CN110325901A - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element - Google Patents

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element Download PDF

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CN110325901A
CN110325901A CN201680092089.6A CN201680092089A CN110325901A CN 110325901 A CN110325901 A CN 110325901A CN 201680092089 A CN201680092089 A CN 201680092089A CN 110325901 A CN110325901 A CN 110325901A
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liquid crystal
formula
aligning agent
film
methyl
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CN110325901B (en
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松本欣也
桥本淳
作本直树
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—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

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Even providing for obtaining negative type liquid crystal, will not generate bright spot, aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal that can obtain the alignment films suitable for light orientation of good image retention speciality indicate element.A kind of aligning agent for liquid crystal contains selected from least one of group by forming with the polyimide precursor of structural unit shown in structural unit shown in formula (1) and formula (2) and the imide amination polymer of polyimide precursor polymer (A).It is recorded in the definition of mark in formula such as specification.

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
Technical field
The present invention relates to the aligning agent for liquid crystal for being suitable for optical alignment method processing, the liquid crystal orientation film obtained by the aligning agent for liquid crystal With the liquid crystal expression element for having used the liquid crystal orientation film.
Background technique
Liquid crystal used in LCD TV, liquid crystal display etc. indicates element, would commonly be used for the arrangement shape of control liquid crystal The liquid crystal orientation film of state is set in element.As liquid crystal orientation film, main use will be with polyamic acid (polyamide ) etc. acid polyimide precursors, soluble polyimide solution make aligning agent for liquid crystal as main component and be coated on glass base The liquid crystal orientation film of polyimides system made of plate etc. and firing.Now according to industrial most popular method, the liquid crystal aligning Film is carried out by the surface of the polyimides system liquid crystal orientation film for being formed on electrode base board with cotton, nylon, polyester etc. Cloth makes in so-called friction treatment that a direction rubs.
Optical alignment method has as the method for orientation treatment to rub less and industrially also can use easy manufacturing process The advantages of production, indicates member in the liquid crystal of IPS (plane switching) driving method, boundary electric field switching (following, FFS) driving method In part, by using the liquid crystal orientation film obtained using optical alignment method, with the liquid crystal orientation film phase obtained using friction treatment method Than, it can expect that liquid crystal indicates the contrast of element, field angle characteristic improvement etc., can improve liquid crystal indicates element function, because This attracts attention as promising liquid crystal aligning processing method.
But the liquid crystal orientation film obtained using optical alignment method is compared with the liquid crystal orientation film obtained using friction treatment, In the presence of the differently- oriented directivity for polymeric membrane anisotropy it is small the problems such as.It cannot get sufficient liquid crystal if anisotropy is small to take There is the problems such as generating ghost in the case where forming liquid crystal expression element in tropism.The liquid obtained as raising using optical alignment method The anisotropic method of brilliant alignment films is proposed after light irradiation, will be irradiated by light, the backbone breaking of aforementioned polyimides And the low molecular weight compositions removal generated.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 9-297313 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2011-107266 bulletin
Non-patent literature
Non-patent literature 1: " liquid crystal photo-alignment film (liquid crystal light alignment film) " the wood Kobe side of body, village, city functional material (function material) In November, 1997 Vol.17No.11 13-22 page
Summary of the invention
Problems to be solved by the invention
IPS driving method, FFS driving method liquid crystal indicate element in, in the past use positive type liquid crystal, but by using Negative type liquid crystal, the transmission loss of electrode upper is small, can improve contrast.If the liquid crystal orientation film that will be obtained using optical alignment method For using the IPS driving method of negative type liquid crystal, the liquid crystal expression element of FFS driving method, then member is indicated with previous liquid crystal Part is compared worthy of expecting with high expression performance.
But the results of study such as present inventor are it is found that the liquid crystal orientation film obtained using light orientation, is using minus In the case that the liquid crystal of liquid crystal indicates element, there is a problem of indicating that the generation rate of bad (bright spot) is high, it is bad to generate expression.
The object of the present invention is to provide for obtaining in the case where using negative type liquid crystal, will not generate bright spot, Can obtain the liquid crystal orientation film of the optical alignment method of good image retention speciality be suitable for optical alignment method processing aligning agent for liquid crystal, by Liquid crystal orientation film that the aligning agent for liquid crystal obtains and the liquid crystal for having the aligning agent for liquid crystal indicate element.
The solution to the problem
The inventors of the present invention further investigate, as a result, it has been found that, include the polyimides based polymer with specific structure Aligning agent for liquid crystal is effectively, so as to complete the present invention for reaching above-mentioned purpose.
Purport of the invention is for example following recorded.
1. a kind of aligning agent for liquid crystal, which is characterized in that it contains selected from by with shown in following formula (1) and following formula (2) The polyimide precursor of structural unit and at least one of the group that forms of the imide amination polymer of the polyimide precursor Polymer (A).
(in formula (1), formula (2), X1And X2It is 4 valence organic groups, R each independently1And R2Be each independently hydrogen atom, Or the alkyl of carbon number 1~4, A1、A2、A3、A4It is the alkyl of hydrogen atom or carbon number 1~4, Z each independently1、Z2、Z3And Z4Respectively From the alkyl for being independently hydrogen atom, halogen atom and carbon number 1~4, the integer that n is 1~4.)
