CN1648726A - Liquid orientation agent and liquid orientation film as well as liquid display element - Google Patents
Liquid orientation agent and liquid orientation film as well as liquid display element Download PDFInfo
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- CN1648726A CN1648726A CNA2005100028154A CN200510002815A CN1648726A CN 1648726 A CN1648726 A CN 1648726A CN A2005100028154 A CNA2005100028154 A CN A2005100028154A CN 200510002815 A CN200510002815 A CN 200510002815A CN 1648726 A CN1648726 A CN 1648726A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B13/00—Conduits for emptying or ballasting; Self-bailing equipment; Scuppers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
- F16K1/00—Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces
- F16K1/02—Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces with screw-spindle
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
- F16K1/00—Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces
- F16K1/32—Details
- F16K1/34—Cutting-off parts, e.g. valve members, seats
- F16K1/36—Valve members
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
- F16K31/00—Actuating devices; Operating means; Releasing devices
- F16K31/44—Mechanical actuating means
- F16K31/50—Mechanical actuating means with screw-spindle or internally threaded actuating means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B2221/00—Methods and means for joining members or elements
- B63B2221/02—Methods and means for joining members or elements by welding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B2221/00—Methods and means for joining members or elements
- B63B2221/08—Methods and means for joining members or elements by means of threaded members, e.g. screws, threaded bolts or nuts
Abstract
The invention relates to a liquid crystal aligning agent and liquid crystal aligning film and liquid crystal display device. The liquid crystal aligning agent and liquid crystal aligning film are composed of a polymer having at least one of an imide bond unit and an amic acid bond unit formed by reaction of a tetracarboxylic acid dianhydride and a diamine or the mixture thereof. The liquid crystal aligning film formed by the liquid crystal aligning agent can provides liquid crystal display device with high reliability, wear resistance and liquid crystal orientation property.
Description
Technical field
The present invention relates to aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells.Relate to the aligning agent for liquid crystal that can obtain following liquid crystal orientation film in more detail, and the above-mentioned liquid crystal display cells of this liquid crystal orientation film and this alignment films of use, this liquid crystal orientation film is to reliability, low image retention, wearing quality and liquid crystal aligning excellence, particularly can be applied on the large substrate, for the recovery of substrate, can easily peel off by any liquid crystal orientation film stripper in commercially available water system, the organic system.
Background technology
Past, what people knew has: the TN type liquid crystal display cells with TN (Twisted Nematic) type liquid crystal cell, this TN type liquid crystal display cells is at 2 pieces of insertion nesa coatings and between the substrate of surface formation liquid crystal orientation film, formation has the anisotropic nematic crystal layer of positive medium and forms the box of rhythmo structure, and the major axis of above-mentioned liquid crystal molecule is turned round continuously towards another substrate from a substrate and turn 90 degrees.
In addition, also there is STN (Super Twisted Nematic) type liquid crystal display cells, in STN type liquid crystal display cells, the major axis of this liquid crystal molecule of interpolation by the chirality agent utilizes consequent birefringence effect at the states that are implemented in 180 degree between substrate or reverse continuously more than 180 degree.And recently, also developed and between the subtend substrate, formed nematic crystal layer with anisotropic vertical (homeotropic) state of orientation of negative medium, or screw axis and substrate normal be the cholesterol liquid crystal layer of parastate, adds visitor (guest)-host (host) the type reflection type liquid crystal display element of pigment in this liquid crystal layer.Here, the liquid crystal aligning membrane material as constituting liquid crystal display cells uses polyimide in the past, and polyamide and polyester etc. is known.Polyimide particularly because thermotolerance, with the compatibility of liquid crystal, excellences such as physical strength are so use in most liquid crystal display cells.
But, recently liquid crystal display cells also from aspects such as maximization, lighting, low power consumption quantifications gradually to significantly developing with the high-performance display element, accompany with it, liquid crystal orientation film required also increasingly stringent of performance.Particularly, the operation that relates to the maximization of following substrate is improved and cost degradation requires also stricter.But, from existing known polyimide precursor polyamic acid, or have the alignment films of the imide polymer formation of the structure that its dehydration closed-loop is obtained, give high adherence, coating in order to realize its high reliability, the high quantitative power of orientation and high-wearing feature to substrate.As a result, large substrate is reclaimed, promptly use commercially available water system and organic system liquid crystal orientation film stripper to peel off alignment films and can not fully peel off for realizing cost degradation.On the other hand, the alignment films that can peel off easily with commercially available liquid crystal orientation film stripper has the problem that reliability, the quantitative power of orientation also have wearing quality to reduce.
Summary of the invention
The object of the present invention is to provide to obtain both can realizing good reliability, orientation characteristic, wearing quality the aligning agent for liquid crystal of the liquid crystal orientation film of again can be easily peeling off with commercially available water system and organic system stripper.
Other purpose of the present invention is to provide possesses the liquid crystal orientation film of various excellent properties as mentioned above.
Further other purpose of the present invention is to provide the liquid crystal display cells that possesses liquid crystal orientation film of the present invention.
Further purpose of the present invention and advantage can be from following explanations and clear and definite.
Above-mentioned purpose of the present invention and advantage, according to the present invention, first, realize that by aligning agent for liquid crystal this aligning agent for liquid crystal constitutes by having the acid imide bonding unit that forms by tetrabasic carboxylic acid dicarboxylic anhydride and diamine reactant and polymkeric substance or its potpourri of at least a bonding unit in the amic acid bonding unit, for above-mentioned polymkeric substance or its potpourri, it is characterized in that above-mentioned tetrabasic carboxylic acid dicarboxylic anhydride contains is selected from 1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride, 3,5,6-three carboxyls norbornane-2-acetate dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dicarboxylic anhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl) naphtho-[1,2-c] furans-1, in 3-diketone and the pyromellitic acid dicarboxylic anhydride at least 3 kinds, and above-mentioned diamines contains and is selected from p-phenylenediamine (PPD), two aminopropyl tetramethyl disiloxanes, 4,4 '-diaminodiphenyl-methane, 2,2 '-dimethyl-4,4 '-benzidine and 3, in two (the 4-aminobenzoic acyl-oxygen base) cholesterol of 6-at least 3 kinds.
