] sulfones of 2-, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-the aminophenyl)-10-hydrogenation anthracenes of 9-, 2,7-diamino fluorenes, 9, two (4-aminophenyl) fluorenes of 9-, 4,4 '-methylene radical-two (2-chloro aminobenzens), 2,2 ', 5,5 '-tetrachloro base-4,4 '-the diamino phenylbenzene, 2,2 '-dichloride base-4,4 '-diamino-5,5 '-the dimethoxy phenylbenzene, 3,3 '-dimethoxy-4 ', 4 '-diamino-diphenyl, 1,4,4 '-(P-phenylene isopropylidene) pentanoic, 4,4 '-(m-phenylene isopropylidene) pentanoic, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-two (trifluoromethyl) phenylbenzene, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-Xin fluorine phenylbenzene and by the diamines of following structural formula (3) representative:
Aromatic diamine has a heteroatoms, such as the diamino 4-phenyl-thiophene; Aliphatic series or alicyclic diamine, such as 1, xylylene between 1-, 1, the 3-propanediamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine, the heptamethylene diamines, eight methylene diamine, nine methylene diamine, 4,4-diamino heptamethylene diamines, 1,4-diamino-cyclohexane, isophorone, tetrahydrochysene is for dicyclopentadienyl subunit diamines, hexahydro--4, the inferior indanyl dimethylene of 7-methylene radical diamines, three rings [6,2,1,0
2.7]-undecylene dimethyl diamines and 4,4 '-methylene-bis (hexahydroaniline); The phenylenediamine that the alkyl of being represented by following structural (4) replaces:
R wherein
9, R
10, R
11And R
12Be respectively hydrogen atom or alkyl, such as methyl, ethyl or sec.-propyl,
Such as the inferior phenylenediamine and 2,3,5 of P-, 6-tetramethyl--1,4-diaminobenzene; Ditan by the replacement of following structural formula (5) representative:
R wherein
13, R
14, R
15, R
16, R
17, R
18, R
19And R
20Be respectively a hydrogen atom or an alkyl, such as methyl, ethyl, or sec.-propyl,
Such as 4,4 '-tetramethyl triaminotriphenyl methane NH2 and 3,3 '-diethyl-4,4 '-diaminodiphenyl-methane;
Phenylenediamine by the replacement of following structural formula (6) representative:
R wherein
21Be from containing-O-,-COO-,-OCO-,-NHCO-,-CONH-and-divalent organic group that chooses in the group of CO-, R
22Be an any monovalent organic radical group,
Such as diamines by following structural (7) representative:
And at R
22Has a steroid skeleton; Have 3 of a trifluoromethyl group, 5-diamino-4 '-trifluoromethyl benzanilide and 3,5-diamino-3 '-the trifluoromethyl benzanilide; Diamino organo-siloxane by following structural formula (8) representative:
R wherein
23Be a hydrocarbyl group with 1 to 12 carbon atom, i.e. groups, such as methyl, ethyl or propyl group, a naphthene group, such as cyclohexyl, perhaps aromatic group, such as phenyl, P is one 1 to 3 a integer, q is one 1 to 20 a integer;
With similar composition.
In the middle of these compositions, P-phenylenediamine preferably, 2,3,5,6-tetramethyl--1, the 4-diaminobenzene, 4,4 '-diaminodiphenyl-methane, 3,3 '-diethyl-4,4 '-diaminodiphenyl-methane, 1,5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-the diamino-diphenyl thioether, 4,4 '-the diamino-diphenyl ether, 9, two (4-aminophenyl) fluorenes of 9-, 2,2-pair [4-(the 4-amino-benzene oxygen] HFC-236fa, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-two (trifluoromethyl) phenylbenzene, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro phenylbenzene, 3,5-amino-4 '-the trifluoromethyl benzanilide, 3,5-diamino-3 '-trifluoromethyl benzanilide and by the diamines of top structural formula (8) representative.Preferred especially P-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-the diamino-diphenyl thioether, 3,5-diamino-4 '-the trifluoromethyl benzanilide, 3,5-diamino-3 '-trifluoromethyl benzanilide and by the diamines of top structural formula (8) representative.They can use separately, also can two or more be used in combination.
The example that is applicable to the acid anhydrides of terminal variant comprises maleic anhydride, Tetra hydro Phthalic anhydride and the compound of being represented by following structural formula (9):
The particular instance that is used for the monoamine of terminal variant comprises: aniline, hexahydroaniline, n-butylamine, the n-amylamine, n-hexylamine, n-heptyl amice, the n-octylame, n-nonyl amine, n-decyl amine, the n-undecylamine, n-amino dodecane, n-tridecyl amine, the n-tetradecy lamine, n-pentadecyl amine, n-cetylamine, the n-heptadecyl-amine, n-stearylamine, n-20 amine and similar substance.
R at specific structure unit I of the present invention and II
1, R
2, R
3And R
4The aliphatic series of an aliphatic hydrocarbyl or alicyclic alkyl is contained at the place or alicyclic alkyl is from aliphatic series or alicyclic tetracarboxylic dianhydride, aliphatic series or alicyclic diamine, or the tetracarboxylic dianhydride of aliphatic series or alicyclic alkyl or diamines derive as mentioned above to contain one.
Can especially preferably tetracarboxylic dianhydride and diamine compound be reacted and obtain to be used for particular polymers I of the present invention by in the temperature of reaction that is preferably 0 to 150 ℃.The component of tetracarboxylic dianhydride and diamine compound is such as down: the component of the anhydride group of tetracarboxylic dianhydride 0.2 to 2 equivalent preferably in the amine groups of amount diamine compound is more preferably 0.3 to 1.2 equivalent.As mentioned above, can when reacting, this add acid anhydrides or the monoamine that is used for terminal variant.
It is not particularly limited organic solvent, as long as can dissolve the particular polymers I that is formed by this reaction.The illustrative example of organic solvent comprises: non-proton transfering polarity solvent, and such as the N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, N, dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea and hexamethylphosphorictriamide; And the phenol solvent, such as m-cresols, xylenol, phenol and halogenated phenol.The amount of preferably setting the organic solvent that uses like this makes the amount of tetracarboxylic dianhydride and diamine compound account for 0.1 to 30% of reaction solvent total amount by weight.
