CN104204925A - Polyimide-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Polyimide-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element Download PDF

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CN104204925A
CN104204925A CN201380016101.1A CN201380016101A CN104204925A CN 104204925 A CN104204925 A CN 104204925A CN 201380016101 A CN201380016101 A CN 201380016101A CN 104204925 A CN104204925 A CN 104204925A
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liquid crystal
aligning agent
acid ester
formula
poly amic
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松本裕充
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Provided is a liquid crystal aligning agent that forms a liquid crystal alignment film having good rubbing resistance, good printability even when the imidization rate is high, an excellent voltage retention rate, a high accumulated charge, and the like. This liquid crystal aligning agent is characterized by comprising a soluble polyimide represented by formula (1), and a polyamic acid ester represented by formula (2). (X1 is a tetravalent organic group, Y1 is a divalent organic group, X2 is a tetravalent organic group, Y2 is a divalent organic group, R1 is a C1-5 alkyl group, A1 and A2 each independently are a hydrogen atom, or a C1-10 alkyl group, alkenyl group, or alkynyl group which may optionally have a substituent.)

Description

The aligning agent for liquid crystal of polyimide, liquid crystal orientation film and liquid crystal display cells
Technical field
The present invention relates to the aligning agent for liquid crystal of polyimide, the liquid crystal orientation film that uses this aligning agent for liquid crystal and liquid crystal display cells.
Background technology
Liquid crystal display cells is to be the structure that liquid crystal orientation film that liquid crystal molecule is formed on substrate is clipped in the middle, the display element that utilizes this liquid crystal molecule to respond according to voltage.
Liquid crystal orientation film has the vital role that the direction of orientation of liquid crystal molecule and tilt angle is controlled to free position.
Liquid crystal orientation film is generally by carrying out so-called " friction treatment " and make being formed at the surface of the polyimide film on substrate, and this friction treatment is with rayon cloth, nylon cloth etc., to be exerted pressure and rubbed in its surface.By this friction treatment, decide the direction of orientation of liquid crystal molecule.
As the means that increase the tilt angle of liquid crystal, the known means (for example, with reference to patent documentation 1) of introducing the alkyl of long-chain in the structure of polyimide that forms liquid crystal orientation film.
As the means that form polyimide film on substrate, there is the solution of coating polyamic acid etc. to make the method for its imidizate on substrate and the method for the solution of coating soluble polyimide.Wherein, even use soluble polyimide solution method lower temperature burn till the good polyimide film of characteristic that also can form while making liquid crystal orientation film, exist but then formed film strength low, easily because friction treatment causes the problem of peeling off to the damage on film surface and film.
In addition, during as making liquid crystal orientation film, polymer solution is coated on to the means on substrate, now the industrial flexographic printing method that is widely used.But, because there is albinism etc. in the solution of the soluble polyimide that acid imide rate is high, printing is poor, so re-use after need to mixing soluble polyimide that acid imide rate is low etc., so relatively spends time (for example, with reference to patent documentation 2).
In addition,, if introduce chain alkyl in order to give liquid crystal with the tilt angle compared with large in the structure of soluble polyimide, there is the tendency of its printing variation.
As improving the means of polymer solution to the printing of substrate, the method (for example, with reference to patent documentation 3) of the solvent of known interpolation butyl cellosolve etc.
But conventionally soluble polyimide and polyamic acid etc. are compared, dissolubility is low, so cannot use in a large number the solvent of butyl cellosolve etc.
Prior art document
Patent documentation
Patent documentation 1: Japanese patent laid-open 2-282726 communique
Patent documentation 2: Japanese patent laid-open 9-297312 communique
Patent documentation 3: Japanese patent laid-open 2-037324 communique
Summary of the invention
Invent technical matters to be solved
The object of the present invention is to provide and can obtain the good liquid crystal orientation film of wear-resisting wiping, and even the acid imide rate of soluble polyimide is high, printing is also good, and voltage retention (VHR), accumulate the aligning agent for liquid crystal of the polyimide that comprises soluble polyimide of the electrical characteristics excellence of electric charge (RDC) etc.
The technical scheme that technical solution problem adopts
The inventor is not damaging under the prerequisite of the characteristic of the aligning agent for liquid crystal of the polyimide that comprises above-mentioned soluble polyimide, electrical characteristics, printing characteristic while forming in order to improve tunicle has carried out special research, found that comprising the aligning agent for liquid crystal that has the soluble polyimide of ad hoc structure and have the poly amic acid ester of ad hoc structure can achieve the above object.
; even if comprise the aligning agent for liquid crystal that there is the soluble polyimide of ad hoc structure and there is the poly amic acid ester of ad hoc structure, can provide acid imide rate high; when filming formation, also albinism can not occur, printing is good, and the good liquid crystal orientation film of wear-resisting wiping of filming.In addition, find that the electrical characteristics of liquid crystal orientation film of gained are excellent, particularly in voltage retention with accumulate aspect electric charge (RDC) and there is unprecedented excellent specific property.
That is, the present invention is the invention completing based on above-mentioned discovery, comprises following technology contents.
1. an aligning agent for liquid crystal, it contains the soluble polyimide representing with following formula (1) and the poly amic acid ester representing with following formula (2),
[changing 1]
In formula (1), X 14 valency organic groups, Y 1it is divalent organic group; In formula (2), X 24 valency organic groups, Y 2divalent organic group, R 1it is the alkyl of carbon number 1～5; A 1and A 2be respectively hydrogen atom or alkyl, alkenyl or the alkynyl can with substituent carbon number 1～10 independently.
2. the aligning agent for liquid crystal as described in above-mentioned 1, wherein, the R in formula (2) 1it is methyl.
3. the aligning agent for liquid crystal as described in above-mentioned 1 or 2, wherein, the X in formula (1), formula (2) 1and X 2respectively independently for being selected from least one of the structure that represents with following formula,
[changing 2]
4. the aligning agent for liquid crystal as described in any one in above-mentioned 1～3, wherein, in formula (2), X 2the following structure with aromatic ring:
[changing 3]
5. the aligning agent for liquid crystal as described in any one in above-mentioned 1～3, wherein, in formula (1), X 1there is aliphatic structure or ester ring type structure.
6. the aligning agent for liquid crystal as described in any one in above-mentioned 1～5, wherein, the weight-average molecular weight of above-mentioned poly amic acid ester is 5000～200000.