Above-mentioned purpose of the present invention and advantage, according to the present invention, the second, realize by the liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 3rd, realize by the liquid crystal display cells that possesses liquid crystal orientation film of the present invention.
Further other purpose and advantage of the present invention, by following explanation as can be known.
According to the present invention, the liquid crystal display cells of high reliability, high liquid crystal aligning, high-wearing feature can be provided, and can easily peel off alignment films for the recovery of substrate.
Liquid crystal display cells with the liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention, except that going for TN type and STN type liquid crystal display cells, by the liquid crystal of selecting to use, can also be applicable to SH (Super Homeotropic) type, IPS (In-Plane Switching) type, the liquid crystal display cells of strong medium and anti-strong medium etc.
And liquid crystal display cells of the present invention can use in various devices effectively, for example uses in display device such as desk-top computer, wrist-watch, timer, parameter display board, word processor, PC, LCD TV.
Embodiment
Below, to the detailed description of the invention.Liquid crystal orientation film of the present invention, usually, can be by after being applied to aligning agent for liquid crystal of the present invention on the transparent electrode plate, dry (usually, heat drying) forms, and the enforcement friction waits to be used after the orientation process on film surface.Aligning agent for liquid crystal of the present invention is to constitute by having the acid imide bonding unit that forms by tetrabasic carboxylic acid dicarboxylic anhydride and diamine reactant and polymkeric substance or its potpourri of at least a bonding unit in the amic acid bonding unit.Contain at aligning agent for liquid crystal under the situation of both bonding units, can contain the potpourri of polyimide and polyamic acid, also can contain polymkeric substance with acid imide bonding unit and amide linkage unit.In this polymkeric substance, acid imide bonding unit and amide linkage unit can contain with any state in random or the block.
Liquid crystal orientation film of the present invention can carry out heat drying when above-mentioned aligning agent for liquid crystal being applied to the operation of carrying out drying on the substrate, make amide linkage unit's dehydration closed-loop of this aligning agent for liquid crystal, becomes acid imide bonding unit.
＜polyamic acid 〉
The polyamic acid that uses among the present invention can be with tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound ring-opening polymerization addition and obtain.
[tetrabasic carboxylic acid dicarboxylic anhydride]
As the tetrabasic carboxylic acid dicarboxylic anhydride, can use 1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride, 3,5,6-three carboxyls norbornane-2-acetate dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dicarboxylic anhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl) naphtho-[1,2-c] furans-1,3-diketone and pyromellitic acid dicarboxylic anhydride.
As the tetrabasic carboxylic acid dicarboxylic anhydride, at least 3 kinds in above-mentioned 8 kinds of compounds are used in combination is necessary.Be used in combination by at least 3 kinds, as required, can easily liquid crystal orientation film be peeled off from substrate with stripper.At least 3 kinds combination preferably contains the pyromellitic acid dicarboxylic anhydride, and especially to contain with 30% ratio at least be particularly preferred to the pyromellitic acid dicarboxylic anhydride.
The polyamic acid that uses among the present invention as the tetrabasic carboxylic acid dicarboxylic anhydride, except that above-mentioned 8 kinds of compounds, can also contain other tetrabasic carboxylic acid dicarboxylic anhydride as required.
As this other tetrabasic carboxylic acid dicarboxylic anhydride, can enumerate for example butanetetra-carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2,3,4-encircles penta tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-hexamethylene tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5 (tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofurfuryl)-and 3-methyl-3-cyclohexane-1,2-dicarboxylic acid dicarboxylic anhydride, following formula (I) and (II) represented aliphatics and ester ring type tetrabasic carboxylic acid dicarboxylic anhydrides such as compound;
[changing 1]
(in the formula, R
1And R
4, expression has the divalent organic group of aromatic rings, R
2And R
3, expression hydrogen atom and alkyl, a plurality of R of existence
2And R
3, can be the same or different respectively.)
3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-xenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-xenyl ether tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-tetraphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-furans tetrabasic carboxylic acid dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dicarboxylic anhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two phthalic acid dicarboxylic anhydrides, 3,3 ', 4,4 '-xenyl tetrabasic carboxylic acid dicarboxylic anhydride, two (phthalic acid) phenyl phosphine oxide dicarboxylic anhydride, to penylene-two (triphenyl phthalic acid) dicarboxylic anhydride, a penylene-two (triphenyl phthalic acid) dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl methane dicarboxylic anhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butylene glycol-two (dehydration trimellitate), 1,6-hexanediol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2, two (4-hydroxy phenyl) propane-two (dehydration trimellitate) of 2-, following formula (1)～(4) represented aromatic tetracarboxylic acid's anhydride compounds such as compound.They can a kind separately or will at least 2 kinds be used in combination.
[changing 2]
These other tetrabasic carboxylic acid dicarboxylic anhydride, for the above-mentioned polymkeric substance that uses among the present invention or its potpourri, preferably with 50～0.1 moles of %, more preferably 30～0.1 moles of % especially preferably use with the amount of 25～0.1 moles of % with respect to whole tetrabasic carboxylic acid dicarboxylic anhydrides.