Under the heating state that has dewatering agent and imidization catalyst, can obtain to be used for particular polymers II of the present invention by the above-mentioned particular polymers I of imidization.The range of reaction temperature that is used for the above-mentioned imidization that carries out under heating is preferably 60 to 250 ℃, more preferably 100 to 170 ℃.When temperature of reaction was lower than 60 ℃, reaction was carried out slowly, and when temperature of reaction was higher than 250 ℃, the molecular weight of particular polymers II was easy to reduce a lot.Can in above-mentioned organic solvent, carry out imidization under the situation that has dewatering agent and imidization catalyst.Temperature of reaction is preferably in 0 to 180 ℃ of scope, more preferably in 60 to 150 ℃ of scopes.For example, can from acid anhydrides (such as diacetyl oxide, propionic anhydride and trifluoroacetic acid), select dewatering agent.For example, can from tertiary amine (such as pyridine, collidine, lutidine and trifluoroacetic anhydride), select imidization catalyst.Preferably 1.6 to 20 moles of the amounts of the dewatering agent that uses in the repeating unit of the particular polymers I of every molar equivalent.The amount of employed imidization catalyst is preferably 0.5 to 10 mole in the dewatering agent of every mole of use.
The poor solvent of above-mentioned organic solvent and particular polymers II (such as alcohol, ketone, ester, ether, halohydrocarbon or hydrocarbon) can be mixed and use, its blended degree should make particular polymers II not be settled out.Can from following material, select poor solvent for instance: alcohol, such as methyl alcohol, ethanol, Virahol, hexalin, ethylidene glycol, trimethylene glycol, 1,4-butyleneglycol, triglycol and ethylidene glycol monomethyl ether; Ketone, such as acetone, methyl ethyl ketone, mibk and pimelinketone; Ester, such as the methyl acetic acid ester, ethylhexoate, butylacetic acid ester, diethyl oxalate and diethyl malonic ester; Ether, such as Anaesthetie Ether, the ethylidene glycol methyl ether, the ethylidene glycol ethyl ether, ethylidene glycol-n-propyl ether, ethylidene glycol-i-propyl ether, ethylidene glycol-n-butyl ether, the ethylidene glycol dimethyl ether, ethylidene glycol ethyl ether acetic ester, diethylidene glycol dimethyl ether and tetrahydrofuran; Halohydrocarbon, such as methylene dichloride, 1,2-ethylene dichloride, 1,4-dichlorobutane, trichloroethane, chlorobenzene and 0-dichlorobenzene; Hydrocarbon, such as hexane, heptane, octane, benzene, toluene and dimethylbenzene.
The limiting viscosity that has of particular polymers I of Huo Deing or II is preferably in 0.05 to 10dl/g scope like this, more preferably in 0.05 to 5dl/g scope (when at such condition [η inh=(ln η rel/c, C=0.5g/dl, under 30 ℃, at the N-N-methyl-2-2-pyrrolidone N-), the inherent viscosity of following records under such condition]).
In order to increase particular polymers I and/or the polymkeric substance II purpose to the viscosity of substrate, liquid crystal aligning agent of the present invention can comprise a kind of silane coupling agent.
The illustrative example of silane coupling agent comprises: the 3-TSL 8330,3-aminopropyl three hexyloxy silane, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl-triethoxysilicane, N-ethoxycarbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4-7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-phenmethyl-3-TSL 8330, N-phenmethyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl 3-aminopropyltriethoxywerene werene, two (oxygen base the ethylidene)-3-TSL 8330 of N-, two (oxygen base ethylidene)-3-aminopropyltriethoxywerene werene of N-and similar material.
Liquid crystal aligning agent of the present invention can comprise some additives, and such as photosensitizers, light trigger (Photoradical generator) and form the reagent of acid by illumination is so that improve the radiating susceptibility.
Photosensitizers; light trigger (Photoradical generator) and be respectively a kind of tonka bean camphor by the representative instance of reagent that rayed forms acid; such as 3-benzoyl benzo [f] tonka bean camphor (producing) by Kodak company; a kind of ketone compound that contains; such as CGI-369 (producing) by CIBAGEIGY; with a kind of triaizine compounds, such as 2, two (tri-chlorination the methyl)-6-(4 '-methoxyl group naphthyl) of 4--S-triazine.
Liquid crystal aligning agent of the present invention shows the ability that changes liquid crystal pretilt angle when film that the exposure back is formed by liquid crystal aligning agent and the film comparison before the exposure.
Utilize this characteristic of liquid crystal aligning agent of the present invention, can be in order to below manufactured partitioning type liquid-crystal display, (see figure 5).
Can adopt roller coating, any method among spin coating and the printing process also 60 to 100 ℃ of prebake conditions and at first applies liquid crystal aligning agent of the present invention in nesa coating one side of the substrate with nesa coating.Then, use such as ultraviolet ray by a mask with predetermined pattern the liquid crystal orientation film of such acquisition is carried out the part exposure, and then under 120 to 300 ℃ of temperature, preferably carry out back under 130 to 250 ℃ of temperature and toast.Normally 0.001 to 1 μ m, preferably 0.005 to 0.5 μ m of the thickness of the coating of Huo Deing at last.The tilt angle of exposure area is different with the tilt angle of unexposed area.The difference of tilt angle approximately is 2 ° to 10 ° in a pixel.
Be not particularly limited radiation,, can adopt ultraviolet ray, electron beam, X ray and laser beam as long as this radiating capacity causes the above-mentioned variation of film.In these radiation, preferably radiation has 300nm or shorter wavelength.From the angle that may expose in batch, especially preferably by metal halide lamp, the mercury xenon lamp, Cooper-Hewitt lamp, the ultraviolet ray that high pressure mercury vapour lamp or analogue send is as light source.
With the cylinder that is tied with synthon (such as nylon) film that forms is above ground and to form liquid crystal orientation film.After coating being carried out back baking or milled processed, coating is exposed with radiation.
Above-mentioned substrate can be selected from by glass (such as floating glass and Su Da glass) and polyoxyethylene glycol terephthalate, polytetramethylene glycol terephthalate, polytrimethylene ether sulfone, the transparent substrate that the plastics film of polycarbonate and analogue forms.
Above-mentioned nesa coating is selected from by SnO
2The NESA film that constitutes and by In
2O
3-SnO
2ITO film that constitutes and similar thing.Can adopt the method for photoetching or adopt the method for mask on nesa coating, to form pattern in advance.
For further improve substrate and nesa coating to the sticky limit of coating can be in advance before the coated with liquid crystal alignment agent on substrate and nesa coating coating silane coupling agent or titanium coupling agent.