The effect of invention
According to the present invention it is possible to which providing can obtain in the case where using negative type liquid crystal, can also inhibit at light orientation High, with good image retention speciality the liquid crystal orientation film of the bright spot and illumination sensitivity that are found in logos, be suitable for light orientation The aligning agent for liquid crystal of method processing.By having the liquid crystal orientation film obtained by above-mentioned aligning agent for liquid crystal, can provide is not indicated Bad, high reliablity liquid crystal indicates element.
Specific embodiment
<particular polymers>
Aligning agent for liquid crystal of the invention contains as described above selected from as with knot shown in above-mentioned formula (1) and above-mentioned formula (2) The polymerization of at least one of the group that the polyimide precursor of structure unit and the imide amination polymer of the polyimide precursor form Object (A) (also referred to as particular polymers (A)).
In formula (1) and formula (2), R1And R2It is the alkyl of hydrogen atom or carbon number 1~4 each independently.From using heat into From the viewpoint of the easy degree of row imidizate, particularly preferably hydrogen atom or methyl.X1And X2For the organic group of 4 valences. It is irradiated preferably by ultraviolet light, is decomposed, the reaction such as isomerization, anisotropic structure can be assigned, be more preferably selected from At least one of the group of the structure composition as shown in following formula (X1-1)~(X1-9).
In formula (X1-1), R3、R4、R5And R6It is hydrogen atom, halogen atom, the alkyl of carbon number 1~6, carbon each independently Alkenyl, alkynyl or the phenyl of number 2~6, can be identical or different.From the viewpoint of liquid crystal aligning, R3、R4、R5And R6It is excellent It is selected as hydrogen atom, halogen atom, methyl or ethyl, more preferable hydrogen atom or methyl.It, can as the specific structure of formula (X1-1) Enumerate structure shown in following formula (X1-10)~(X1-11).It is especially excellent from the viewpoint of liquid crystal aligning and sensitivity It is selected as (X1-11).
In formula (1) and formula (2), A1、A2、A3、A4It is the alkyl of hydrogen atom or carbon number 1~4 each independently.It is taken from liquid crystal From the viewpoint of tropism, preferably hydrogen atom or methyl, more preferable hydrogen atom.
In formula (1) and formula (2), Z1、Z2、Z3And Z4It is the alkane of hydrogen atom, halogen atom or carbon number 1~4 each independently Base.From the viewpoint of liquid crystal aligning, preferably hydrogen atom, halogen atom or methyl.The integer that n is 1~4.
In particular polymers (A), from the viewpoint of liquid crystal aligning and bright spot inhibition, relative to its entire infrastructure unit 1 mole, the ratio of structural unit shown in above-mentioned formula (1) is preferably 10~50 moles of %, more preferable 30~50 moles of %.
In addition, in particular polymers (A), the containing ratio of structural unit shown in above-mentioned formula (2) from liquid crystal aligning and From the viewpoint of bright spot inhibits, relative to 1 mole of its entire infrastructure unit, preferably 20~90 moles of %, more preferable 20~50 Mole %.
Particular polymers (A) are from the viewpoint of the mechanical strength of alignment films, preferably in addition to shown in above-mentioned formula (1) and (2) Structural unit other than, also have following formula (3) shown in structural unit.
In formula (3), X3X including preference, in meaning and above-mentioned formula (1) and formula (2)1And X2It is identical.R3Including excellent Including selecting example, meaning and above-mentioned R1And R2It is identical.Y1For the group selected from the structure composition as shown in following formula [1d-1]~[1d-7] At least one of.
In above-mentioned formula [1d-1]~formula [1d-7], D is tert-butoxymethoxy carbonyl.n1~n5It is 1~5 each independently Integer.
As Y1More specific example, following formula [1d1-1]~[1d1-6] can be enumerated.
In above-mentioned [1d1-1]~[1d1-6], D is tert-butoxymethoxy carbonyl.
The containing ratio of structural unit shown in formula (3) is excellent relative to 1 mole of entire infrastructure unit of particular polymers (A) It is selected as 10~50 moles of %, more preferable 20~30 moles of %.
Particular polymers (A) can have the structural unit shown in above-mentioned formula (1)~(3) other than, also containing following The polyimide precursor of structural unit shown in formula (4) and the imidizate condensate of the polyimide precursor.
In formula (4), R4R including preference, in meaning and above-mentioned formula (1)1It is identical.A5And A6Exist including preference It is interior, the A of meaning and above-mentioned formula (1)1And A2It is identical.X is 4 valence organic groups, its structure is not particularly limited.
Above-mentioned formula (X1-1)~(X1-9) or following formula (X-9)~(X-42) can be enumerated if enumerating concrete example.From Compound it is acquired from the viewpoint of, X can enumerate X1-1~X1-9, X-17, X-25, X-26, X-27, X-28, X-32 or X-39.In addition consider from viewpoints such as the fast liquid crystal orientation films of the decaying for the residual charge for obtaining accumulating due to DC voltage, it is excellent It is selected as the tetracarboxylic dianhydride with aromatic ring structure, as X, more preferably X-26, X-27, X-28, X-32, X-35 or X- 37。
In above-mentioned formula (4), Y is divalent organic group, its structure is not particularly limited.If enumerating Y2Concrete example Following formula (Y-1)~(Y-84) can then be enumerated.