[diamine compound]
As diamine compound, can use p-phenylenediamine (PPD), two aminopropyl tetramethyl disiloxanes, 4,4 '-diaminodiphenyl-methane, 2,2 '-dimethyl-4,4 '-benzidine and 3, two (the 4-aminobenzoic acyl-oxygen base) cholesterol of 6-.As diamines, at least 3 kinds in these 5 kinds of diamines are used in combination is necessary.
Be used in combination by at least 3 kinds, as required, liquid crystal orientation film easily can be peeled off with stripper from substrate.
The polyamic acid that uses among the present invention except that above-mentioned 5 kinds of compounds, can also contain other diamine compound as diamine compound as required.
As this other diamine compound, can enumerate m-phenylene diamine, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 4,4 '-diamino-diphenyl ether, 1,5-diaminonaphthalene, 3,3 '-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 2,2 '-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2 ,-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-two (4-aminophenyl) HFC-236fa, 2,2 '-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 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-hydrogen anthracenes of 9-, 2, the 7-diamino-fluorene, 9, two (4-aminophenyl) fluorenes of 9-, 4,4 '-methylene-two (2-chloroaniline), 2,2 '-xylyl methyl fluoride-4,4 '-diamido hexichol, 2,2 ', 5,5 '-tetrachloro-4,4,-benzidine, 2,2 '-two chloro-4,4 '-diamido-5,5 '-dimethoxy-biphenyl, 3,3 ,-dimethoxy-4 ', 4 '-benzidine, 1,4,4 '-(to the penylene isopropylidene) biphenylamine, 4,4 ,-(a penylene isopropylidene) biphenylamine, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl;
Terephthaldehyde's base diamines, 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene bicyclopentadiene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three rings [6,2,1,0
2.7]-undecylene dimethyl diamines, 4,4 '-di-2-ethylhexylphosphine oxide aliphatics and ester ring type diamines such as (cyclo-hexylamine);
Single-substituted support two amines that following formula (III) is represented; The diamido organosiloxane (still, except two aminopropyl tetramethyl disiloxanes) that following formula (IV) is represented;
[changing 3]
(in the formula, X represents to be selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R
5Expression has 1 valency organic group of steroid skeleton or trifluoromethyl.R
9The alkyl of expression carbon number 1～12, the R of a plurality of existence
9Can be the same or different respectively, p is 1～3 integer, and q is 1～20 integer.)
The change thing that following formula (5)～(8) are represented etc.These diamine compounds can also can be used in combination at least 2 kinds separately.
[changing 4]
(in the formula, y is 2～12 integer, and z is 1～5 integer.)
These other diamine compound, for the above-mentioned polymkeric substance that uses among the present invention or its potpourri, with respect to whole diamine compounds, preferably with 80～0.1 moles of %, more preferably 60～0.1 moles of % especially preferably use with 50～0.1 moles of %.
For the tetrabasic carboxylic acid dicarboxylic anhydride of polyamic acid synthetic reaction and the usage ratio of diamine compound, the amino that in diamine compound, contains with respect to 1 equivalent, the anhydride group that contains in the tetrabasic carboxylic acid dicarboxylic anhydride is preferably 0.2～2 equivalent, and the ratio of 0.3～1.4 equivalent more preferably.The situation of ratio less than 0.2 equivalent of the anhydride group that contains in the tetrabasic carboxylic acid dicarboxylic anhydride and surpass any situation of the situation of 2 equivalents, it is too small that the molecular weight of the polymkeric substance of gained can become, and has the situation of the coating variation of aligning agent for liquid crystal.
Constitute the polyamic acid of aligning agent for liquid crystal of the present invention, synthesize by above-mentioned tetrabasic carboxylic acid dicarboxylic anhydride and the reaction of above-mentioned diamine compound.The synthetic reaction of polyamic acid in organic solvent, at 0～150 ℃, is more preferably carried out under 0～100 ℃ temperature conditions usually.If below 0 ℃, there is the situation of the dissolubility variation of compound in solvent in temperature of reaction, if surpass 150 ℃, the situation that exists the resulting polymers molecular weight to reduce.
As the synthetic middle organic solvent that uses of polyamic acid, as long as can dissolve by the tetrabasic carboxylic acid dicarboxylic anhydride, the polyamic acid that the diamine compound reaction generates just is not particularly limited, for example, can enumerate for example gamma-butyrolacton, the N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, N, the N-dimethyl acetamide, dimethyl sulfoxide, 4-methyl urea, HMPA, 1,3-dimethyl-aprotic polar solvents such as 2-imidazolidinone; Metacresol, xylenols, phenol, phenol solvents such as halogenated phenol.
The use amount of organic solvent (A) is preferably the total amount (B) that makes reaction raw materials tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound, is the amount of 0.1～30 weight % with respect to the total amount (A+B) of reaction solution.
In addition, in above-mentioned organic solvent, can in the scope that the polyamic acid that is generated is not separated out, unite the alcohols of the Weak solvent that uses polyamic acid, ketone, the ester class, ethers,, halogenated hydrocarbon, hydro carbons etc.As the instantiation of this Weak solvent, for example, can enumerate methyl alcohol, ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, the 4-butylene glycol, triethylene glycol, acetone, MEK, methylisobutylketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethy-aceto oxalate, diethyl malonate, ether, the glycol monomethyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, Ethylene Glycol Methyl ether acetic acid ester, methyl proxitol, propylene glycol ethylether, the propylene glycol dimethyl ether, propylene glycol Anaesthetie Ether, dipropylene glycol methyl ether, the dipropylene glycol ethylether, dipropylene glycol dimethyl ether, dipropylene glycol Anaesthetie Ether, ethylene glycol monoethyl ether acetate, 4-hydroxy-4-methyl-2-pentane, 2-hydroxypropanone-acetoacetic ester, ethyl lactate, methyl lactate, butyl lactate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-methyl-3-methoxybutanol, 3-ethyl-3-methoxybutanol, 2-methyl-2-methoxybutanol, 2-ethyl-2-methoxybutanol, 3-methyl-3-ethoxy butanols, 3-ethyl-3-ethoxy butanols, 2-methyl-2-ethoxy butanols, 2-ethyl-2-ethoxy butanols, tetrahydrofuran, methylene chloride, 1, the 2-ethylene dichloride, 1,4-dichloroetane, trichloroethanes, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene etc.They can be used in combination separately or with at least 2 kinds.