7. the aligning agent for liquid crystal as described in any one in above-mentioned 1～6, wherein, above-mentioned soluble polyimide has more than 50% acid imide rate, and weight-average molecular weight is 5000～200000.
8. the aligning agent for liquid crystal as described in any one in above-mentioned 1～7 wherein, the ratio of the content of above-mentioned soluble polyimide and the content of above-mentioned poly amic acid ester, is that the content of the content/poly amic acid ester of soluble polyimide is 1/9～9/1 by quality ratio.
9. the aligning agent for liquid crystal as described in any one in above-mentioned 1～8, wherein, comprise the organic solvent that dissolves above-mentioned soluble polyimide and above-mentioned poly amic acid ester, with respect to the organic solvent of 100 quality %, the content of soluble polyimide and the total amount of poly amic acid ester are 0.5～15 quality %.
10. the aligning agent for liquid crystal as described in above-mentioned 9, wherein, above-mentioned organic solvent contains at least one that is selected from N-methyl-pyrrolidone, N-ethyl-pyrrolidone and gamma-butyrolacton.
11. aligning agent for liquid crystal as described in any one in above-mentioned 1～10, it also comprises solvent.
12. aligning agent for liquid crystal as described in above-mentioned 11, wherein, above-mentioned solvent is butyl cellosolve.
13. 1 kinds of liquid crystal orientation films, obtain by the aligning agent for liquid crystal described in any one in above-mentioned 1～12 being coated with, burning till.
14. liquid crystal orientation films as described in above-mentioned 13, wherein, by above-mentioned aligning agent for liquid crystal coating, burn till and the thickness of filming be 5～300nm.
15. 1 kinds of liquid crystal display cells, it has the liquid crystal orientation film described in above-mentioned 13 or 14.
The effect of invention
According to aligning agent for liquid crystal of the present invention, even if it is high to obtain the acid imide rate of soluble polyimide, films, while forming, albinism does not occur yet, printing is good, and the good liquid crystal orientation film of wear-resisting wiping of filming.In addition, the electrical characteristics of the liquid crystal orientation film obtaining are excellent, particularly in voltage retention with accumulate aspect electric charge (RDC) and have unprecedented excellent specific property.
In the present invention, think by using poly amic acid ester, due to polarity and fat-soluble approaching with soluble polyimide, so can not form as described below two-layerly, even at the interface contacting with liquid crystal, poly amic acid ester also exists with finite concentration.
On the other hand, in replacing aligning agent for liquid crystal of the present invention with polyamic acid during contained poly amic acid ester, albinism while forming though film can improve, the liquid crystal orientation film of gained in voltage retention, accumulate aspect the characteristic of electric charge (RDC) etc. and can not bring satisfied result.
Although the reason that causes electrical characteristics to decline while replacing poly amic acid ester for use polyamic acid is not very clear, but think because in the situation that using polyamic acid, because polarity is with fat-soluble different from soluble polyimide, so formation soluble polyimide composition is positioned at the cause that upper strata, the polyamic acid composition of liquid crystal orientation film are positioned at two coating systems of lower floor.
Embodiment
< soluble polyimide >
The soluble polyimide using in the present invention has the structure representing with following formula (1).
[changing 4]
In above-mentioned formula (1), X 14 valency organic groups.
If enumerate X 1preferred concrete example, can exemplify the following X-1～X-46 illustrating.From the acquired consideration of monomer, X 1preferred X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-19, X-21, X-25, X-26, X-27, X-28 or X-32.
Wherein, X 1have in the situation of aliphatic structure or ester ring type structure, the liquid crystal orientation film of gained has high voltage holding ratio characteristic, because of but preferred.The X preferably with aliphatic structure 1for X-1, X-16, X-19, particularly preferably X-1, X-19.
[changing 5]
[changing 6]
[changing 7]
[changing 8]
In addition, in formula (1), Y 1be divalent organic group, be not particularly limited.If enumerate Y 1preferred concrete example, can exemplify following Y-1～Y-97.
Wherein, as Y 1more preferably Y-7, Y-10, Y-11, Y-12, Y-13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y-45, Y-46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, Y-98, preferably have the diamine compound of these structures.
In addition Y, 1be in the situation of Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96 or Y-97, can improve tilt angle.
[changing 9]
[changing 10]
[changing 11]
[changing 12]
[changing 13]
[changing 14]
[changing 15]
[changing 16]
[changing 17]
[changing 18]
[changing 19]
[changing 20]
[changing 21]
The soluble polyimide using in the present invention can obtain by polyimide precursor is carried out to imidizate by known method.Polyimide precursor refers to polyamic acid or poly amic acid ester.
In imidizate, in the situation that using polyamic acid, by polyamic acid dehydration closed-loop is manufactured; In addition, in the situation that using poly amic acid ester, by poly amic acid ester is heated to closed loop manufacture.
Wherein, in the present invention, by the method for polyamic acid dehydration closed-loop because can improve acid imide rate, so more preferably.
The acid imide rate of the soluble polyimide in the present invention can be controlled by the catalytic amount in adjusting imidization reaction, temperature of reaction, reaction time etc.In the present invention, even because the high polyimide of acid imide rate also can be used, so acid imide rate is preferably more than 50%, more preferably more than 70%, particularly preferably more than 80%.Wherein, acid imide rate more preferably 80～90%.
Polyamic acid can, by two amine components and tetracarboxylic dianhydride's reaction, obtain by known method.
In addition, poly amic acid ester can react two amine components and tetrabasic carboxylic acid diester diacid chloride by accordance with known methods under the existence of alkali, or tetrabasic carboxylic acid diester and diamines are reacted under the existence of suitable condensation agent, alkali and obtains.
< poly amic acid ester >
The poly amic acid ester using in the present invention has the structure shown in following formula (2).
[changing 22]
In above-mentioned formula (2), R 1alkyl for carbon number 1～5.
Along with the carbon number in alkyl increases, the temperature that poly amic acid ester carries out imidizate raises.Therefore, from being easy to adopt the viewpoint of hot imidizate to consider, R 1preferably carbon number 1 or 2 alkyl, be particularly preferably methyl.