Preferably place two substrates like this, on each of this two substrates, form and have a liquid crystal orientation film that in a pixel, has the pattern of different tilt angles, so that liquid crystal orientation film toward each other, their grinding direction is rectangular or antiparallel, and make the high tilt angle zone of between upper and lower substrate film and low tilt angle zone toward each other, fringe region between substrate seals with sealing agent, filling liquid crystal, and the sealing filling orifice is to form liquid crystal cell.Load onto polarizer in each side of liquid crystal cell by this way, so that the polarization direction of each polarizer is consistent or rectangular with the grinding direction of liquid crystal orientation film.So just made liquid-crystal display.
Can adopt as sealing agent and to contain solidifying agent and as the Resins, epoxy of the alumina particle of spacer.
Can adopt nematic liquid crystal and smectic liquid crystal as liquid crystal.Wherein preferably use nematic liquid crystal.Liquid crystal can be selected from: Schiff bases liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, Santosol 360 liquid crystal, ester liquid crystal, terphenyl liquid crystal, phenylbenzene hexanaphthene liquid crystal, pyrimidine liquid crystal ， diox liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal or the like.In addition, liquid crystal can comprise cholesteryl liquid crystal, and such as the cholesterol muriate, cholesteryl nonanoate and cholesteryl carbonate, and the chiral reagent that can obtain by commercial sources are such as C-15 and CB-15 (trade name is produced by Merck Ltd. company).Also can use ferroelectric liquid crystals in addition, such as P-removal monosilane oxygen base Ben Yajiaji-P-amino-2-methyl butyl laurate.
The polaroid that is contained in the liquid crystal cell outside can be selected from such polaroid; can be by stretching with the orientation polyvinyl alcohol so that it can absorb iodine forms the alignment films that is called the H film and then polarizing coating is clipped in and obtain such polaroid between the rhodia protective membrane, also can be selected from only by the film formed polaroid of H.
According to the present invention, by with radiation liquid crystal orientation film being exposed selectively, can obtain the liquid crystal orientation film that tilt angle wherein can be changed by the radiation with little radiating capacity, and can easily obtain the liquid-crystal display at the good wide visual angle of reliability.Alignment films is exposed to radiation and absorbs its energy, thus since the condition of surface of the variation alignment films of tilt angle change.
Only radiation for liquid crystal aligning agent of the present invention is ultraviolet ray and laser.For obtain can be fine the control orientation 2 " the tilt angle difference, need 20J/cm usually
2Perhaps bigger radiation quantity (metal halide lamp, 365nm).In addition, use the alignment films that is formed by liquid crystal aligning agent of the present invention, needed radiation quantity can be reduced to 10J/cm
2Or lower, thereby just might produce wide viewing angle LCD very efficiently.Because the liquid-crystal display of producing does not need photolithography technology like this, thereby can not damage liquid crystal property, thereby its reliability is good.
Be further explained in detail the present invention below with reference to example.But the present invention is not limited to these examples.
According to by people such as T.J.Scheffer at J.Appl.Phys., the methods of describing in 19,2013 (1980) adopt He-Ne Lasers to carry out the measurement of the tilt angle described with the crystal spinning solution in example.
The orientation characteristic of following assessment liquid crystal cell: when connecting voltage and shutoff voltage, observe liquid crystal cell so that find out whether there is abnormal zone by a polarizing microscope.When not having undesired zone, think that then such liquid crystal cell is good.
Use such liquid crystal cell to carry out the measurement of tilt angle, this liquid crystal cell is to make by stacked two substrates by this way, so that the grinding direction of two substrates is antiparallel, and between two substrates high tilt angle zone toward each other, low tilt angle zone is (see figure 6) toward each other also.
Use such liquid crystal cell to be orientated characteristic evaluation, this liquid crystal cell is to make by stacked two substrates by this way, so that the grinding direction of two substrates is rectangular, each high tilt angle zone and the relative (see figure 7) in low tilt angle zone between two substrates.
Synthetic example 1
With 2 of 29.80 grams, 3,5-tricarboxylic basic ring amyl group acetic ester dianhydride (being called acid anhydrides later on), the P-phenylenediamine of 14.16 grams, be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 405 grams with the diamines by structural formula (8) representative of 1.04 grams, mixture reacted 6 hours under 60 ℃ of temperature.
Reaction mixture is injected in the excessive methanol with the precipitin reaction product.After this, cure 15 hours to provide the particular polymers I (Ia) that 40.35 grams have the 1.06dl/g limiting viscosity with the methanol wash reaction product and under the decompression situation with 40 ℃ of temperature.
Synthetic example 2
Decide to add among the polymkeric substance I (Ia) 800 gram N-N-methyl-2-2-pyrrolidone N-s to 40.00 cuts that in synthetic example 1, obtain, 52.58 gram pyridines and 40.71 gram diacetyl oxides, mixture carried out imidization reaction 4 hours under 115 ℃.
After this, in the mode identical reaction product solution is precipitated to obtain 35.65 grams and have 1.08dl/g limiting viscosity particular polymers II (IIa) with synthetic example 1.
Synthetic example 3
Except that following variation, repeat the step of synthetic example 1: the quantitative change of acid anhydrides is 28.58 grams, and the quantity of P-phenylenediamine changes 13.10 grams into, and changes 3.32 grams into to produce a kind of specific polymkeric substance I (Ib) by the amount of the diamines of top structural formula (8) expression.In addition, according to the mode identical, utilize this specific polymkeric substance I (Ib) to carry out the particular polymers IIs (IIb) of imidization reaction with 36.30 grams of the limiting viscosity that obtains to have 0.99 deciliter/gram with synthetic example 2.
Synthetic example 4
Except that following variation, repeat the step of synthetic example 1: the amount of acid anhydrides changes 27.00 grams into, and the amount of P-phenylenediamine changes 11.72 grams into and changes 6.28 grams into to obtain a kind of particular polymers I (Ic) by the amount of the diamines of said structure formula (8) representative.In addition, utilize this particular polymers I (Ic), carry out imidization reaction, obtain the particular polymers II (IIc) of the limiting viscosities with 0.94 deciliter/gram of 36.55 grams according to the mode identical with synthetic example 2.
Synthetic example 5
Except that following change, repeat the step of synthetic example 1: the acid anhydrides that adopts 26.24 grams, 10, the P-phenylenediamine of 13 grams, 6.10 the diamines by said structure formula (8) expression of gram, and 2.53 the gram as diamines 4,4 '-diaminodiphenyl sulfide to be to produce a kind of particular polymers I (Id), in addition, utilize this particular polymers I (Id), carry out imidization reaction according to the mode identical with synthetic example 2, the limiting viscosities that obtain 35.43 grams are the particular polymers II (IId) of 0.92 deciliter/gram.