By above-mentioned synthetic reaction, can obtain dissolving the polymer solution that polyamic acid forms.Then, this reaction solution is infused in a large amount of Weak solvents obtains precipitate, by this precipitate drying under reduced pressure can be obtained polyamic acid.In addition, by carry out 1 time or for several times this polyamic acid be dissolved in once more in the organic solvent, the operation of separating out in Weak solvent then can be made with extra care polyamic acid.
＜polyimide 〉
Constitute the polyimide of aligning agent for liquid crystal of the present invention, can prepare by following method (1)～(2).In addition, make recurring unit's part polymkeric substance dehydration closed-loop, so-called imidizate rate less than 100% of polyamic acid, also be applicable to aligning agent for liquid crystal of the present invention.
Method (1): polyamic acid is heated and the method for dehydration closed-loop.
The temperature of reaction of this method is preferably 60～300 ℃, more preferably 120～250 ℃.60 ℃ of temperature of reaction less thaies, imidization reaction can not fully be carried out, and temperature of reaction surpasses 250 ℃, and the molecular weight of gained polyimide can reduce.
Method (2): polyamic acid is dissolved in the organic solvent, in this solvent, adds dewatering agent and imidization catalyst, Jia Re method as required.
In this method,, for example can use acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride as dewatering agent.The use amount of dewatering agent is preferably 1.6～20 moles with respect to 1 mole of polyamic acid recurring unit.In addition, as imidization catalyst, can use for example pyridine, trimethylpyridine, lutidines, tertiary amines such as triethylamine.But, be not limited to these.The use amount of imidization catalyst is preferably 0.5～10 mole with respect to 1 mole of employed dewatering agent.In addition, as the organic solvent that uses in the imidization reaction, can enumerate the identical organic solvent of the illustrated organic solvent of solvent that in polyamic acid is synthetic, uses with conduct.And the temperature of reaction of imidization reaction is preferably 0～180 ℃, more preferably 60～150 ℃.
The intrinsic viscosity of＜polyamic acid and polyimide 〉
The as above intrinsic viscosity of the polyamic acid of gained and polyimide (30 ℃ are measured in the N-N-methyl-2-2-pyrrolidone N-.Below identical.), be preferably 0.05～10dl/g, more preferably 0.05～5dl/g.
＜end modified type polymkeric substance 〉
Forming the polyamic acid and the polyimide that use in the aligning agent for liquid crystal of liquid crystal orientation film of the present invention, can be end modified type polymkeric substance.This end modified type polymkeric substance, molecular weight can be regulated, and can can't harm effect of the present invention, and improves coating characteristics of aligning agent for liquid crystal etc.End modified type polymkeric substance can add acid anhydrides, monoamine compound by in synthesizing polyamides when acid in reaction system, or monoisocyanates compound etc. and synthesizing.
As in order to obtain the acid anhydrides that end modified type polymkeric substance the time adds in synthesizing polyamides acid in reaction system, can enumerate maleic anhydride, phthalic anhydride, the itaconicacid acid anhydride, positive decyl succinic anhydride, the dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc.In addition, as the monoamine that in reaction system, adds, can enumerate for example aniline, cyclo-hexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive undecylamine, positive lauryl amine, positive tridecyl amine, positive tetradecy lamine, positive pentadecyl amine, positive cetylamine, positive heptadecyl-amine, positive octadecylamine, alkyl amines such as positive 20 amine; 3-aminopropyl methyldiethoxysilane, 3-[N-allyl-N-(2-amino-ethyl)] TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, the N-[(3-trimethoxysilyl) propyl group] diethylentriamine etc.In addition, as the monoisocyanates compound, can enumerate for example phenyl isocyanate, naphthyl isocyanate etc.
＜aligning agent for liquid crystal 〉
Liquid crystal orientation film of the present invention is contained by dissolving in organic solvent normally that aligning agent for liquid crystal that above-mentioned polyimide and/or polyamic acid constitute forms.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, can enumerate the identical solvent of the illustrated solvent of solvent that in the polyamic acid synthetic reaction, uses with conduct.In addition, use is united in use when the polyamic acid synthetic reaction the illustrated Weak solvent of solvent that also can suit to select and unite.
Solid component concentration in the aligning agent for liquid crystal of formation liquid crystal orientation film of the present invention can considered viscosity, and back selection such as volatility is preferably in 1～10 weight % scope.That is, aligning agent for liquid crystal of the present invention is coated on substrate surface, becomes filming of liquid crystal orientation film, but under the situation of solid component concentration less than 1 weight %, and this thickness of filming is too small and be difficult to obtain good liquid crystal orientation film.Solid component concentration surpasses under the situation of 10 weight %, and the thickness of filming is excessive and can not obtain good liquid crystal orientation film, and in addition, the viscosity of aligning agent for liquid crystal increases the easy variation of coating characteristics.In addition, the temperature when preparing aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
＜contain the compound of epoxy radicals 〉
Form the aligning agent for liquid crystal of liquid crystal orientation film of the present invention, can contain the compound that has 1 epoxy radicals in the molecule at least as required.As the compound that has at least one epoxy radicals in the molecule, for example can enumerate ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2 '-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexanediol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (N, the N-diglycidyl amino methyl) cyclohexanes of 3-, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methanes etc. are as preferred, contain the blending ratio of epoxy compounds as this, with respect to 100 parts by weight polymer, be preferably and be not higher than 40 weight portions, more preferably 0.1～30 weight portion.