In above-mentioned formula (2), X 2have with above-mentioned formula (1) in X 1identical definition, the Y of above-mentioned formula (2) 2have with above-mentioned formula (1) in Y 1identical definition.Wherein, the X in formula (2) 2have in the situation of aromatic structure, the liquid crystal orientation film of gained has high voltage holding ratio characteristic, because of but preferred.As the preferred X with aromatic structure 2, can exemplify above-mentioned X-26～X-45, particularly preferably X-26.
In above-mentioned formula (2), A 1and A 2be respectively hydrogen atom or alkyl, alkenyl or the alkynyl can with substituent carbon number 1～10 independently.
As the concrete example can with the alkyl of substituent carbon number 1～10, can exemplified by methyl, ethyl, propyl group, butyl, the tert-butyl group, hexyl, octyl group, decyl, cyclopentyl, cyclohexyl, dicyclohexyl etc.
As the alkenyl can with substituent carbon number 1～10, can exemplify 1 the above CH existing in abovementioned alkyl 2-CH 2structure is substituted by the group of CH=CH structure, more specifically, and can exemplified by vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl group, 1,3-butadiene base, 2-pentenyl, 2-hexenyl, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc.
As the alkynyl can with substituent carbon number 1～10, can exemplify 1 the above CH existing in abovementioned alkyl 2-CH 2structure is substituted by the group of C ≡ C-structure, more specifically, can exemplify ethinyl, 1-propinyl, 2-propynyl etc.
As A 1and A 2, be preferably independently respectively hydrogen atom, methyl, ethyl, vinyl, allyl, more preferably hydrogen atom, methyl.
Abovementioned alkyl, alkenyl, alkynyl need only whole carbon number and are 1～10 and also can have substituting group, can also form ring structure by substituting group.By substituting group, forming ring structure represents between substituting group or a part for substituting group and main body framework is combined into as ring structure.
The poly amic acid ester being represented by above-mentioned formula (2) can be by the tetracarboxylic acid derivatives that represented by following formula (6)～(8) the reaction of any and the diamine compound that represented by formula (9) obtain.
[changing 23]
[changing 24]
(in above-mentioned formula, X 2, Y 2, R 1, A 1and A 2identical with above-mentioned definition respectively).
The poly amic acid ester representing with above-mentioned formula (2) can be by following (A) recording～(C) method of middle any one is synthetic.
(A) by polyamic acid, carry out synthetic situation
Poly amic acid ester can synthesize by the polyamic acid being obtained by tetracarboxylic dianhydride and diamines is carried out to esterification.
[changing 25]
Particularly, can be by making polyamic acid and esterifying agent under the existence of organic solvent, in-20 ℃～150 ℃, preferably 0 ℃～50 ℃ reactions 30 minutes～24 hours, preferably within 1～4 hour, synthesize.
As esterifying agent, the esterifying agent that preferably can easily remove by purifying, can exemplify N, dinethylformamide dimethylacetal, N, dinethylformamide diethyl acetal, N, dinethylformamide dipropyl acetal, N, dinethylformamide di neo-pentyl butyl acetal, N, dinethylformamide di-t-butyl acetal, 1-methyl-3-p-methylphenyl triazenes, 1-ethyl-3-p-methylphenyl triazenes, 1-propyl group-3-p-methylphenyl triazenes, chlorination 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methyl morpholine salt etc.Wherein, preferred DMF dimethylacetal.
The repetitive of the polyamic acid of the addition of esterifying agent with respect to 1 mole is preferably 2～6 molar equivalents, more preferably 3～4 molar equivalents.
From the viewpoint of the dissolubility of polymkeric substance, the organic solvent using in above-mentioned reaction is better DMF, METHYLPYRROLIDONE, gamma-butyrolacton etc., and these organic solvents can be used a kind or two or more mix is used.
From being difficult for occurring the viewpoint consideration of separating out and easily obtain high molecular body of polymkeric substance, when synthetic, polymer concentration is preferably 1～30 quality %, more preferably 5～20 quality %.
(B) by the reaction of tetrabasic carboxylic acid diester diacid chloride and diamines, carry out synthetic situation
Poly amic acid ester can be synthetic by tetrabasic carboxylic acid diester diacid chloride and diamines.
[changing 26]
Particularly, can be by making tetrabasic carboxylic acid diester diacid chloride and diamines under the existence of alkali and organic solvent, in-20～150 ℃, preferably 0～50 ℃ of reaction 30 minutes～24 hours, preferably within 1～4 hour, synthesize.
As alkali, can use pyridine, triethylamine, 4-dimethylaminopyridine etc., for reaction is leniently carried out, preferred pyridine.
From being that the amount of easily removing and the viewpoint that easily obtains high molecular body are considered, the addition of alkali is preferably 2～4 times moles with respect to tetrabasic carboxylic acid diester diacid chloride, more preferably 2～3 times moles.
From the dissolubility of monomer and polymkeric substance, consider, the organic solvent using in above-mentioned reaction is preferably METHYLPYRROLIDONE, gamma-butyrolacton, and these solvents can be used a kind or two or more is mixed and is used.
From being difficult for occurring the viewpoint consideration of separating out and easily obtain high molecular body of polymkeric substance, when synthetic, polymer concentration is preferably 1～30 quality %, more preferably 5～20 quality %.
In addition,, in order to prevent the hydrolysis of tetrabasic carboxylic acid diester diacid chloride, the organic solvent using in poly amic acid ester synthetic is the state of dehydration as far as possible preferably, preferably in nitrogen atmosphere, carries out, to prevent sneaking into of extraneous gas body.
(C) by tetrabasic carboxylic acid diester and diamines, carried out the situation of synthesizing polyamides acid
Poly amic acid ester can be by synthesizing tetrabasic carboxylic acid diester and diamines polycondensation.
[changing 27]
Particularly, can be by making tetrabasic carboxylic acid diester and diamines under the existence of condensation agent, alkali and organic solvent, in 0～150 ℃, preferably 0～100 ℃ of reaction 30 minutes～24 hours, preferably within 3～15 hours, synthesize.
Condensation agent can be used triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazines methyl morpholine , O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea tetrafluoro boric acid ester, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea hexafluorophosphoric acid ester, (2,3-dihydroxy-2-sulfo--3-benzo azoles base) phosphonic acid diphenyl ester etc.
The addition of condensation agent is preferably 2～3 times moles with respect to tetrabasic carboxylic acid diester, more preferably 2～2.5 times moles.