Synthetic example 6
Except that following change, repeat the step of synthetic example 1: the acid anhydrides that adopts 20.05 grams, 13.30 4 of gram, 4 '-diaminodiphenyl-methane and 11.65 grams as diamines by the diamines of said structure formula (8) representative to obtain a kind of particular polymers I (Ie), in addition, utilize this particular polymers I (Ie), carry out imidization reaction according to the mode identical with synthetic example 2, the limiting viscosities that obtain 36.07 grams are the particular polymers II (IIe) of 0.91 deciliter/gram.
Synthetic example 7
Except that following change, repeat the step of synthetic example 1: adopt 25.12 gram acid anhydrides, the P-phenylenediamine of 4.85 grams, 9.20 2,3,5 of gram, 6-tetramethyl--1,4-diaminobenzene and 5.84 grams as diamines by the diamines of top structural formula (8) representative to produce a kind of particular polymers I (If).In addition, utilize this particular polymers I (If), carry out imidization reaction according to the mode identical with synthetic example 2, the limiting viscosities that obtain 36.60 grams are the particular polymers II (IIf) of 0.99 deciliter/gram.
Synthetic example 8
Except that following change, repeat the step of synthetic example 1: the acid anhydrides that adopts 19.25 grams, 14.57 3,3 of gram '-dimethyl-4,4 '-diaminodiphenylmethane and 11.18 grams by as the diamines of the said structure formula (8) of diamines expression to obtain a kind of specific polymkeric substance I (Ig).In addition, utilize this particular polymers I (Ig), carry out imidization reaction according to the mode identical with synthetic example 2, the limiting viscosities that obtain 35.30 grams are the particular polymers II (IIg) of 0.94 deciliter/gram.
Synthetic example 9
Except that following change, repeat the step of synthetic example 1: the acid anhydrides of 23.47 grams, 7.36 the P-phenylenediamine of gram, 8.18 grams by the diamines of said structure formula (4) representative and 6.00 grams by the diamines of top structural formula (8) representative as diamines to produce a kind of particular polymers I (Ih).In addition, utilize this particular polymers I (Ih), carry out imidization reaction according to the mode identical with synthetic example 2, the limiting viscosities that obtain 35.44 grams are the particular polymers II (IIh) of 0.96 deciliter/gram.
Synthetic example 10
Except that following change, repeat the step of synthetic example 1: the acid anhydrides that adopts 29.98 grams, 13.42 the P-phenylenediamine of gram, 1.35 grams by the diamines of structural formula (8) representative and 1.25 grams as the n-hexadecylamine of diamines to produce a kind of particular polymers I (Ii).In addition, utilize this particular polymers I (Ii), carry out imidization reaction according to the mode identical with synthetic example 2, the limiting viscosities that obtain 34.85 grams are the particular polymers II (IIi) of 0.93 deciliter/gram.
Synthetic example 11
Except that following change, repeat the step of synthetic example 1: adopt the acid anhydrides of 28.74 grams, 13.17 grams as the P-phenylenediamines of diamines and 3.09 grams as the n-hexadecylamine of monoamine to produce a kind of particular polymers I (Ij).In addition, utilize this particular polymers, carrying out imidization reaction according to the mode identical with synthetic example 2 is the particular polymers II (IIj) of 0.89 deciliter/gram with the limiting viscosities that obtain 34.08 grams.
Synthetic example 12
Except that following change, repeat the step of synthetic example 1: the 5-(2 that adopts a kind of acid anhydrides of conduct of 26.14 grams, 5-dioxy tetrahydrofuran base)-3-methyl-3-hexanaphthene-1, the 2-dicarboxylic acid dianhydride, the P-phenylenediamines of 8.56 grams and 10.30 grams as diamines by the diamines of top structural formula (8) representative to produce a kind of particular polymers I (Ik).In addition, utilize this particular polymers I (Ik), carrying out imidization reaction according to the mode identical with synthetic example 2 is the particular polymers II (IIk) of 0.88 deciliter/gram with the limiting viscosities that obtain 34.90 grams.
Synthetic example 13
Except that following change, repeat the step of synthetic example 1: adopt 27.52 grams as 1 of acid anhydrides, 3,3a, 4,5,9b-hexahydro--5-tetrahydro--2,5-titanium dioxide-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, the P-phenylenediamines of 7.93 grams and 9.55 grams as diamines by the diamines of top structural formula (8) representative to produce a kind of particular polymers I (Il).In addition, utilize this particular polymers I (Il), carry out imidization reaction according to the mode identical with examples of compounds 2, the limiting viscosities that obtain 34.30 grams are the particular polymers II (IIl) of 0.87 deciliter/gram.
Synthetic example 14
Except that following change, repeat the step of synthetic example 1: two rings [2 that adopt a kind of acid anhydrides of conduct of 25.45 grams, 2,2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic anhydride, 8.87 the P-phenylenediamine of gram and 10.68 grams as diamines by the diamines of top structural formula (8) representative to produce a kind of specific polymkeric substance I (Im), in addition, utilize this particular polymers I (Im), carry out imidization reaction according to the mode identical with synthetic example 2, the limiting viscosities that obtain 36.51 grams are the particular polymers II (IIm) of 0.86 deciliter/gram.
Synthetic example 15
Except that following change, repeat the step of synthetic example 1: the acid anhydrides that adopts 32.78 grams, 7.91 the gram the P-phenylenediamine and 4.32 the gram as 3 of diamines, 5-two amidos-4 '-the trifluoromethyl benzanilide to be to produce a kind of particular polymers I (In), in addition, utilize this particular polymers I (In), carrying out imidization reaction according to the mode identical with synthetic example 2 is the particular polymers II (IIn) of 0.91 deciliter/gram with the limiting viscosities that obtain 36.40 grams.
Synthetic example 16
Except that following change, repeat the step of synthetic example 1: the acid anhydrides that adopts 32.78 grams, 7.91 the gram the P-phenylenediamine and as diamines 4.32 the gram 3,5-diamino-3 '-the trifluoromethyl benzanilide to be to produce a kind of particular polymers I (Io), in addition, utilize this particular polymers I (Io), carry out imidization reaction according to the mode identical with synthetic example 2, the limiting viscosities that obtain 36.45 grams are the particular polymers II (IIo) of 0.89 deciliter/gram.