Form in the aligning agent for liquid crystal of liquid crystal orientation film of the present invention,, can also contain the compound of functional silanes to improving the fusible viewpoint of substrate surface.Contain the compound of functional silanes as this, can enumerate for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 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 trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide three ethylene triamines, N-trimethoxy-silylpropyl three ethylene triamines, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, two (the ethylene oxide)-3-TSL 8330s of N-, two (the ethylene oxide)-3-aminopropyltriethoxywerene werene of N-etc.These contain the blending ratio of the compound of functional silanes, with respect to 100 parts by weight polymer, are preferably and are not higher than 40 weight portions, more preferably 0.1～30 weight portion.
＜liquid crystal display cells 〉
The liquid crystal display cells that uses liquid crystal orientation film of the present invention to obtain can pass through for example following method manufacturing.
(1) by for example roll coating process, rotary process, methods such as print process, coating forms the aligning agent for liquid crystal of liquid crystal orientation film of the present invention on the one side of the substrate that is provided with patterned nesa coating, then, films by coated face is added thermosetting.Here, as substrate, for example can use glass such as float glass, soda-lime glass; By polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, the transparency carrier that plastics such as polycarbonate form.Nesa coating as being arranged on the substrate one side can use by tin oxide (SnO
2) the NESA film (U.S. PPG register of company trade mark) that forms, indium oxide-tin oxide (In
2O
3-SnO
2) the ITO film that forms etc.The pattern of these nesa coatings can use photo-engraving process or with the method for pre-mask.During the coating of aligning agent for liquid crystal, for the cohesive that makes substrate surface and nesa coating and film better, can be on this surface of substrate, coating in advance contain functional silanes compound, contain the compound of functionality titanium etc.Heating-up temperature after the aligning agent for liquid crystal coating is preferably 80～300 ℃, more preferably 120～250 ℃.In addition, contain the aligning agent for liquid crystal of the present invention of polyamic acid, become filming of alignment films, carry out dehydration closed-loop by heating again, can become filming of further imidizate by removing organic solvent after the coating.The thickness that formation is filmed is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) to formed coated surface with being tied with the friction treatment that the cylinder for example rolled by fibroplastic cloth such as nylon, rayon, cottons rubs in a certain direction.Like this, on filming, provide the liquid crystal molecular orientation ability and form liquid crystal orientation film.
In addition; the liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention; by carrying out shown in Japanese kokai publication hei 6-222366 communique or Japanese kokai publication hei 6-281937 communique; change the processing at pre-oblique angle by the local irradiation ultraviolet ray; perhaps carry out shown in Japanese kokai publication hei 5-107544 communique; form diaphragm at the liquid crystal orientation film surface local of implementing friction treatment; carry out removing diaphragm after the friction treatment along the direction different with previous friction treatment direction; with the processing of the liquid crystal aligning ability that changes liquid crystal orientation film, can improve the visual field characteristic of liquid crystal display cells.
(3) make two substrates that form liquid crystal orientation film as mentioned above, two plate bases are inserted gap (unit interval) subtend configuration, peripheral part of two plate bases is pasted with sealant, inject filling liquid crystal in the cell gap of distinguishing by substrate surface and sealant, the sealing filling orifice also constitutes liquid crystal cell.And the outside surface of liquid crystal cell promptly, at the opposite side of the transparency carrier that constitutes liquid crystal cell, by pasting polarized light piece, obtains liquid crystal display cells respectively.
Here, as sealant, can use hardening agent for example and as epoxy resin that contains alumina balls of pad etc.
As liquid crystal, can enumerate nematic crystal.For example can use the Schiff bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, terphenyl class liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal; dioxane liquid crystal, bicyclooctane class liquid crystal, cube alkanes liquid crystal etc.In addition, can in these liquid crystal, add for example cholesterol chloride, Cholesteryl pelargonate, the cholesterol liquid crystal such as cholesterol carbonic ester or the chirality agent of selling as trade name " C-15 " " CB-15 " (メ Le Network society system) etc. and use.
In addition; as the polarized light piece on the outside surface that sticks on liquid crystal cell, can enumerate the polarization film that is called as the H film that will absorb iodine when for example will make polyvinyl alcohol (PVA) stretch the orientation polarized light piece of cellulose acetate diaphragm clamping or the polarized light piece that H film self forms.
＜liquid crystal orientation film stripper 〉
As stripper, can enumerate the aqueous solution class stripper that for example contains glycol solvent and alkali compounds and/or nonionic class surfactant or contain N-Methyl pyrrolidone or the organic solvent class stripper of gamma-butyrolacton for liquid crystal orientation film of the present invention is used from strippable substrate.
The glycol solvent that contains in the above-mentioned aqueous solution class stripper can be enumerated for example ethylene glycol monoethyl ether, diethylene glycol single-butyl ether, propylene glycol monoisopropyl ether, diethylene glycol single-butyl ether acetic acid esters etc.
In addition, as alkali compounds, can enumerate for example lithium hydroxide, NaOH, potassium hydroxide, dibastic sodium phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, sodium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium metasilicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, sal tartari, lithium borate, sodium borate, potassium borate, ammonia, tetramethyl ammonium hydroxide, hydroxide dihydroxy ethyl trimethyl ammonium, monomethyl amine, dimethyl amine, Trimethylamine, single ethylamine, diethylamide, triethylamine, single isopropylamine, diisopropylamine, monoethanolamine, N-methyl piperidine, hydroxide trimethyl hydroxyethyl ammonium etc.