Alkali can be used the tertiary amines such as pyridine, triethylamine.
From being that the amount of easily removing and the viewpoint that easily obtains high molecular body are considered, the addition of alkali is preferably 2～4 times moles with respect to two amine components, more preferably 2～3 times moles.
From the dissolubility of monomer and polymkeric substance, consider, the organic solvent using in above-mentioned reaction is preferably METHYLPYRROLIDONE, gamma-butyrolacton, and these solvents can be used a kind or two or more is mixed and is used.
In addition,, in above-mentioned reaction, add lewis acid can make reaction carry out efficiently as adjuvant.As lewis acid, the lithium halides such as preferred lithium chloride, lithium bromide.Lewis acidic addition is preferably 0～1.0 times mole with respect to two amine components, more preferably 0.2～0.5 times mole.
In the synthetic method of above-mentioned 3 kinds of poly amic acid esters, in order to obtain the poly amic acid ester of high molecular, the synthetic method of above-mentioned (A) or above-mentioned (B) particularly preferably.
The solution of the poly amic acid ester making as mentioned above can be by separate out polymkeric substance well-beaten in being injected into poor solvent simultaneously.After carrying out that several is separated out and cleaning with poor solvent, at normal temperatures or heat drying, can obtain the powder of purified poly amic acid ester.
Poor solvent is not particularly limited, can exemplifies water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc., particular methanol, ethanol.
< aligning agent for liquid crystal >
Aligning agent for liquid crystal of the present invention comprises the above-mentioned soluble polyimide representing with (1) and the poly amic acid ester representing with formula (2).Conventionally, aligning agent for liquid crystal of the present invention is the form that soluble polyimide and poly amic acid ester (being sometimes referred to as below polymkeric substance) are dissolved in the solution in organic solvent.As long as there is described solution state, can be the reaction solution itself for example obtaining when synthesizing polyamides acid esters and/or polyamic acid in organic solvent, or with this reaction solution of suitable solvent dilution must solution.In addition, during with Powdered acquisition poly amic acid ester and/or polyamic acid, can be dissolved in organic solvent and solution.
Deliquescent aspect from organic solvent considers, the weight-average molecular weight of soluble polyimide preferably 5000～200000, more preferably 10000～100000.In addition, number-average molecular weight is preferably 5000～100000, and more preferably 10000～50000.
On the other hand, the weight-average molecular weight of poly amic acid ester is preferably 5000～200000, and more preferably 10000～100000.In addition, number-average molecular weight is preferably 5000～100000, and more preferably 10000～50000.
The content of the above-mentioned polyimide in aligning agent for liquid crystal of the present invention and the content of above-mentioned poly amic acid ester, in poly amic acid ester/polyamic acid (mass ratio), are preferably 1/9～9/1, and more preferably 2/8～8/2, particularly preferably 3/7～7/3.By making this ratio within the scope of this, can provide all good aligning agent for liquid crystal of liquid crystal aligning and electrical characteristics.
The content of the polymkeric substance in aligning agent for liquid crystal of the present invention (concentration) also can suitably change according to the thickness of the liquid crystal orientation film that will form, but consider from forming even and flawless angle of filming, organic solvent with respect to 100 quality %, more than the content of component of polymer is preferably 0.5 quality %, from the angle of the storage stability of solution, consider to be preferably below 15 quality %, more preferably 1～10 quality %.
In addition, in this situation, can manufacture in advance the dense solution of concentration of polymkeric substance, this strong solution is diluted when making aligning agent for liquid crystal.The concentration of the strong solution of this component of polymer is 10～30 quality % preferably, more preferably 10～15 quality %.
While in addition, the powder dissolution of component of polymer being prepared to solution at organic solvent, can heat.Preferably 20～150 ℃ of heating-up temperatures, particularly preferably 20～80 ℃.
The organic solvent that aligning agent for liquid crystal of the present invention is contained so long as the solvent of component of polymer uniform dissolution be not particularly limited.If enumerate its concrete example, can exemplify N, dinethylformamide, N, N-diethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-Pyrrolidone, NVP, dimethyl sulfoxide, dimethyl sulfone, gamma-butyrolacton, 1,3-dimethyl-2-imidazolidinone, 3-methoxyl-N, N-dimethyl propylene acid amides etc.Wherein, from deliquescent angle, consider, preferably the large solvent of polarity of N-methyl-pyrrolidone, N-ethyl-pyrrolidone etc.
These organic solvents can be used a kind or two or more mix is used.In addition, even the organic solvent of dissolve polymer composition equably while using separately, as long as in the scope of not separating out at polymkeric substance, also can mix use.
Aligning agent for liquid crystal of the present invention be take the organic solvent that dissolve polymer composition is object except comprising, and also can comprise to improve the solvent that painting film uniformity when aligning agent for liquid crystal is coated to substrate is object.This solvent is conventionally used and compares the solvent of low surface tension with above-mentioned organic solvent.If lift its concrete example, can exemplify ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, butyl carbitol, ethyl carbitol acetic acid esters, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, single acetic acid propylene glycol ester, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, mono-ether-the 2-of propylene glycol-1-acetic acid esters, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.Wherein, preferred butyl cellosolve, ethyl carbitol etc.These solvents can and be used two or more.
In aligning agent for liquid crystal of the present invention, use for the above-mentioned organic solvent of dissolve polymer composition with for improving the inhomogeneity solvent of filming sometimes simultaneously, the use amount of organic solvent and solvent counts 30/70～90/10 with volumetric ratio, and preferably 60/40～80/20.
In addition, aligning agent for liquid crystal of the present invention can contain the various adjuvants of silane coupling agent and crosslinking chemical etc.The substrate that silane coupling agent improves for coating of liquid crystalline aligning agent is that object is added with the adaptation that is formed at the liquid crystal orientation film on this substrate.Exemplify the object lesson of silane coupling agent below, but be not limited to this.