In order to improve liquid crystal aligning, Y is preferably the high structure of linearity.As concrete example, more preferably Y-7, Y-43 ~Y-48, Y63 or Y-71~Y-76.The liquid crystal that the decaying for the residual charge accumulated in order to obtain due to DC voltage is fast takes To film, more preferably Y-77~Y-84.
<manufacturing method of poly amic acid ester>
The poly amic acid ester of polyimide precursor used in the present invention can by (1) as shown below, (2) or (3) method manufacture.
(1) the case where being synthesized by polyamic acid
Poly amic acid ester can be synthesized by the way that the polyamic acid obtained by tetracarboxylic dianhydride and diamines to be esterified.
Specifically, can by make polyamic acid and esterifying agent in presence of organic solvent, -20 DEG C~150 DEG C, It is preferred that carrying out reaction in 30 minutes~24 hours, preferably 1~4 hour at 0 DEG C~50 DEG C to synthesize.
As esterifying agent, the esterifying agent that can be preferably readily removable by purifying can enumerate N, N- dimethyl Formamide dimethylacetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N, N- bis- Methylformamide di neo-pentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal, 1- methyl -3- p-methylphenyl three Nitrence, 1- ethyl -3- p-methylphenyl triazenes, 1- propyl -3- p-methylphenyl triazenes, 4- (4,6- dimethoxy -1,3,5- three Piperazine -2- base) -4- methyl morpholine hydrochloride etc..The dosage of esterifying agent relative to polyamic acid 1 mole of repetitive unit, preferably 2 ~6 molar equivalents.
Solvent used in above-mentioned reaction from the dissolubility viewpoint of polymer consider, preferably n,N-Dimethylformamide, N-methyl-2-pyrrolidone or gamma-butyrolacton, they can be used one kind or two or more.Concentration when synthesis is from being not likely to produce It the precipitation of polymer and is easy to get from the viewpoint of high molecular weight body, preferably 1~30 mass %, more preferable 5~20 matter Measure %.
(2) the case where being synthesized by tetracarboxylic acid acid diesters dichloride with the reaction of diamines
Poly amic acid ester can be synthesized by tetracarboxylic acid acid diesters dichloride and diamines.
Specifically, can by making tetracarboxylic acid acid diesters dichloride and diamines in the presence of alkali and organic solvent ,- Reaction in 30 minutes~24 hours, preferably 1~4 hour is carried out at 20 DEG C~150 DEG C, preferably 0 DEG C~50 DEG C to synthesize.
Pyridine, triethylamine, 4-dimethylaminopyridine etc. can be used in aforementioned bases, but in order to leniently be reacted, Preferably pyridine.For the additive amount of alkali, from for the amount easily removed and from the viewpoint of being easy to get high molecular weight body, phase It is preferably 2~4 times moles for tetracarboxylic acid acid diesters dichloride.
Solvent used in above-mentioned reaction considers from the dissolubility of monomer and polymer, preferably N- methyl -2- pyrrolidines Ketone or gamma-butyrolacton, they can be used one kind or two or more.Polymer concentration when for synthesis is from being not likely to produce polymer Precipitation and be easy to get from the viewpoint of high molecular weight body, preferably 1~30 mass %, more preferable 5~20 mass %. In addition, the hydrolysis of tetracarboxylic acid acid diesters dichloride in order to prevent, solvent used in the synthesis of poly amic acid ester is preferably as far as possible It is dehydrated, preferably in nitrogen atmosphere, extraneous gas is prevented to be mixed into.
(3) by the reaction synthesis of tetracarboxylic acid acid diesters and diamines the case where
Poly amic acid ester can be synthesized by tetracarboxylic acid acid diesters with diamines polycondensation.
Specifically, can be by making tetracarboxylic acid acid diesters and diamines in the presence of condensing agent, alkali and organic solvent at 0 DEG C Reaction in 30 minutes~24 hours, preferably 3~15 hours is carried out at~150 DEG C, preferably 0 DEG C~100 DEG C to synthesize.
Triphenyl phosphite, dicyclohexylcarbodiimide, 1- ethyl -3- (3- dimethyl can be used in aforementioned condensation agent Aminopropyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-cyanuro 1,3,5 methyl morpholine, O- (benzene And triazol-1-yl)-N, N, N ', N '-tetramethylurea tetrafluoroborate, O- (benzotriazole -1- base)-N, N, N ', N '-tetramethyl Urea hexafluorophosphate, (thio -3- benzoxazolyl of 2,3- dihydro -2-) phosphonic acid diphenyl ester etc..The additive amount of condensing agent relative to Tetracarboxylic acid acid diesters are preferably 2~3 times moles.