In addition, as nonionic surfactant, can enumerate for example polyoxyethylene alkyl ether, the polyoxyethylene allyl ether, polyxyethylated allyl ether, polyoxyethylene deriv, ethylene oxide-oxypropylene block copolymer, the D-sorbite fatty acid ester, the polyoxyethylene sorbitol fatty acid ester, polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine etc.
In addition, as above-mentioned organic solvent class stripper, can enumerate that N-Methyl pyrrolidone for example or gamma-butyrolacton form or contain the stripper that is not less than 20% above-mentioned solvent and 0～20% above-mentioned alkali compounds etc.
[embodiment]
Below, be described more specifically the present invention by embodiment, but the present invention is not limited to these embodiment.
Whether the embodiment of this instructions and the fissility of the liquid crystal orientation film in the comparative example are by visualization to confirm exist film to obtain in the front and back that filming on the glass substrate are immersed in stripper.In addition, wearing quality is to confirm to have or not scratch to obtain by filming of will forming carried out 10 friction backs on glass substrate.And using the orientation and the fail-test of the liquid crystal display cells of alignment films making is to estimate by the following method.
(orientation test)
On the substrate of this alignment films of coating, make liquid crystal cell, whether produce the evaluation of flow orientation when vacuum is injected liquid crystal in box as orientation by affirmation.
(fail-test)
Liquid crystal display cells put into 70 ℃ calibration cell, continuous drive was confirmed having or not of contrast spots, display defect after 24 hours in drive waveforms generating means " Function/arbitrary waveform generator " (Hewlett Packard society system).
Synthesis example 1
As the tetrabasic carboxylic acid dicarboxylic anhydride with 224.17g (0.5 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride, (157.14g 0.5 mole) 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, as diamine compound with 94.62g (0.875 mole) p-phenylenediamine (PPD), 32.02g (0.1 mole) 2,2 '-two trifluoromethyls-4,4 '-benzidine, (6.43g 0.01 mole) 3,6-two (4-aminobenzoic acyl-oxygen base) cholesterol, 4.04g (0.03 mole) 4-aminophenyl octadecyl ether is dissolved in 4, in the 500gN-N-methyl-2-2-pyrrolidone N-, 60 ℃ of reactions 6 hours.Then, reactant liquor is injected excessive methyl alcohol precipitation reaction product.Then, by using methanol wash, 40 ℃ of dryings 15 hours, obtaining 410g logarithm viscosity was 0.87dl/g, the polyamic acid of imidizate rate 0% down in decompression.30g gained polyamic acid is dissolved in the 570gN-N-methyl-2-2-pyrrolidone N-, to wherein adding 23.4g pyridine and 18.1g acetic anhydride and 110 ℃ of dehydration closed-loops 4 hours, similarly precipitate with above-mentioned, washing, drying under reduced pressure, obtaining 17.5g logarithm viscosity is 0.80dl/g, and the polyimide of imidizate rate 100% (is referred to as " polyimide " (A-1).)。
Synthesis example 2
As the tetrabasic carboxylic acid dicarboxylic anhydride with 224.17g (0.5 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride, 157.14g (0.5 mole) 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, as diamine compound with 94.62g (0.875 mole) p-phenylenediamine (PPD), (24.85g 0.1 mole) two aminopropyl tetramethyl disiloxanes, (6.43g 0.01 mole) 3,6-two (4-aminobenzoic acyl-oxygen base) cholesterol, 4.04g (0.03 mole) 4-aminophenyl octadecyl ether is dissolved in 4, in the 500gN-N-methyl-2-2-pyrrolidone N-, 60 ℃ of reactions 6 hours.Then, reactant liquor is injected excessive methyl alcohol precipitation reaction product.Then, by using methanol wash, 40 ℃ of dryings 15 hours, obtaining 370g logarithm viscosity was 0.82dl/g, the polyamic acid of imidizate rate 0% down in decompression.30g gained polyamic acid is dissolved in the 570gN-N-methyl-2-2-pyrrolidone N-, to wherein adding 23.4g pyridine and 18.1g acetic anhydride and 110 ℃ of dehydration closed-loops 4 hours, similarly precipitate with above-mentioned, washing, drying under reduced pressure, obtaining 18.5g logarithm viscosity is 0.77dl/g, and the polyimide of imidizate rate 100% (is referred to as " polyimide " (A-2).)。
Synthesis example 3
With 218.12g (1 mole) pyromellitic acid dicarboxylic anhydride, 108.14g (1 mole) is dissolved in 4 to the penylene diamines as the tetrabasic carboxylic acid dicarboxylic anhydride, in the 500gN-N-methyl-2-2-pyrrolidone N-, 60 ℃ of reactions 6 hours as diamine compound.Then, reactant liquor is injected into precipitation reaction product in the excessive methyl alcohol.Then, by using methanol wash, 40 ℃ of dryings 15 hours, obtaining 410g logarithm viscosity was 0.90dl/g down in decompression, and the polyamic acid of imidizate rate 0% (is referred to as " polyamic acid (B-1) ".)。
Synthesis example 4
Remove in synthesis example 3 as the tetrabasic carboxylic acid dicarboxylic anhydride with 109.06 (0.5 mole) pyromellitic acid dicarboxylic anhydrides and 98.06g (0.5 mole) 1,2,3, similarly obtain the 485g polyamic acid with synthesis example 1 beyond the 4-ring butanetetra-carboxylic acid dicarboxylic anhydride and (be referred to as " polyamic acid (B-2) ".)。
Synthesis example 5
Remove in synthesis example 3 diamines with 198.28g (1 mole) 4, beyond 4 '-diaminodiphenyl-methane, similarly obtain the 406g polyamic acid with synthesis example 3 and (be referred to as " polyamic acid (B-3) ".)。
Synthesis example 6
Remove in synthesis example 3 diamines with 212g (1.0 moles) 2, similarly obtain the 475g polyamic acid with synthesis example 3 beyond the 2 '-dimethyl-4,4 '-benzidine and (be referred to as " polyamic acid (B-4) ".)。
Compare synthesis example 1
Remove and use 196.12g (1 mole) 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride is as the tetrabasic carboxylic acid dicarboxylic anhydride, and 108.14g (1 mole) p-phenylenediamine (PPD) is as beyond the diamine compound, with synthesis example 3 similarly, obtain the polyamic acid that 276g logarithm viscosity is 1.95dl/g and (be referred to as " polyamic acid (B-5) ".)。