The amine silane coupling agent of APTES, 3-(2-amino-ethyl) TSL 8330,3-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, 3-TSL 8330,3-phenyl amino propyl trimethoxy silicane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine, 3-aminopropyl diethoxymethyl silane etc.; The vinyl-based silane coupling agent of vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, vinyl methyl dimethoxysilane, vinyltriacetoxy silane, vinyl silane triisopropoxide, allyltrimethoxysilanis, p-styryl trimethoxy silane etc.; The epoxies silane coupling agent of 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc.; The methacryl one type of silane coupling agent of 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane etc.; The acryloyl one type of silane coupling agent of 3-acryloxy propyl trimethoxy silicane etc.; The ureide derivative silane coupling agent of 3-uride propyl-triethoxysilicane etc.; The thioether one type of silane coupling agent of two (3-(triethoxysilyl) propyl group) disulfide, two (3-(triethoxysilyl) propyl group) four thioethers etc.; The sulfydryl one type of silane coupling agent of 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-decoyl sulfenyl-1-propyl-triethoxysilicane etc.; The isocyanates silane coupling agent of 3-isocyanates propyl-triethoxysilicane, 3-isocyanates propyl trimethoxy silicane etc.; The aldehydes silane coupling agent of triethoxysilyl butyraldehyde etc.; The carbamates silane coupling agent of triethoxysilylpropyltetrasulfide methyl carbamate, (3-triethoxysilylpropyltetrasulfide)-tert-butyl group carbamate etc.
When the addition of above-mentioned silane coupling agent is too much, unreacted reactant can cause harmful effect to liquid crystal aligning, therefore when very few, the effect to adaptation be cannot manifest, with respect to the solid constituent of polymkeric substance, 0.01～5.0 % by weight, more preferably 0.1～1.0 % by weight are preferably.
While adding above-mentioned silane coupling agent, in order to prevent separating out of polymkeric substance, preferably above-mentionedly before improving the inhomogeneity solvent of filming, add adding.In addition, while adding silane coupling agent, can, before mixed polyamide acid esters solution and polyamic acid solution, be added in polyamic acid ester solution, polyamic acid solution or polyamic acid ester solution and polyamic acid solution.In addition can be added in the mixed solution of poly amic acid ester and polyamic acid.
Due to be the adaptation that improves polymkeric substance and substrate be that object is added silane coupling agent, therefore as the adding method of silane coupling agent, more preferably be added on and can concentrate in the polyamic acid solution that is present in film inside and substrate interface, after polymkeric substance and silane coupling agent are fully reacted, the method for mixing with polyamic acid ester solution.
After aligning agent for liquid crystal of the present invention is coated on substrate, in order to carry out efficiently the imidizate of poly amic acid ester burning till while filming, can add imidizate promoter.
Exemplify the concrete example of the imidizate promoter of poly amic acid ester below, but be not limited thereto.
[changing 28]
[changing 29]
D in above-mentioned formula (B-1)～(B-17) is tert-butoxycarbonyl or 9-fluorenyl methoxy carbonyl respectively independently.In addition, (B-14)～(B-17) in, in a formula, there are a plurality of D, they can be identical or different.
So long as in the scope of effect that can obtain the hot-imide that promotes poly amic acid ester, content to imidizate promoter is not particularly limited, but 1 mole, the amic acid esters position of the following formula (12) contained with respect to the poly amic acid ester in aligning agent for liquid crystal, be preferably more than 0.01 mole, more preferably more than 0.05 mole, further preferably more than 0.1 mole.In addition, from the harmful effect that the imidizate promoter in the film residuing in burning till itself is caused each characteristic of liquid crystal orientation film, being controlled at minimal angle considers, 1 mole, the amic acid esters position of the following formula (12) contained with respect to the poly amic acid ester in aligning agent for liquid crystal, imidizate promoter is preferably below 2 moles, more preferably below 1 mole, further preferably below 0.5 mole.
[changing 30]
While adding imidizate promoter, owing to there is the possibility of carrying out imidizate by heating, be better therefore interpolation after using good solvent and poor solvent dilution.
< liquid crystal orientation film >
Liquid crystal orientation film of the present invention is that above-mentioned aligning agent for liquid crystal is coated to substrate, dry after, burn till and the film that makes.
Substrate as coating aligning agent for liquid crystal of the present invention, so long as the high substrate of the transparency is not particularly limited, can use the plastic bases such as glass substrate, silicon nitride board, acrylic acid substrate, polycarbonate substrate etc., from the angle that production technology is simplified, preferably use the substrate being formed with for the ITO electrode of liquid crystal drive etc.In addition, in the liquid crystal display cells of reflection-type, can use the opaque materials such as silicon wafer, but only limit to one-sided substrate, electrode now can be used the reflectorized materials such as aluminium.
As the coating process of aligning agent for liquid crystal of the present invention, can exemplify spin-coating method, print process, ink-jet method etc.Dry, the firing process that are coated with after aligning agent for liquid crystal of the present invention can be selected temperature and time arbitrarily.Conventionally, in order fully to remove contained organic solvent, in 50～120 ℃ dry 1 minute～10 minutes, be preferable over 60～100 ℃ dry 2～5 minutes, then burn till 5 minutes～120 minutes in 150～300 ℃, be preferable over 180～230 ℃ and burn till 10～60 minutes.
The thickness of filming after burning till is not particularly limited, if but excessively thin, the reliability of liquid crystal display cells can reduce sometimes, is therefore better 5～300nm, is more preferably 10～200nm.
As the liquid crystal orientation film of gained being carried out to the method for orientation process, can exemplify rubbing manipulation, light orientation process method etc., particularly useful when aligning agent for liquid crystal of the present invention is used in the situation that adopting rubbing manipulation.
[liquid crystal display cells]
Liquid crystal display cells of the present invention is obtained with the substrate of liquid crystal orientation film and carried out after orientation process by aligning agent for liquid crystal of the present invention by said method, by known method, manufactures the liquid crystal display cells that liquid crystal structure cell is made.
Manufacture method to liquid crystal structure cell is not particularly limited, as enumerated an example, normally adopt using be formed with liquid crystal orientation film the 1 pair of substrate so that liquid crystal aligning face as inner side and be better clamping 1～30 μ m, be more preferably the sept (Japanese: after mode ス ペ ー サ ー) arranges of 2～10 μ m, around fixing with sealant, and inject the method that liquid crystal seals.
To enclosing the method for liquid crystal, have no particular limits, can exemplify the vacuum method that injects liquid crystal in the liquid crystal structure cell to making after reducing pressure, drip the dripping method of the laggard row sealing of liquid crystal etc.
Embodiment
Enumerate embodiment below, further illustrate the present invention.But the present invention is not construed as limited to these embodiment certainly.