The tertiary amines such as pyridine, triethylamine can be used in aforementioned bases.The additive amount of alkali is from the amount to easily remove and is easy It is preferably 2~4 times moles relative to diamine component to from the viewpoint of high molecular weight body.
In addition, by the way that lewis acid is added as additive, reaction is effectively performed in above-mentioned reaction.As Louis The lithium halides such as acid, preferably lithium chloride, lithium bromide.Lewis acidic additive amount is preferably 0~1.0 times relative to diamine component and rubs You.
In the synthetic method of above-mentioned three kinds of poly amic acid esters, the poly amic acid ester of high molecular weight in order to obtain, particularly preferably For the synthetic method of above-mentioned (1) or above-mentioned (2).
Solution for the poly amic acid ester obtained as described above, it is bad molten by being injected into while being sufficiently stirred Agent can be such that polymer is precipitated.It is precipitated for several times, after being washed with poor solvent, carries out room temperature or heat drying, it is available The powder of sublimed poly amic acid ester.Poor solvent is not particularly limited, water outlet, methanol, ethyl alcohol, hexane, fourth can be enumerated Base cellosolve, acetone, toluene etc..
<manufacturing method of polyamic acid>
The polyamic acid of polyimide precursor used in the present invention can be synthesized by method as shown below.
Specifically, can by make tetracarboxylic dianhydride and diamines in presence of organic solvent, -20 DEG C~150 DEG C, It is preferred that carrying out reaction in 30 minutes~24 hours, preferably 1~12 hour at 0 DEG C~50 DEG C to synthesize.
Organic solvent used in above-mentioned reaction from the dissolubility viewpoint of monomer and polymer consider, preferably N, N- diformazan Base formamide, n-methyl-2-pyrrolidone or gamma-butyrolacton, they can be used one kind or two or more.The concentration of polymer From the viewpoint of the precipitation for being not likely to produce polymer and being easy to get high molecular weight body, preferably 1~30 mass %, more It is preferred that 5~20 mass %.
It is bad molten by being injected into while reaction solution is sufficiently stirred for the polyamic acid obtained as described above Agent can make polymer be precipitated and recycle.In addition, being precipitated for several times, after being washed with poor solvent, carries out room temperature or heating is dry It is dry, the powder of available sublimed polyamic acid.Poor solvent can enumerate water outlet, methanol, ethyl alcohol, hexane, the molten fibre of butyl Agent, acetone, toluene etc..
<manufacturing method of polyimides>
Polyimides used in the present invention can be by carrying out imidizate for foregoing polyamides acid esters or polyamic acid To manufacture.In the case where manufacturing polyimides by poly amic acid ester, Xiang Qianshu poly amic acid ester solution or by poly amic acid ester tree Cosmetics end be dissolved in polyamic acid solution obtained from organic solvent add basic catalyst imidizate chemically be Easy.Imidizate chemically due to carrying out imidization reaction at relatively low temperatures, in the process of imidizate In be not likely to produce polymer molecular weight reduce, thus preferably.
Imidizate chemically can by by the poly amic acid ester of desired imidizate in organic solvent, in alkalinity It is stirred in the presence of catalyst to carry out.As organic solvent, the solvent used when polymerization reaction above-mentioned can be used.Make For basic catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated.Wherein, triethylamine due to have pair It is adequately alkaline for being reacted, thus preferably.
The temperature for carrying out imidization reaction is -20 DEG C~140 DEG C, preferably 0 DEG C~100 DEG C, the reaction time is preferably 1~ 100 hours.The amount of basic catalyst is 0.5~30 mole times of amic acid ester group, preferably 2~20 moles times.It is obtained poly- The acid imide rate for closing object can be controlled by adjusting catalytic amount, temperature, reaction time.After imidization reaction Catalyst added by remaining in solution etc., therefore preferably gathered obtained imidizate by means as described below Object recycling is closed, is redissolved with organic solvent, aligning agent for liquid crystal of the invention is made.
In the case where manufacturing polyimides by polyamic acid, react to obtain to by diamine component and tetracarboxylic dianhydride Foregoing polyamides acid solution in add catalyst imidizate chemically be easy.Imidizate chemically by In the molecular weight drop for carrying out imidization reaction at relatively low temperatures, being not likely to produce during imidizate polymer It is low, thus preferably.
Imidizate chemically can by by the polymer of desired imidizate in organic solvent, in base catalysis It is stirred in the presence of agent and acid anhydrides to carry out.As organic solvent, what is used when polymerization reaction above-mentioned can be used is molten Agent.As basic catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated.Wherein, pyridine is due to tool Have appropriate alkalinity for reacting and it is preferred that.In addition, as acid anhydrides, acetic anhydride, trimellitic anhydride, can be enumerated Benzene tetracarboxylic acid acid anhydride etc., wherein if using acetic anhydride, due to purifying after reaction becomes easy and it is preferred that.
Temperature when carrying out imidization reaction is -20 DEG C~140 DEG C, preferably 0 DEG C~100 DEG C, and the reaction time can be 1 ~100 hours.The amount of basic catalyst is 0.5~30 mole times of amide acidic group, preferably 2~20 moles times, and the amount of acid anhydrides is 1~50 mole of amide acidic group times, preferably 3~30 moles times.The acid imide rate of obtained polymer can pass through adjusting Catalytic amount, temperature, reaction time control.