Compare synthesis example 2
Remove and use 314.28g (1 mole) 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone is as the tetrabasic carboxylic acid dicarboxylic anhydride, 410.52g (1.0 moles) 2, and two [4-(4-amino-benzene oxygen) phenyl] propane of 2-are as beyond the diamine compound, with synthesis example 1 similarly, obtain the polyamic acid that 300g logarithm viscosity is 0.83dl/g and (be referred to as " polyamic acid (B-6) ".)。And similarly carry out imidization reaction with itself and synthesis example 2, obtain the polyimide that logarithm viscosity is 1.28dl/g and (be referred to as " polyimide (A-3) ".)。
Embodiment 1
The polyamic acid (B-1) that polyimide (A-1) that synthesis example 1 is obtained and synthesis example 3 obtain is dissolved in the mixed solvent of N-N-methyl-2-2-pyrrolidone N-/gamma-butyrolacton (1/9), become the solution that solid component concentration is 4 weight %, is the filtrator filtration of 1 μ m with this solution with the aperture, the preparation aligning agent for liquid crystal.Above-mentioned aligning agent for liquid crystal is applied to printing machine on the transparency electrode face of the glass substrate with transparency electrode that ITO forms with liquid crystal orientation film coating, on 180 ℃ electric hot plate dry 10 minutes, forms the diaphragm that dry average film thickness is 500 dusts.This diaphragm was flooded 10 minutes in the alignment films stripper that contains glycol solvent and nonionic class surfactant, with the naked eye confirm fissility, the result can peel off.This diaphragm is made a rubbing machine of cloth cylinder with having the winder, and with cylinder revolution 400rpm, the platform translational speed is 3cm/ second, and it is that 0.4mm carries out friction treatment 10 times that hairbrush is pressed into length, carries out abrasion test, and the result fails to confirm to cut, peel off etc.On the other hand, the above-mentioned alignment films coated substrates of implementing 1 friction treatment flood 1 minute in water after, with two substrates drying 10 minutes in 100 ℃ of Green's stoves.Then, with a pair of liquid crystal orientation film periphery separately with liquid crystal clamping substrate of friction treatment, after the epoxy adhesive of Butut diameter 5.5 μ m, a pair of liquid crystal clamping substrate is made the overlapping relatively crimping of liquid crystal orientation film, bonding agent is solidified with divinylbenzene ball.Then, from liquid crystal injecting port at a pair of substrate gap, fill nematic crystal (メ Le Network society system, MLC-6221) after, with propylene class Photocurable adhesive encapsulated liquid crystals inlet, paste polarized light piece on the two sides, the outside of substrate, make liquid crystal display cells.Can't see flow orientation, after the fail-test, can't see contrast spots, display defect.
Embodiment 2～8, comparative example 1～2
Remove and use the synthesis example 2～6 that becomes liquid crystal orientation film, compare synthesis example 1,2 and Japanese kokai publication hei 8-220541 in beyond the polyamic acid and/or polyimide of the liquid crystal orientation film gained that forms of the mixed solution of the polyimide precursor solution of embodiment 1 to 5 record and soluble polyimide solution, make liquid crystal display cells similarly to Example 1.In addition, in embodiment, comparative example, polyamic acid and polyimide, with polyamic acid: the ratio of polyimide=4: 1 (weight ratio) is used.The results are shown in the table 1.
[table 1]
| Embodiment/comparative example | Polyimide | Polyamic acid | Fissility | Wearing quality | Orientation | Reliability |
| Embodiment 2 | ????A-2 | ????B-1 | Peelable | Do not have cutting, peel off | No flow orientation | Unmatchful than spot, display defect |
| Embodiment 3 | ????A-1 | ????B-2 | Peelable | Do not have cutting, peel off | No flow orientation | Unmatchful than spot, display defect |
| Embodiment 4 | ????A-2 | ????B-2 | Peelable | Do not have cutting, peel off | No flow orientation | Unmatchful than spot, display defect |
| Embodiment 5 | ????A-1 | ????B-3 | Peelable | Do not have cutting, peel off | No flow orientation | Unmatchful than spot, display defect |
| Embodiment 6 | ????A-2 | ????B-3 | Peelable | Do not have cutting, peel off | No flow orientation | Unmatchful than spot, display defect |
| Embodiment 7 | ????A-1 | ????B-4 | Peelable | Do not have cutting, peel off | No flow orientation | Unmatchful than spot, display defect |
| Embodiment 8 | ????A-2 | ????B-4 | Peelable | Do not have cutting, peel off | No flow orientation | Unmatchful than spot, display defect |
| Comparative example 1 | ????A-3 | ????B-4 | Can not peel off | Do not have cutting, peel off | No flow orientation | Unmatchful than spot, display defect |
| Comparative example 2 | ????A-3 | ????B-4 | Can not peel off | Do not have cutting, peel off | No flow orientation | Unmatchful than spot, display defect |
Claims (5)
1. aligning agent for liquid crystal constitutes by having the acid imide bonding unit that forms by tetrabasic carboxylic acid dicarboxylic anhydride and diamine reactant and polymkeric substance or its potpourri of at least a bonding unit in the amic acid bonding unit, it is characterized in that, for above-mentioned polymkeric substance or its potpourri, above-mentioned tetrabasic carboxylic acid dicarboxylic anhydride contains and is selected from 1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride, 3,5,6-three carboxyls norbornane-2-acetate dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dicarboxylic anhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl) naphtho-[1,2-c] furans-1, in 3-diketone and the pyromellitic acid dicarboxylic anhydride at least 3 kinds, and above-mentioned diamines contains and is selected from p-phenylenediamine (PPD), two aminopropyl tetramethyl disiloxanes, 4,4 '-diaminodiphenyl-methane, 2,2 '-dimethyl-4,4 '-benzidine and 3, in two (the 4-aminobenzoic acyl-oxygen base) cholesterol of 6-at least 3 kinds.