The abbreviation of using in embodiment and comparative example and the assay method of each characteristic are as described below.
(tetracarboxylic dianhydride)
CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
PMDA:2, two (methoxycarbonyl) terephthalic acid (TPA)s of 5-
TDA:3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride
(dicarboxylic diester)
CBDE:2, two (methoxycarbonyl) cyclo-butane 1 of 4-, 3-dicarboxylic acid
PMDE:2, two (methoxycarbonyl) terephthalic acid (TPA)s of 5-
(diamines)
Me-DADPA:N1-(4-aminophenyl)-N1-methylbenzene-Isosorbide-5-Nitrae-diamines
DADPA:4,4 '-diamino-diphenylamine
P-PDA: p-phenylenediamine (PPD)
DDM:4,4 '-diaminodiphenyl-methane
B76:2,4-diamino-N, N-diallyl aniline
3-ABA:3-(amino methyl) aniline
C16DAB:4-hexadecane Oxy-1,3-diaminobenzene
C18DAB:4-octadecane Oxy-1,3-diaminobenzene
(condensation agent)
DMT-MM:4-(4,6-dimethoxy-1,3,5-triazines-2-yl)-4-methyl morpholine-4-
(organic solvent)
NMP:N-N-methyl-2-2-pyrrolidone N-
BC: butyl cellosolve
γ-BL: gamma-butyrolacton
(embodiment 1)
CBDA(70)PMDA/B76(30)3ABA(50)APC16
As tetracarboxylic dianhydride's composition, use the PMDA of CBDA, the 6.54g (0.030 mole) of 13.53g (0.069 mole), as two amine components, use the C18DAB of 3-ABA, 6.96g (0.020 mole) of B76, the 6.11g (0.050 mole) of 6.10g (0.030 mole), make its in the NMP of 222.39g in room temperature reaction 24 hours, obtain polyamic acid solution (PAA-1).
In the polyamic acid solution (PAA-1) of 20.00g, add the pyridine of the NMP of 30.00g, the acetic anhydride of 3.90g and 1.81g, in stirring at room, after 30 minutes, in 50 ℃ of stirrings 3 hours, make its reaction.After reaction finishes, slowly inject the methyl alcohol of 195g, after polymkeric substance is separated out, stir 30 minutes, by filtered and recycled solid.With methyl alcohol, fully clean after the solid obtaining, by 100 ℃ by its vacuum drying, obtain polyimide powder (SPI-1).The number-average molecular weight of this polyimide is 13600, and weight-average molecular weight is 33800, and acid imide rate is 90%.
In the polyimide powder (SPI-1) of 6.47g, add γ-BL of 58.23g, in 50 ℃, stir and within 24 hours, make it dissolve, confirm to dissolve completely.Then, add γ-BL of 15.28g, the BC of 19.73g, by stirring 24 minutes in 50 ℃, obtaining polyimide is that 6.0 quality %, γ-BL are that 74 quality %, BC are the polyimide solution (SPI-1) of 20 quality %.Using the polyimide solution obtaining as aligning agent for liquid crystal (AL-1).With the rub evaluation of patience, albefaction and voltage retention (VHR) of this coating fluid.
Together with each evaluation result of friction patience, albefaction and VHR of using the coating fluid of embodiment 1 and obtaining and the ratio of components (weight ratio) of polymer solution, be shown in Table 1.
(embodiment 2)
TDA/p-PDA(90)APC18
As tetracarboxylic dianhydride's composition, use the TDA of 7.51g (0.025 mole), as two amine components, use the C18DAB of p-PDA, the 0.94g (0.0025 mole) of 2.43g (0.023 mole), make its in the NMP of 61.66g in 50 ℃ reaction 24 hours, obtain polyamic acid solution (PAA-2).
In the polyamic acid solution (PAA-2) of 20.00g, add the pyridine of the NMP of 30.67g, the acetic anhydride of 7.18g and 3.33g, in stirring at room, after 30 minutes, in 40 ℃ of stirrings 3 hours, make its reaction.After reaction finishes, slowly inject the methyl alcohol of 214g, after polymkeric substance is separated out, stir 30 minutes, by filtered and recycled solid.With methyl alcohol, fully clean after the solid obtaining, by 100 ℃ by its vacuum drying, obtain polyimide powder (SPI-2).The number-average molecular weight of this polyimide is 12400, and weight-average molecular weight is 27400, and acid imide rate is 86%.
In the polyimide powder (SPI-2) of 2.60g, add γ-BL of 29.90g, in 50 ℃, stir and within 24 hours, make it dissolve, confirm to dissolve completely.Then, add γ-BL of 2.16g, the BC of 8.67g, by stirring 24 minutes in 50 ℃, obtaining polyimide is that 6.0 quality %, γ-BL are that 94 quality %, BC are the polyimide solution (SPI-2) of 20 quality %.Using the polyimide solution obtaining as aligning agent for liquid crystal (AL-2).Use this coating fluid to carry out the evaluation identical with embodiment 1.
(embodiment 3)
CBDE(50)PMDE/DDM
As dicarboxylic diester composition, use the PMDE of CBDE, the 14.12g (0.050 mole) of 11.97g (0.046 mole), as two amine components, use the DDM of 19.83g (0.10 mole), as alkali, use the triethylamine of 5.10g (0.050 mole), as condensation agent, use the DMT-MM of 83.20g (0.30 mole), make its in the NMP of 719.18g in room temperature reaction 3 hours, obtain polyamic acid ester solution (PAE-1).
This polyamic acid ester solution is dropped in 4692g methyl alcohol, reclaim the solid matter of precipitation.Then, by this solid matter with washed with methanol for several times after, drying under reduced pressure at 100 ℃, obtains the white powder of poly amic acid ester (PAE-1).The number-average molecular weight of this poly amic acid ester is 12900, and weight-average molecular weight is 28800.
In the poly amic acid ester obtaining at 2.15g (PAE-1), add the NMP of 15.77g, in stirring at room 4 hours.When stirring end, poly amic acid ester dissolves completely.Then, add the NMP of 5.47g and the BC of 9.20g in this solution, in stirring at room 2 hours, making poly amic acid ester was that 6 quality %, NMP are that 74 quality %, BC are the solution of 20 quality %.Using the polyamic acid ester solution making as aligning agent for liquid crystal (AL-3).Use this coating fluid to carry out the evaluation identical with embodiment 1.