Catalyst added by remaining in solution after the imidization reaction of poly amic acid ester or polyamic acid etc., because This preferably by means as described below, obtained imide amination polymer is recycled, is redissolved with organic solvent, this is made The aligning agent for liquid crystal of invention.
For the polyimide solution obtained as described above, by being injected into poor solvent while being sufficiently stirred, Polymer can be made to be precipitated.It is precipitated for several times, after being washed with poor solvent, carries out room temperature or heat drying, it is available pure The powder for the poly amic acid ester changed.
Aforementioned poor solvent is not particularly limited, methanol, acetone, hexane, butyl cellosolve, heptane, first can be enumerated Ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene etc..
<aligning agent for liquid crystal>
Solution made of there is aligning agent for liquid crystal used in the present invention particular polymers (A) to be dissolved in organic solvent Form.The molecular weight of particular polymers (A) by Weight-average molecular meter is preferably 2000~500000, it is more preferable 5000~ 300000, further preferred 10000~100000.In addition, number-average molecular weight be preferably 1000~250000, it is more preferable 2500~ 150000, further preferred 5000~50000.
It, can be appropriate according to the setting for the thickness for thinking film to be formed for the concentration of the polymer in aligning agent for liquid crystal Change, but be formed from uniformly and from the viewpoint of not having defective film, preferably 1 weight % or more, from the preservation of solution It is preferably 10 weight % or less from the viewpoint of stability.
Solvent used in aligning agent for liquid crystal of the invention is (also referred to as good molten if the solvent of dissolution particular polymers (A) Agent), it is not particularly limited.It is exemplified below out the concrete example of good solvent.
Such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- second can be enumerated Base -2-Pyrrolidone, dimethyl sulfoxide, gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4- hydroxy-4-methyl-2-pentanone etc..Wherein, it is preferable to use n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, γ-fourth Lactone.
In turn, in the case that the dissolubility of particular polymers (A) in a solvent is high, preferably following formula [D-1]~formula [D- 3] solvent shown in.
In formula [D-1]~formula [D-3], D1Indicate alkyl, the D of carbon number 1~32Indicate alkyl, the D of carbon number 1~33Indicate carbon The alkyl of number 1~4.
The content of good solvent in aligning agent for liquid crystal is preferably 20~99 mass % of whole solvents, more preferable 20~90 matter Measure %, particularly preferred 30~80 mass %.
Painting film property, the surface smoothness of liquid crystal orientation film when aligning agent for liquid crystal can be containing improvement coating of liquid crystalline alignment agent Solvent (also referred to as poor solvent).These poor solvents are preferably 1~80 matter of the whole solvents contained in aligning agent for liquid crystal Measure %, more preferable 10~80 mass %, particularly preferred 20~70 mass %.
It is exemplified below out the concrete example of poor solvent.
Ethyl alcohol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohol, 2- amylalcohol, 3- amylalcohol, 2- methyl- N-butyl alcohol, isoamyl alcohol, tert-pentyl alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1- hexanol, 2- methyl-1-pentene alcohol, 2- methyl -2- amylalcohol, 2- ethyl-n-butyl alcohol, 1-heptanol, 2- enanthol, 3- enanthol, 1- octanol, sec-n-octyl alcohol, 2- ethyl -1- hexanol, cyclohexanol, 1- methyl Cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2- ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,5- pentanediol, 2- methyl -2,4-PD, 2- ethyl -1,3- oneself two Alcohol, dipropyl ether, dibutyl ethers, hexyl ether, dioxanes, ethylene glycol dimethyl ether, ethylene glycol Anaesthetie Ether, two fourth of ethylene glycol Base ether, 1,2- butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol (DEG) methyl ethyl ether, two fourth of diethylene glycol (DEG) Base ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4- heptanone, 3- ethoxybutyl acetic acid esters, 1- methyl amyl acetic acid esters, 2- ethyl-butyl acetic acid esters, 2- ethylhexyl acetate, ethylene glycol acetate, ethylene acetate, propylene carbonate, carbon Sour ethyl, 2- (methoxymethoxy) ethyl alcohol, ethylene glycol monobutyl ether, ethylene glycol list isoamyl ether, ethylene glycol mono hexyl ether, 2- (hexyloxy) ethyl alcohol, furfuryl alcohol, diethylene glycol (DEG), propylene glycol, glycol monobutyl ether, 1- (Butoxyethoxy) propyl alcohol, propylene glycol Monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, a contracting two Propylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, second Glycol monobutyl ether acetate, ethylene glycol acetate, ethylene acetate, diethylene glycol monoethyl ether acetate, diethylene glycol (DEG) Monobutyl ether acetate, 2- (2- ethoxy ethoxy) ethylhexoate, diethylene glycol (DEG) acetic acid esters, triethylene glycol, triethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list Ethylether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxy propyl Acetoacetic ester, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, methyl lactate, Ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate or previously described formula [D-1]~formula [D-3].