2. aligning agent for liquid crystal as claimed in claim 1, wherein above-mentioned tetrabasic carboxylic acid dicarboxylic anhydride contains at least 30% pyromellitic acid dicarboxylic anhydride.
3. aligning agent for liquid crystal as claimed in claim 1 or 2 wherein also contains the compound that has an epoxy radicals in the molecule at least.
4. a liquid crystal orientation film is formed by each described aligning agent for liquid crystal in the claim 1～3.
5. a liquid crystal display cells possesses the described liquid crystal orientation film of claim 4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP018149/04 | 2004-01-27 | ||
| JP2004018149 | 2004-01-27 | ||
| JP018149/2004 | 2004-01-27 |
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| CN1648726A true CN1648726A (en) | 2005-08-03 |
| CN100412623C CN100412623C (en) | 2008-08-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100028154A Expired - Fee Related CN100412623C (en) | 2004-01-27 | 2005-01-25 | Liquid orientation agent and liquid orientation film as well as liquid display element |
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| Country | Link |
|---|---|
| KR (1) | KR100850242B1 (en) |
| CN (1) | CN100412623C (en) |
| TW (1) | TWI359189B (en) |
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| CN101144943B (en) * | 2006-09-11 | 2011-07-06 | Jsr株式会社 | Liquid crystal orientating agent and liquid crystal displaying element |
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| JP5365774B2 (en) * | 2008-11-14 | 2013-12-11 | Ｊｓｒ株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
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| JP4514247B2 (en) * | 1998-11-12 | 2010-07-28 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| TWI283783B (en) * | 1999-12-09 | 2007-07-11 | Jsr Corp | Liquid crystal alignment film and liquid crystal display device |
| TW548491B (en) * | 2000-07-07 | 2003-08-21 | Nissan Chemical Ind Ltd | Liquid crystal orientating agent and liquid crystal display element using the same |
| JP2002062537A (en) * | 2000-08-21 | 2002-02-28 | Jsr Corp | Liquid crystal aligning agent for stn (supertwisted nematic) liquid crystal display element and stn liquid crystal display element |
-
2005
- 2005-01-11 TW TW094100689A patent/TWI359189B/en not_active IP Right Cessation
- 2005-01-13 KR KR1020050003360A patent/KR100850242B1/en active IP Right Grant
- 2005-01-25 CN CNB2005100028154A patent/CN100412623C/en not_active Expired - Fee Related
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| CN101024773B (en) * | 2006-02-22 | 2013-01-23 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display device |
| CN101042504B (en) * | 2006-03-22 | 2011-02-09 | Jsr株式会社 | Liquid crystal aligning agent and film and liquid crystal display device |
| CN101144943B (en) * | 2006-09-11 | 2011-07-06 | Jsr株式会社 | Liquid crystal orientating agent and liquid crystal displaying element |
| CN101246283B (en) * | 2007-02-15 | 2011-02-16 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| TWI427102B (en) * | 2007-02-22 | 2014-02-21 | Jsr Corp | Liquid crystal alignment agent and liquid crystal display element |
| CN101256314B (en) * | 2007-02-26 | 2011-07-13 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| CN101627333B (en) * | 2007-03-08 | 2011-08-03 | Jsr株式会社 | Liquid crystal aligning agent and in-plane switching mode liquid crystal display |
| CN101359130B (en) * | 2007-08-01 | 2012-02-29 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device |
| CN101815966B (en) * | 2007-08-21 | 2012-04-04 | Jsr株式会社 | Liquid crystal aligning agent, method for forming liquid crystal alignment film, and liquid crystal display device |
| CN101874225B (en) * | 2007-11-27 | 2012-12-05 | Jsr株式会社 | Liquid crystal aligning agent, method for forming liquid crystal alignment film, and liquid crystal display device |
| CN101910928B (en) * | 2007-12-26 | 2013-08-07 | Jsr株式会社 | Liquid crystal aligning agent and method for forming liquid crystal alignment film |
| CN101591544B (en) * | 2008-05-26 | 2013-06-12 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| US8329264B2 (en) | 2008-12-02 | 2012-12-11 | Cheil Industries Inc. | Liquid crystal alignment agent, and liquid crystal alignment film and liquid crystal display including same |
| CN107304363A (en) * | 2016-04-18 | 2017-10-31 | 达兴材料股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device using same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200530376A (en) | 2005-09-16 |
| TWI359189B (en) | 2012-03-01 |
| CN100412623C (en) | 2008-08-20 |
| KR100850242B1 (en) | 2008-08-04 |
| KR20050077261A (en) | 2005-08-01 |
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