(embodiment 4)
CBDE/Me-DADPA(50)DADPA(30)DDM
As dicarboxylic diester composition, use the CBDE of 8.57g (0.033 mole), as two amine components, use the DDM of DADPA, 1.39g (0.0070 mole) of Me-DADPA, the 2.10g (0.011 mole) of 3.73g (0.018 mole), as alkali, use the triethylamine of 1.81g (0.018 mole), as condensation agent, use the DMT-MM of 25.19g (0.091 mole), make its in the NMP of 247.11g in room temperature reaction 4 hours, obtain polyamic acid ester solution (PAE-2).
This polyamic acid ester solution is dropped in 1594g methyl alcohol, reclaim the solid matter of precipitation.Then, by this solid matter with washed with methanol for several times after, drying under reduced pressure at 100 ℃, obtains the white powder of poly amic acid ester (PAE-2).The number-average molecular weight of this poly amic acid ester is 12300, and weight-average molecular weight is 33500.
In the poly amic acid ester obtaining at 2.18g (PAE-2), add the NMP of 19.62g, in stirring at room 5 hours.When stirring end, poly amic acid ester dissolves completely.Then, add γ-BL of 1.01g and the BC of 6.54g in this solution, in stirring at room 1 hour, making poly amic acid ester was that 6 quality %, γ-BL are that 57 quality %, NMP are that 17 quality %, BC are the solution of 20 quality %.Using the polyamic acid ester solution making as aligning agent for liquid crystal (AL-4).Use this coating fluid to carry out the evaluation identical with embodiment 1.
(embodiment 5)
CBDA(50)PMDA/DDM
As tetracarboxylic dianhydride's composition, use the PMDA of CBDA, the 10.25g (0.047 mole) of 9.81g (0.050 mole), as two amine components, use the DDM of 19.83g (0.0060 mole), make its in γ-BL of 113.00g and the NMP of 113.00g in room temperature reaction 3 hours, obtain polyamic acid solution (PAA-1).
BC dilution by the polyamic acid solution of 198.97g (PAA-1) with γ-BL of 204.23g, the NMP of 14.63g and 73.74g, making solid state component (polyamic acid) is that 6 quality %, γ-BL are that 59 quality %, NMP are that 20 quality %, BC are the solution of 15 quality %.The number-average molecular weight of this polyamic acid is 20900, and weight-average molecular weight is 57900.
(embodiment 6)
(embodiment 1)/(embodiment 3)=3/7
The condition that reaches 30:70 according to the weight ratio of the polyimide solution being made by embodiment 1 (SPI-1) and the polyesteramide acid solution (PAE-1) that made by embodiment 3 is mixed, in stirring at room 1 hour, obtain aligning agent for liquid crystal (AL-5).Use this coating fluid to carry out the evaluation identical with embodiment 1.
(embodiment 7)
(embodiment 2)/(embodiment 3)=3/7
The condition that reaches 30:70 according to the weight ratio of the polyimide solution being made by embodiment 2 (SPI-2) and the polyesteramide acid solution (PAE-1) that made by embodiment 3 is mixed, in stirring at room 1 hour, obtain aligning agent for liquid crystal (AL-6).Use this coating fluid to carry out the evaluation identical with embodiment 1.
(embodiment 8)
(embodiment 1)/(embodiment 4)=3/7
The condition that reaches 30:70 according to the weight ratio of the polyimide solution being made by embodiment 1 (SPI-1) and the polyesteramide acid solution (PAE-2) that made by embodiment 4 is mixed, in stirring at room 1 hour, obtain aligning agent for liquid crystal (AL-7).Use this coating fluid to carry out the evaluation identical with embodiment 1.
(embodiment 9)
(embodiment 2)/(embodiment 4)=3/7
The condition that reaches 30:70 according to the weight ratio of the polyimide solution being made by embodiment 2 (SPI-2) and the polyesteramide acid solution (PAE-2) that made by embodiment 4 is mixed, in stirring at room 1 hour, obtain aligning agent for liquid crystal (AL-8).Use this coating fluid to carry out the evaluation identical with embodiment 1.
(comparative example 1)
(embodiment 2)/(embodiment 5)=3/7
The condition that reaches 30:70 according to the weight ratio of the polyimide solution being made by embodiment 2 (SPI-2) and the polyamic acid solution (PAA-1) that made by embodiment 5 is mixed, in stirring at room 1 hour, obtain aligning agent for liquid crystal (AL-9).Use this coating fluid to carry out the evaluation identical with embodiment 1.
The mensuration > of < molecular weight
The molecular weight of the polyimide being obtained by polyreaction is measured as follows: by GPC (normal temperature gel permeation chromatography) device, measure this polyimide, as polyglycol and polyethylene oxide scaled value, calculate number-average molecular weight and weight-average molecular weight.
GPC device: Showa Denko K. K (Shodex society) system (GPC-101)
Post: Showa Denko K. K's system (series connection of KD803 and KD805)
Column temperature: 50 ℃
Eluent: DMF (as adjuvant, lithium bromide monohydrate (LiBrH 20) be that 30 mMs/L (liter), phosphoric acid anhydrous crystal (o-phosphoric acid) are that 30 mMs/L, tetrahydrofuran (THF) are 10ml/L)
Flow velocity: 1.0ml/ minute
Calibration curve making standard sample: TOSOH Co., Ltd's (Eastソ ー society) TSK standard polyethylene oxide processed (molecular weight is about 900000,150000,100000 and 30000), and the polyglycol (molecular weight is about 12000,4000 and 1000) of polymkeric substance laboratory company (Port リ マ ー ラ ボ ラ トリ ー society) system.
The manufacture > of < liquid crystal structure cell
For the aligning agent for liquid crystal being made by embodiment 1～4 and 6～10, according to method as follows, make liquid crystal structure cell.
Aligning agent for liquid crystal is spun on the glass substrate with transparency electrode, dry after 70 seconds on the heating plate of 70 ℃, on the heating plate of 210 ℃, carry out 10 minutes burn till, what to form thickness be 100nm films.With the rubbing device of roller footpath 120mm, under the condition of roller rotating speed 1000rpm, roller gait of march 50mm/ second, the amount of being pressed into 0.3mm, with rayon cloth, this coated surface is rubbed, obtain the substrate with liquid crystal orientation film.