Wherein, preferably 1- hexanol, cyclohexanol, 1,2- ethylene glycol, 1,2-PD, glycol monobutyl ether, ethylene glycol Single-butyl ether or dipropylene glycol dimethyl.
In aligning agent for liquid crystal of the invention, preferably importing has epoxy group, isocyanate group, oxetanyl or ring carbon The cross-linked compound of perester radical, with select free hydroxyl, hydroxy alkyl and low-grade alkoxy alkyl composition group at least 1 Plant the cross-linked compound of substituent group or the cross-linked compound with polyunsaturated bond.These substituent groups, polymerism There are 2 or more in cross-linked compound for unsaturated bond needs.
As the cross-linked compound with epoxy group or isocyanate group, such as bisphenol acetone glycidol can be enumerated Ether (bisphenol acetone glycidyl ether), phenol novolac epoxy resins, cresol novolak epoxy tree Rouge, triglycidyl group isocyanuric acid ester, four glycidyl group aminobphenyl, four glycidyl group m-xylene diamine, four are shunk Bis- (amino-ethyl) hexamethylenes of glyceryl -1,3-, tetraphenyl glycidol ether ethane, trisphenyl glycidyl ether ethane, bis-phenol Hexafluoro acetyl group diglycidyl ether, 1,3- bis- (1- (2,3- glycidoxy) -1- trifluoromethyl -2,2,2- trifluoromethyls) Bis- (2,3- glycidoxy) octafluorobiphenyls of benzene, 4,4-, triglycidyl group para-aminophenol, four glycidyl group isophthalic diformazan Amine, 2- (4- (2,3- glycidoxy) phenyl) -2- (4- (bis- (4- (2,3- glycidoxy) phenyl) ethyls of 1,1-) phenyl) Propane or bis- (4- (1- (4- (2,3- glycidoxy) phenyl) -1- (4- (1- (4- (2,3- glycidoxy) benzene of 1,3- Base) -1- Methylethyl) phenyl) ethyl) phenoxy group) -2- propyl alcohol etc..
Cross-linked compound with oxetanyl is with oxetanes shown at least two following formula [4A] The compound of base.
Specifically, the 58~59 of International Publication bulletin No. WO2011/132751 (2011.10.27 is disclosed) can be enumerated Cross-linked compound shown in formula [4a]~formula [4k] disclosed in page.
As the cross-linked compound with cyclocarbonate radical, for cyclic carbonate ester shown at least two following formula [5A] The cross-linked compound of base.
Specifically, page 76~82 of International Publication bulletin No. WO2012/014898 (2012.2.2 is disclosed) can be enumerated Cross-linked compound shown in disclosed formula [5-1]~formula [5-42].
It, can as the cross-linked compound at least one kind of substituent group in the group for selecting free hydroxyl and alkoxy to form Enumerate amino resins, such as melamine resin, urea resin, guanamine resin, the glycoluril-for example with hydroxyl or alkoxy Formaldehyde resin, succinyl amine-formaldehyde resin or ethylene urea-formaldehyde resins etc..Specifically, the hydrogen that amino can be used is former Melamine derivative made of son is replaced by methylol or alkoxy methyl or the two, benzoguanamine derivative or sweet Urea.The melamine derivative or benzoguanamine derivative can also exist in the form of dimer or tripolymer.They are preferably Every 1 triazine ring has average 3 or more and 6 methylols or alkoxy methyl below.
As above-mentioned melamine derivative or the example of benzoguanamine derivative, every 1 three of commercially available product can be enumerated Piperazine ring, which replaces the MX-750 for having average 3.7 methoxies, every 1 triazine ring to replace, average 5.8 methoxies MW-30 (the above are Sanwa Chemical Co., Ltd's systems), CYMEL 300,301,303,350,370,771,325,327,703,712 Etc. methoxymethylated melamine；The methoxymethylated butoxymethyl such as CYMEL235,236,238,212,253,254 Melamine；The butoxymethyls melamine such as CYMEL506,508；The carboxylic methoxy methyl of CYMEL 1141 etc Base isobutoxymethyl melamine；The methoxymethylated ethoxyl methyl benzoguanamine of CYMEL 1123 etc； The methoxymethylated butoxymethyl benzoguanamine of CYMEL 1123-10 etc；The butoxy first of CYMEL 1128 etc Base benzoguanamine；CYMEL 1125-80 etc carboxylic methoxymethylated ethoxyl methyl benzoguanamine (more than For Mitsui Cyanamid Ltd. system).
In addition, the example as glycoluril, can enumerate butoxymethyl glycoluril, the CYMEL of CYMEL 1170 etc Methoxyl group methylolation glycoluril of 1172 etc methylolation glycoluril etc., Powder link 1174 etc etc..
As benzene or phenoloid with hydroxyl or alkoxy, such as 1,3,5- tri- (methoxy) can be enumerated Benzene, 1,2,4- tri- (i-propoxymethyl) benzene, bis- (sec-butoxymethyl) benzene of 1,4- or 2,6- bishydroxymethyl are to tert-butyl benzene Phenol etc..