Synthetic example 17
Except that following change, repeat the step of synthetic example 1: the acid anhydrides that adopts 15.14 grams, 2.74 the gram the P-phenylenediamine and 27.12 the gram as 2 of diamines, two [4-(4-amino-2-4-trifluoromethylphenopendant)-phenyl] HFC-236fa of 2-are to produce a kind of particular polymers I (Ip), in addition, utilize this particular polymers I (Ip), carrying out imidization reaction according to the mode identical with synthetic example 2 is the particular polymers II (IIp) of 0.92 deciliter/gram with the limiting viscosities that obtain 36.54 grams.
Synthetic example 18
Except that following change, repeat the step of synthetic example 1: the acid anhydrides that adopts 25.94 grams, 9.39 the gram the P-phenylenediamine and as diamines 9.67 the gram 2, two (4-aminophenyl) HFC-236fa of 2-are to produce a kind of particular polymers I (Iq), in addition, utilize this particular polymers I (Iq), carry out imidization reaction according to the mode identical with synthetic example 2, the intrinsic viscosities that obtain 36.00 grams are the particular polymers II (IIq) of 0.92 deciliter/gram.
Synthetic example 19
Except that following change, repeat the step of synthetic example 1: adopt 25.54 grams as 1 of acid anhydrides, 2,3,4-tetramethylene tetracarboxylic dianhydride, the P-phenylenediamines of 12.68 grams and as diamines by the diamines of 6.78 grams of top structural formula (8) representative to produce a kind of particular polymers I (Ir) of 39.76 grams.
Synthetic example 20
Except that following change, repeat the step of synthetic example 1: adopt 21.51 grams as 1 of acid anhydrides, 2,3,4-tetramethylene tetracarboxylic dianhydride, and 5.93 the gram the P-phenylenediamines and as diamines 17.5 the gram 4,4 '-diamino-2,2 '-two (three oxygen methyl) biphenyl with produce 40.12 the gram a kind of particular polymers I (Is).
Synthetic example 21
Except that following change, repeat the step of synthetic example 1: 1,2 of a kind of acid anhydrides of conduct of 14.55 grams, 3,2 of a kind of diamines of conduct of 4-tetramethylene tetracarboxylic dianhydride and 30.45 grams, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-are to produce a kind of particular polymers I (It) of 39.11 grams.
Synthetic example 22
Except that following change, repeat the step of synthetic example 1: adopt 1 of the 14.46 a kind of acid anhydrides of conduct that restrain, 2,3,4-tetramethylene tetracarboxylic dianhydride, as 2 of 28.76 grams of diamines, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, and 1.78 grams as the n-hexadecylamine of monoamine to produce a kind of particular polymers I (Iu) of 40.54 grams.
Synthetic example 23
Except that following change, repeat the step of synthetic example 1: adopt the P-phenylenediamines of the pyromellitic acid dianhydride of a kind of acid anhydrides of conduct of 28.30 grams and 13.33 grams and 3.34 grams as diamines by the diamines of top structural formula (7) representative to produce a kind of particular polymers I (Iv) of 39.76 grams.
Synthetic example 24
Except that following change, repeat the step of synthetic example 1: the pyromellitic acid dianhydride that adopts a kind of acid anhydrides of conduct of 26.99 grams, 12.04 the P-phenylenediamine as diamines of gram, and 5.97 grams as the n-hexadecylamine of monoamine to produce a kind of particular polymers I (Iw) of 39.77 grams.
Synthetic example 25
Except that following change, repeat the step of synthetic example 1: the pyromellitic acid dianhydride that adopts 22.70 grams as acid anhydrides, with 5.63 the gram the P-phenylenediamines and 16.67 the gram as 4 of diamines, 4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl with produce 40.16 the gram a kind of particular polymers I (Ix).
Synthetic example 26
Except that following change, repeat the step of synthetic example 1: the pyromellitic acid dianhydride that adopts a kind of acid anhydrides of conduct of 23.38 grams, with 5,80 the gram the P-phenylenediamines and 15.82 the gram the 3.5-diamino-3 as diamines '-the trifluoromethyl benzanilide with produce 40.22 the gram a kind of particular polymers I (Iy).
Example 1
The particular polymers (IIa) that is obtained by above-mentioned synthetic example 2 of 5 grams is dissolved in 120 gamma-butyrolactones that restrain to prepare a kind of solution that contains 4% solids component of weight.With having 1 tm screen purpose strainer this solution is filtered to obtain a kind of liquid crystal aligning agent solution.
The solution that obtains above is coated to transparency electrode one side of each sheet of two sheet glass substrates with a kind of ito thin film transparency electrode with the spin rate of changeing in per 3 minutes 3,000 with a spinner, and 100 ℃ of following prebakes 30 seconds.
Then, by the figure mask of liquid-crystal display that is used to be orientated feature measurement of one 3 * 3 centimetres the figure masks that are used for the liquid-crystal displays that tilt angle measures and 100 * 100 microns, substrate is exposed to by a ultraviolet ray of sending as the metal halide lamp of light source (10 joules/centimetre 2 light intensity under the wavelength of 365 nanometers).After this, substrate is baked 1 hour to form the mulch film of 0.05 micron thickness after under 180 ℃.The quantity of specific structure unit II in the polymkeric substance that constitutes this mulch film is 92 molar percentages (mol%).
With a shredder with cylinder, under the movable workbench speed of 500 drum rotational speeds that change and 1 cel, mulch film is carried out milled processed, wherein have the nylon fabrics of a 0.6mm lamination lamination (pile Compression) on every side around described cylinder.After this, with a kind of methanol vapor mulch film is cleaned the substrate that has liquid crystal orientation film with generation, wherein alignment films has definite shape and has the difference at inclination angle in the pixel.
Then, by screen printing, a kind of epoxy resin adhesive that will contain alumina particle with 17 micron diameters be applied to every substrate on the borderline region of liquid crystal orientation film one side that milled processed is crossed.Then, under pressure, two substrates are connected to each other so that the surface of liquid crystal orientation film toward each other, and caking agent is cured.
Next, (by the MLC-2001 of Merk company manufacturing) puts into the space between the substrate from a liquid crystal filling port with a kind of nematic liquid crystal, and this hole is sealed with a kind of epoxy adhesive.Polarizer links to each other so that the grinding direction one of the polarization direction of each polarizer and corresponding liquid crystal orientation film is shown the generation liquid-crystal display with two side external surfaces of substrate.