Then, prepare two substrates with liquid crystal orientation film, after scattering the sept of 6 μ m on the liquid crystal aligning face of therein, printing and sealing agent thereon, then make liquid crystal aligning face relatively and under the condition of frictional direction quadrature by after another piece baseplate-laminating, make sealant cures, make negative crystal born of the same parents.Adopt decompression injection method, in this negative crystal born of the same parents, inject liquid crystal MLC-2003 (Merck Japanese firm (メ ルク ジャパン society) system), by inlet sealing, made stable twisted nematic liquid crystal structure cell.
Mensuration and the evaluating characteristics of the physical property of each liquid crystal structure cell of making are as described below.
In addition, the composition of each aligning agent for liquid crystal in embodiment 2～4, embodiment 6～9 and comparative example 1, the result of the physical property measurement of each liquid crystal orientation film and evaluating characteristics etc. is gathered and is shown in table 1.
The mensuration > of < voltage retention (VHR)
Being determined as follows of voltage retention to the stable twisted nematic liquid crystal structure cell making carried out: at the temperature of 90 ℃, apply the voltage 60 μ s of 4V, measure the voltage after 166.7ms, calculating voltage can keep how many, using this as voltage retention.
In addition, the mensuration of voltage retention adopts the voltage retention determinator (VHR-1) of Toyo Corp. (East Yang テ クニ カ society) system.
< accumulates the estimation > of electric charge (RDC)
At the temperature of 23 ℃, at the interval with 0.1V, from the condition of OV to 1.0V, the stable twisted nematic liquid crystal structure cell making is applied to DC voltage, measure the flicker amplitude level under each voltage, make calibration curve.After ground connection 5 minutes, apply alternating voltage 3.0V and DC voltage 5.0V, measure the flicker amplitude level after 1 hour, by contrasting ready-made calibration curve, estimate RDC (evaluation method of this RDC is called flicker reference entry).
Here, RDC (disconnect after) represents just to have applied the alternating voltage 3.0V of 1 hour and the value after DC voltage 5.0V, after RDC (after 5 minutes) represents just to have disconnected alternating voltage and the value of accumulating electric charge that disconnects latter 30 minutes.
[table 1]
The possibility of industrial utilization
If adopt aligning agent for liquid crystal of the present invention, even if the acid imide rate of soluble polyimide is high, also can obtain filming while forming, not there is not albinism, printing is good, and the good liquid crystal orientation film of wear-resisting wiping of filming, and the voltage retention that the liquid crystal orientation film obtaining has (VHR) and to accumulate the electrical characteristics of electric charge (RDC) etc. also excellent, the liquid crystal display cells with this liquid crystal orientation film can be widely used in TN element, STN element, TFT liquid crystal cell, and the liquid crystal display cells of vertical orientating type etc.
Quote the full content of instructions, claims and specification digest of No. 2012-082729, the Japanese patent application of filing an application on March 30th, 2012 here as the announcement of instructions of the present invention.

Claims (15)

1. an aligning agent for liquid crystal, is characterized in that, contains the soluble polyimide representing with following formula (1) and the poly amic acid ester representing with following formula (2),
[changing 1]
In formula (1), X 14 valency organic groups, Y 1it is divalent organic group; In formula (2), X 24 valency organic groups, Y 2divalent organic group, R 1it is the alkyl of carbon number 1～5; A 1and A 2be respectively hydrogen atom or alkyl, alkenyl or the alkynyl can with substituent carbon number 1～10 independently.
2. aligning agent for liquid crystal as claimed in claim 1, is characterized in that, the R in formula (2) 1it is methyl.
3. aligning agent for liquid crystal as claimed in claim 1 or 2, is characterized in that, the X in formula (1), formula (2) 1and X 2respectively independently for being selected from least one of the structure that represents with following formula,
[changing 2]
4. the aligning agent for liquid crystal as described in any one in claim 1～3, is characterized in that, in formula (2), and X 2the following structure with aromatic ring:
[changing 3]
5. the aligning agent for liquid crystal as described in any one in claim 1～3, is characterized in that, in formula (1), and X 1there is aliphatic structure or ester ring type structure.
6. the aligning agent for liquid crystal as described in any one in claim 1～5, is characterized in that, the weight-average molecular weight of described poly amic acid ester is 5000～200000.
7. the aligning agent for liquid crystal as described in any one in claim 1～6, is characterized in that, described soluble polyimide has more than 50% acid imide rate, and weight-average molecular weight is 5000～200000.
8. the aligning agent for liquid crystal as described in any one in claim 1～7, it is characterized in that, the ratio of the content of described soluble polyimide and the content of described poly amic acid ester, be that the content of the content/poly amic acid ester of soluble polyimide is 1/9～9/1 by quality ratio.
9. the aligning agent for liquid crystal as described in any one in claim 1～8, it is characterized in that, comprise the organic solvent that dissolves described soluble polyimide and described poly amic acid ester, the content of soluble polyimide and the total amount of poly amic acid ester are 0.5～15 quality %.
10. aligning agent for liquid crystal as claimed in claim 9, is characterized in that, described organic solvent contains at least one that is selected from N-methyl-pyrrolidone, N-ethyl-pyrrolidone and gamma-butyrolacton.
11. aligning agent for liquid crystal as described in any one in claim 1～10, is characterized in that, also comprise solvent.
12. aligning agent for liquid crystal as claimed in claim 11, is characterized in that, described solvent is butyl cellosolve.
13. 1 kinds of liquid crystal orientation films, is characterized in that, by the aligning agent for liquid crystal described in any one in claim 1～12 being coated with, burning till, obtain.
14. liquid crystal orientation films as claimed in claim 13, is characterized in that, the thickness of filming that described aligning agent for liquid crystal is coated with, is burnt till and obtains is 5～300nm.
15. 1 kinds of liquid crystal display cells, is characterized in that, possess the liquid crystal orientation film described in claim 13 or 14.
CN201380016101.1A 2012-03-30 2013-03-28 Polyimide-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element Pending CN104204925A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110191909A (en) * 2017-01-20 2019-08-30 住友化学株式会社 The manufacturing method of film, resin combination and polyamide-imide resin
CN115716914A (en) * 2022-11-24 2023-02-28 天津科技大学 Imidization method of polyamide acid and polyimide

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