More specifically, can enumerate International Publication bulletin No. WO2011/132751 (2011.10.27 is disclosed) 62~ Formula [6-1] disclosed in page 66~formula [6-48] cross-linked compound.
As the cross-linked compound with polyunsaturated bond, such as trimethylolpropane tris (methyl) can be enumerated Acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) acryloyl-oxies The intramoleculars such as base oxethyl trimethylolpropane or more (methyl) acrylate of glycerol polyglycidyl ether have 3 polymerisms not The cross-linked compound of saturated group；And ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, Tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, poly- third Glycol two (methyl) acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene oxide Bisphenol A-type two (methyl) acrylate, propylene oxide bisphenol type two (methyl) acrylate, 1,6-HD two (methyl) propylene Acid esters, glycerol two (methyl) acrylate, pentaerythrite two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) Acrylate, diethylene glycol diglycidyl glycerin ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) The intramoleculars such as acrylate or hydroxy new pentane acid neopentyl glycol two (methyl) acrylate have 2 polymerism unsaturated groups Cross-linked compound；And (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 2- phenoxy group -2- hydroxy propyl ester, 2- (methyl) acryloxy -2- hydroxypropyl neighbour's benzene Dicarboxylic acid esters, (methyl) acrylic acid 3- chlorine-2-hydroxyl propyl ester, glycerol list (methyl) acrylate, 2- (methyl) acryloxy The intramoleculars such as ethyl phosphonic acid ester or N- methylol (methyl) acrylamide have the bridging property chemical combination of 1 polymerism unsaturated group Object etc..
In turn, following formula [7A] compound represented also can be used.
(in formula [7A], E1Indicate selected from by cyclohexane ring, bis cyclohexane ring, phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus, Group in the group of fluorenes ring, anthracene nucleus and phenanthrene ring composition, E2Group of the expression in following formula [7a] or formula [7b], n expression 1~ 4 integer).
Above compound is an example of cross-linked compound, but is not limited to them.In addition, used in aligning agent for liquid crystal Cross-linked compound can be a kind, can also combine two or more.
The content of cross-linked compound in aligning agent for liquid crystal is preferably relative to whole 100 mass parts of component of polymer 0.1~150 mass parts.Wherein, target effect is shown in order to promote cross-linking reaction, relative to whole component of polymer 100 mass parts, preferably 0.1~100 mass parts.More preferably 1~50 mass parts.
The uniform film thickness of liquid crystal orientation film when improving coating of liquid crystalline alignment agent can be used in aligning agent for liquid crystal of the invention The compound of property, surface smoothness.
As the film thickness uniformity of liquid crystal orientation film, the compound of surface smoothness is improved, it is living that fluorine system surface can be enumerated Property agent, silicone based surfactants, nonionic surfactants etc..
More specifically, can enumerate such as Eftop EF301, EF303, EF352 (more than, Tohkem products Corporation system)；Megafac F171, F173, R-30 (more than, big Japanese ink Co. Ltd. system)；Fluorad FC430, FC431 (more than, Sumitomo 3M Limited system)；AsahiGuard AG710,Surflon S-382,SC101, SC102, SC103, SC104, SC105, SC106 (more than, Asahi Glass Co., Ltd's system) etc..
The dosage of surfactant is preferably relative to 100 mass parts of whole component of polymer contained in aligning agent for liquid crystal 0.01~2 mass parts, more preferable 0.01~1 mass parts.
In turn, in aligning agent for liquid crystal, as the charge movement promoted in liquid crystal orientation film, the chemical combination for promoting element to take off charge Object can also add formula disclosed in page 69~73 of International Publication bulletin No. WO2011/132751 (2011.10.27 is disclosed) Nitrogen-containing heterocycle amine compounds shown in [M1]~formula [M156].The amine compounds can be added directly in aligning agent for liquid crystal, but It is to be added again after being preferably made the solution that concentration is 0.1~10 mass %, preferably 1~7 mass %.If solvent dissolution is specific poly- Object (A) is closed to be not particularly limited.
In aligning agent for liquid crystal of the invention, in addition to above-mentioned poor solvent, cross-linked compound, improve resin coating or liquid crystal Except the compound of the film thickness uniformity of alignment films, the compound of surface smoothness and the de- charge of promotion, as long as not damaging In the range of effect of the present invention, then the polymer in addition to the polymer recorded in the present invention can also be added, take for improving To the silane coupling agent of the adaptation of film and substrate and for heating utilizing for polyimide precursor when film to be burnt into The imidizate promotor etc. that the imidizate of progress is effectively performed.
<liquid crystal orientation film/liquid crystal indicates element>
Liquid crystal orientation film is film obtained from being coated on substrate by above-mentioned aligning agent for liquid crystal and be dried, be burnt into.As It is coated with the substrate of aligning agent for liquid crystal of the invention, is not particularly limited if the high substrate of the transparency, glass also can be used While substrate, silicon nitride board, plastic bases such as acrylic compounds substrate, polycarbonate substrate etc. are used.At this point, from technique letter , it is preferable to use being formed with the substrate of ITO electrode for driving liquid crystal etc. from the viewpoint of change.In addition, the liquid crystal watch of reflection-type Show in element, if only side substrate, even the opaque materials such as Silicon Wafer also can be used, electrode at this time also be can be used The material of the reflected lights such as aluminium.