So, when the liquid-crystal display that produces is used to the tilt angle measurement, find: owing to be exposed to ultraviolet ray, and tilt angle is existed than big-difference, that is, the tilt angle of exposed region is 0.7 °, and exposed region is not 3.5 °.The orientation characteristic of liquid-crystal display all is good in these two zones.
Example 2
The liquid crystal orientation film that will obtain in example 1 is used for preparing a kind of liquid-crystal display.
As shown in Figure 8, in substrate 11, form pixel area 12 and 13, and cover with liquid crystal orientation film 14.A mask 15 that is used in the irradiation step of exposure that after this will describe is positioned over a position towards the surface of substrate.According to this example, adopt traditional method in substrate 1, to form pixel area 12 and 13.Then, on the surface of whole substrate 11, form a liquid crystal orientation film 14, to cover pixel area 12 and 13.In this embodiment, be used as liquid crystal orientation film 14 to form a kind of liquid crystal orientation film of 0.05 micron thickness by the liquid crystal aligning agent that obtains in the example 1.The quantity of specific structure unit II in the polymkeric substance that forms liquid crystal orientation film is 92 molar percentages.After prebake, the mulch film of liquid crystal aligning agent will pass through milled processed.After this, liquid crystal orientation film 14 is exposed by shining 16.Whenever this can carrying out after forming liquid crystal orientation film if shining 16 step of exposure, promptly apply liquid crystal aligning agent, prebake, after cure and grinding steps after.
Using mask 15 to shine under the situation of exposure, the 15a representative of being represented by oblique line does not see through the overlay area of irradiation 16, and does not have the 15b of oblique line to represent the overlay area that sees through irradiation 16.Transmission region is similar to the photomask that generally adopts with one and is used as mask 15 in the face of the partial-pixel zone, perhaps without mask cover is discharged on the desired zone of substrate.
Owing to will shine dispensing on liquid crystal orientation film 14, therefore will use ultraviolet ray in this example.
After all illuminated exposure of upper and lower substrate that constitutes liquid-crystal display, two substrates are stacked together in such a way, promptly exposure area and unexposed area are toward each other.Therefore differently-oriented directivity owing to controlling each pixel area as the unexposed area in high dip angle zone, all can form normal and opposite visual direction in each pixel.So there is not the rapid decline of contrast gradient yet in the liquid-crystal display that obtains, and compares with 45 ° of visual angles of routine along all not having reversal development on normal and the opposite visual direction, has 80 ° of visual angles of a broad.
Embodiment 3 to 18
Except that following change, repeat the step of example 1: be used to prepare liquid-crystal display by the particular polymers IIb to IIq that obtains in the synthetic example 3 to 18.Measure orientation characteristic and the tilt angle of liquid-crystal display, the results are shown in the table 1 at exposure area and unexposed area place.
Table 1
| Example | Particular polymers II | Contain aliphatic series/alicyclic hydrocarbon group | Tilt angle (°) | The liquid crystal aligning characteristic | The II of ad hoc structure unit content (*) | |||
| Exposed portion | Unexposed portion | |||||||
| Dianhydride | Diamines | Terminal | ||||||
| 3 | IIb | ○ | ○ | - | 0.9 | 7.0 | Well | 93 |
| 4 | IIc | ○ | ○ | - | 2.3 | 10.5 | The same | 94 |
| 5 | IId | ○ | ○ | - | 1.8 | 9.8 | The same | 89 |
| 6 | IIe | ○ | ○ | - | 2.5 | 10.4 | The same | 93 |
| 7 | IIf | ○ | ○ | - | 2.3 | 8.2 | The same | 85 |
| 8 | IIg | ○ | ○ | - | 2.0 | 6.9 | The same | 78 |
| 9 | IIh | ○ | ○ | - | 2.0 | 7.0 | The same | 92 |
| 10 | IIi | ○ | ○ | ○ | 1.5 | 9.2 | The same | 92 |
| 11 | IIj | ○ | - | ○ | 2.0 | 5.4 | The same | 95 |
| 12 | IIk | ○ | ○ | - | 2.4 | 6.0 | The same | 100 |
| 13 | IIl | ○ | ○ | - | 2.5 | 5.9 | The same | 87 |
| 14 | IIm | ○ | - | - | 2.7 | 6.3 | The same | 100 |
| 15 | IIn | ○ | - | - | 2.4 | 6.9 | The same | 98 |
| 16 | IIo | ○ | - | - | 2.1 | 4.2 | The same | 80 |
| 17 | IIp | ○ | - | - | 1.4 | 3.5 | The same | 75 |
| 18 | IIq | ○ | - | - | 0.9 | 3.0 | The same | 99 |
This amount of (notes) * is the content (mol%) of the II of ad hoc structure unit in the polymkeric substance that forms liquid crystal orientation film
Example 19 to 23
Except that following change, repeat the step of example 1: adopt the particular polymers Ir or the Iv that obtain by synthetic example 19 to 23, after cure after, under 250 ℃, exposed 1 hour, with nematic liquid crystal (ZLI-2293 is produced by Merck company) preparation liquid-crystal display.Measure the orientation characteristic and the tilt angle of liquid-crystal display, the results are shown in the table 2.
Table 2
| Example | Particular polymers II | Contain aliphatic series/alicyclic hydrocarbon group | Tilt angle (°) | The liquid crystal aligning characteristic | The II of ad hoc structure unit content (*) | |||
| Exposed portion | Unexposed portion | |||||||
| Dianhydride | Diamines | Terminal | ||||||
| 19 | Ir | ○ | ○ | - | 0.4 | 8.3 | Well | 90 |
| 20 | Is | ○ | - | - | 0.7 | 7.5 | The same | 85 |
| 21 | It | ○ | - | - | 0.4 | 4.1 | The same | 90 |
| 22 | Iu | ○ | - | ○ | 0.5 | 6.8 | The same | 96 |
| 23 | Iv | - | ○ | - | 3.5 | 8.5 | The same | 94 |
The definition that (notes) * table 1 provides also is applicable to table 2.
Comparison example 1
Except that following change, repeat the step of example 1: utilize the particular polymers I (Iw) that from synthetic example 24, obtains to prepare liquid-crystal display.When measuring the tilt angle of liquid crystal indicator, find: owing to use ultraviolet exposure, only have fine difference between the tilt angle, that is, the tilt angle of exposure area is 4.6 °, and the unexposed area is 5.5 °.As a result, can't obtain desirable subregion alignment-type liquid crystal indicating meter.
Comparison example 2
Except that following change, repeat the step of example 19 to 23: utilize the particular polymers I (Ix) that obtains by synthetic example 25 to prepare liquid-crystal display.When measuring the tilt angle of liquid-crystal display, find: owing to use ultraviolet exposure, only there is less difference in tilt angle, that is, the tilt angle of exposure area is 5.3 °, and unexposed area is 5.1 °.As a result, can't obtain required subregion alignment-type liquid crystal indicating meter.
Comparison example 3
Except that following change, repeat the step of example 19 to 23: utilize the particular polymers I (Iy) that obtains by synthetic example 26 to prepare liquid-crystal display.Find that owing to use ultraviolet exposure, only there is less difference in tilt angle when measuring the tilt angle of liquid-crystal display, promptly, the tilt angle of exposure area is 7.2 °, and the tilt angle of unexposed area is 7.0 ° of results, can't obtain desirable subregion alignment-type liquid crystal indicating meter.
Liquid crystal aligning agent of the present invention make to obtain a kind of be applicable to make a kind ofly demonstrate fabulous liquid crystal aligning characteristic and become possibility with the bigger change of less irradiation energy generation tilt angle and liquid crystal orientation film with the subregion orientating type TN-STN indicating meter at wide visual angle.
Liquid-crystal display with the liquid crystal orientation film that is formed by liquid crystal aligning agent of the present invention can be applicable to SH (super anisotropy), ferroelectric and Antiferroelectric liquid crystal display by selecting a kind of liquid crystal that adopts.
Further, liquid-crystal display with the liquid crystal orientation film that is formed by liquid crystal aligning agent of the present invention has fabulous liquid crystal aligning characteristic and reliability, and can be by effectively as all kinds of indicating meters as equipment such as desk-top calculator, wrist-watch, clock and watch, digital indicator, WP, Personal Computer and LCD TV and device.
Claims (6)
1. method that is used to make liquid-crystal display, comprising the following step:
Be coated to a kind of liquid crystal aligning agent in the pair of substrate at least one and cure substrate to form a kind of liquid crystal orientation film; Wherein said liquid crystal aligning agent comprises a kind of polymkeric substance that at least one is selected from the structural unit of the group that contains the structural unit of being represented by following structural (1) and (2) that contains:
R wherein
1And R
2Be respectively tetravalence and divalent organic group, and one of them organic group is aliphatic series or alicyclic alkyl group or a group that contains aliphatic series or alicyclic alkyl group,
And
R wherein
3And R
4Be respectively tetravalence and divalent organic group, and one of them group is aliphatic series or alicyclic alkyl group, or a group that contains aliphatic series or alicyclic alkyl, it is characterized in that described method also comprises the following steps:
Thereby will be formed with the substrate sections ground of liquid crystal orientation film on it with shining the tilt angle that exposure is changed partly.
2. described method that is used to make liquid-crystal display of claim 1, wherein said liquid crystal aligning agent comprises a kind of polymkeric substance, in this polymkeric substance, contain account for the structural unit total amount 40 to 100mol% be selected from structural unit in the group of forming by the structural unit of the structural unit of said structure formula (1) representative and said structure formula (2) representative.
3. described method that is used to make liquid-crystal display of claim 1, wherein said liquid crystal aligning agent comprise being selected from and contain by following structural (A) and (B) at least a polymkeric substance in the polymkeric substance group of representative:
R wherein
1And R
2Be respectively tetravalence and divalent organic group, wherein at least one organic group is aliphatic series or alicyclic alkyl group, or contains the group of aliphatic series or alicyclic alkyl, and n is number of repeating units,
R wherein
3And R
4Be respectively tetravalence and divalent organic group, and one of them organic group is aliphatic series or alicyclic alkyl group or a group that contains aliphatic series or alicyclic alkyl, and n is a number of repeating units.
4. described method that is used to make liquid-crystal display of claim 1, wherein when when measuring in N-Methyl pyrrolidone under 30 ℃, described polymkeric substance has the limiting viscosity of 0.05 to 10 deciliter/gram.
5. described method that is used to make liquid-crystal display of claim 1, the R in its Chinese style (I)
1And the R in the formula (2)
3Be alicyclic alkyl group or a group that contains the alicyclic alkyl group.
6. described method that is used to make liquid-crystal display of claim 1, the R in its Chinese style (1)
2And the R in the formula (2)
4Be divalent organic group, the diamines that this group is represented derived from following formula:
R wherein
21Be divalent organic group, be selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-CO-, and R
22It is a steroid skeleton.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6102923A JPH07309351A (en) | 1994-05-17 | 1994-05-17 | Bag with fastener |
| EP95303246A EP0683105B1 (en) | 1994-05-17 | 1995-05-15 | Venting valve for a re-closable bag |
| DE69506167T DE69506167T2 (en) | 1994-05-17 | 1995-05-15 | Vent valve for reclosable bags |
| CN95107115A CN1092506C (en) | 1994-05-17 | 1995-05-17 | A snap-fastener bag |
| TW086207329U TW397051U (en) | 1994-05-17 | 1995-06-30 | Bag with couple type fastener |
| CNB951150189A CN1196768C (en) | 1994-05-17 | 1995-07-10 | Liquid crystal aligning agent and liquid crystal display device |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6102923A JPH07309351A (en) | 1994-05-17 | 1994-05-17 | Bag with fastener |
| CNB951150189A CN1196768C (en) | 1994-05-17 | 1995-07-10 | Liquid crystal aligning agent and liquid crystal display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1140195A CN1140195A (en) | 1997-01-15 |
| CN1196768C true CN1196768C (en) | 2005-04-13 |
Family
ID=37734292
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95107115A Expired - Lifetime CN1092506C (en) | 1994-05-17 | 1995-05-17 | A snap-fastener bag |
| CNB951150189A Expired - Lifetime CN1196768C (en) | 1994-05-17 | 1995-07-10 | Liquid crystal aligning agent and liquid crystal display device |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95107115A Expired - Lifetime CN1092506C (en) | 1994-05-17 | 1995-05-17 | A snap-fastener bag |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0683105B1 (en) |
| JP (1) | JPH07309351A (en) |
| CN (2) | CN1092506C (en) |
| DE (1) | DE69506167T2 (en) |
| TW (1) | TW397051U (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2691881B2 (en) * | 1995-05-31 | 1997-12-17 | 株式会社サンエー化研 | Packaging bag with check valve having filtration surface and manufacturing apparatus thereof |
| US5973768A (en) | 1996-07-03 | 1999-10-26 | Imation Corp. | Light-tight bag having a trapped air exit |
| US6139185A (en) * | 1997-05-09 | 2000-10-31 | The Procter & Gamble Company | Flexible bag with selectively-activatible support-engagement feature |
| US6149304A (en) * | 1997-05-09 | 2000-11-21 | The Procter & Gamble Company | Flexible storage bag with selectively-activatible closure |
| EP0887285B1 (en) * | 1997-06-19 | 1999-09-01 | Hisao Kai | Vacuum packaging bag and vacuum packaging method |
| JP3579660B2 (en) * | 2001-04-20 | 2004-10-20 | 有限会社アピィール | Degassing bag |
| KR100543093B1 (en) * | 2003-04-09 | 2006-01-20 | 제일모직주식회사 | Diamine containing Triazine group, Polyamic Acid synthesized from the Diamine, and LC Alignment Layer Prepared by the Polyamic acid |
| CN100334493C (en) * | 2004-05-28 | 2007-08-29 | 友达光电股份有限公司 | Monomer for stabilizing orientation of polymer and liquid crystal display panel with polymer therefrom |
| US7290660B2 (en) * | 2004-07-23 | 2007-11-06 | Tilman Paul A | Storage system having a disposable vacuum bag |
| US20100021092A1 (en) * | 2004-12-28 | 2010-01-28 | Ryouichi Ootsubo | Structure of air vent passage for sealed bag, sealed bag and method of manufacturing sealed bag |
| US7748904B2 (en) * | 2005-05-12 | 2010-07-06 | Illinois Tool Works Inc. | Multicompartment evacuable storage bag |
| US20060257533A1 (en) * | 2005-05-12 | 2006-11-16 | Plourde Eric P | Self-venting reclosable packages |
| CN101135813B (en) * | 2006-08-29 | 2011-03-16 | Jsr株式会社 | Liquid crystal tropism agent, liquid crystal tropism film and liquid crystal display element |
| JP4904360B2 (en) * | 2006-09-25 | 2012-03-28 | 修 河合 | Sealed bag |
| JP2008176304A (en) * | 2006-12-22 | 2008-07-31 | Jsr Corp | Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display element, and optical member |
| JP5046418B2 (en) * | 2007-04-16 | 2012-10-10 | 壽一 葛西 | Package using laminated film |
| JP5067570B2 (en) * | 2007-08-01 | 2012-11-07 | Ｊｓｒ株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP5651953B2 (en) * | 2008-01-25 | 2015-01-14 | 日産化学工業株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| WO2010026721A1 (en) * | 2008-09-03 | 2010-03-11 | シャープ株式会社 | Alignment film, alignment film material, liquid crystal display device comprising alignment film, and method for manufacturing same |
| US9126734B2 (en) | 2011-01-31 | 2015-09-08 | Ultraperf Technologies Inc. | Self venting steam valve for flexible packaging bags and pouches used in cooking of foods |
| KR101864914B1 (en) * | 2011-03-31 | 2018-06-05 | 닛산 가가쿠 고교 가부시키 가이샤 | Liquid crystal aligning agent and liquid crystal alignment film using same |
| KR101444190B1 (en) | 2011-12-19 | 2014-09-26 | 제일모직 주식회사 | Liquid crystal alignment agent, liquid crystal alignment film using the same, and liquid crystal display device including the liquid crystal alignment film |
| KR101387735B1 (en) * | 2011-12-22 | 2014-04-25 | 제일모직주식회사 | Liquid crystal alignment agent, liquid crystal alignment film using the same, and liquid crystal display device including the liquid crystal alignment film |
| CN105579897B (en) * | 2013-07-24 | 2019-03-15 | 日产化学工业株式会社 | Aligning agent for liquid crystal and the liquid crystal orientation film for having used it |
| MY175020A (en) * | 2013-10-17 | 2020-06-03 | Sin Sheng Kuang M Sdn Bhd | Package with pressure venting seal carrying surface profile |
| WO2019009139A1 (en) * | 2017-07-04 | 2019-01-10 | 株式会社柏原製袋 | Closing valve made of sheet and bag with closing valve |
| CN111838901B (en) * | 2019-04-30 | 2023-01-31 | 黄振正 | Chain clamping belt |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE6608077U (en) * | 1965-11-17 | 1971-06-09 | Hesser Ag Maschf | PRESSURE VALVE ON PACKAGING MADE OF SEALABLE OR WELDABLE FILM. |
| US4532652A (en) * | 1983-11-16 | 1985-07-30 | Mobil Oil Corporation | Plastic bag with air exhaustion valve |
| JPH0314614Y2 (en) * | 1985-12-04 | 1991-04-02 | ||
| KR900000414B1 (en) * | 1986-02-22 | 1990-01-30 | 주식회사 크린랲 | Wrap film for food |
| FR2695108B1 (en) * | 1992-09-02 | 1995-04-21 | Georges Paul | Packaging, process and packaging device for liquid, solid or pasty product pasteurized or sterilized. |
-
1994
- 1994-05-17 JP JP6102923A patent/JPH07309351A/en active Pending
-
1995
- 1995-05-15 EP EP95303246A patent/EP0683105B1/en not_active Expired - Lifetime
- 1995-05-15 DE DE69506167T patent/DE69506167T2/en not_active Expired - Fee Related
- 1995-05-17 CN CN95107115A patent/CN1092506C/en not_active Expired - Lifetime
- 1995-06-30 TW TW086207329U patent/TW397051U/en unknown
- 1995-07-10 CN CNB951150189A patent/CN1196768C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1122216A (en) | 1996-05-15 |
| TW397051U (en) | 2000-07-01 |
| CN1140195A (en) | 1997-01-15 |
| EP0683105A1 (en) | 1995-11-22 |
| CN1092506C (en) | 2002-10-16 |
| JPH07309351A (en) | 1995-11-28 |
| DE69506167D1 (en) | 1999-01-07 |
| EP0683105B1 (en) | 1998-11-25 |
| DE69506167T2 (en) | 1999-05-06 |
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| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: JSR CORP.; SHARP CORP. Free format text: FORMER NAME OR ADDRESS: JSR CORP; SHARP CORP. |
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| CP03 | Change of name, title or address |
Address after: Tokyo, Japan Patentee after: JSR Co., Ltd. Patentee after: Sharp company Address before: Tokyo, Japan Patentee before: Jeschya Co., Ltd. Patentee before: Sharp company |
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| CX01 | Expiry of patent term |
Expiration termination date: 20150710 Granted publication date: 20050413 |
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| EXPY | Termination of patent right or utility model |