The coating method of aligning agent for liquid crystal is not particularly limited, industrial is usually to utilize silk-screen printing, graph The method of the progress such as brush, flexible printing or ink-jet method.As other coating methods, have infusion process, rolling method, slot coated method, Spin-coating method or spray coating method etc. can use these methods according to purpose.
After aligning agent for liquid crystal is coated on substrate, heating plate, thermal cycle type baking oven or IR (infrared ray) type baking oven are utilized Etc. heating meanss, evaporate solvent, so as to which liquid crystal orientation film is made.Drying after being coated with aligning agent for liquid crystal of the invention, Firing process can choose arbitrary temperature and time.Generally for the contained solvent of abundant removal, can enumerate 50~ The condition be burnt into 1~10 minute at 120 DEG C, be then burnt into 5~120 minutes at 150~300 DEG C.Liquid crystal aligning after firing The thickness of film liquid crystal if excessively thin indicates that the reliability of element reduces sometimes, thus preferably 5~300nm, it is more preferable 10~ 200nm。
The method for carrying out orientation process for the liquid crystal orientation film obtained by aligning agent for liquid crystal of the invention can be friction Facture, it is preferred that being light orientation position logos.As the preference of light orientation position logos, it can enumerate and foregoing liquid crystal is orientated Film surface irradiate to certain orientation deflect radiation, as needed preferably 150~250 DEG C at a temperature of carry out at heating Reason, the method for assigning liquid crystal aligning (also referred to as liquid crystal aligning ability).As radiation, can be used with 100~800nm Wavelength ultraviolet light or luminous ray.Wherein, it is however preferred to have 100~400nm, more preferable 200~400nm wavelength purple Outside line.
In addition, in order to improve liquid crystal aligning, can substrate to film liquid crystal orientation film on one side at 50~250 DEG C into Row heating one side illumination radiation line.In addition, the exposure of aforementioned radiation line is preferably 1~10000mJ/cm2, it is more preferable 100~ 5000mJ/cm2.Liquid crystal molecule can be made steadily to be orientated on certain direction using this liquid crystal orientation film made.
The extinction ratio of polarized UV rays is higher, can assign higher anisotropy, it is advantageous to.Specifically, with straight line The extinction ratio of the ultraviolet light of polarization is preferably 10:1 or more, more preferable 20:1 or more.
In turn, in preceding method, for having irradiated the liquid crystal orientation film of polarized radiation line, also can be used water, solvent into Row contact treatment.
As solvent used in above-mentioned contact treatment, if what will be generated by irradiation with radiation by liquid crystal orientation film The solvent of decomposition product dissolution, is not particularly limited.As concrete example, can enumerate water outlet, methanol, ethyl alcohol, 2- propyl alcohol, acetone, It is methyl ethyl ketone, 1- methoxy-2-propanol, 1- methoxy-2-propanol acetic acid esters, butyl cellosolve, ethyl lactate, methyl lactate, double Pyruvic alcohol, 3- methoxy methyl propionate, 3- ethoxyl ethyl propionate, propyl acetate, butyl acetate or cyclohexyl acetate etc..Its In, from versatility, solvent safety from the viewpoint of, preferably water, 2- propyl alcohol, 1- methoxy-2-propanol or ethyl lactate, More preferable water, 1- methoxy-2-propanol or ethyl lactate.Solvent can be two or more for a kind of or combination.
As above-mentioned contact treatment, that is, the place that liquid crystal orientation film water, solvent for having irradiated polarized radiation line carry out Reason can enumerate impregnation, spraying (spray) processing.These processing in time from effectively dissolution by radiation by From the viewpoint of the decomposition product that liquid crystal orientation film generates, preferably 10 seconds~1 hour, preferably carry out impregnating for 1 minute~30 minutes Processing.In addition, solvent when contact treatment can be room temperature or heating, it is preferred that for 10~80 DEG C, wherein preferably 20~50 ℃.Also, from the viewpoint of the dissolubility of decomposition product, ultrasonication etc. can be carried out as needed.
After aforementioned contact processing, preferably carry out utilizing the low boiling points such as water, methanol, ethyl alcohol, 2- propyl alcohol, acetone or methyl ethyl ketone The firing of rinsing (also referred to as rinsing), liquid crystal orientation film that solvent carries out.At this point it is possible to any one in being rinsed and being burnt into Person or both.Firing temperature is preferably 150~300 DEG C, 180~250 DEG C more preferable, 200~230 DEG C particularly preferred.When firing Between preferably 10 seconds~30 minutes, it is 1~10 minute more preferable.
Liquid crystal orientation film of the invention indicates the liquid of element as the liquid crystal of the Transverse electric-field types such as IPS mode, FFS mode Brilliant alignment films are suitably, to indicate that element is useful especially for the liquid crystal of FFS mode.Liquid crystal indicate element obtain band by After the substrate for the liquid crystal orientation film that aligning agent for liquid crystal of the invention obtains, liquid crystal cells are made by known method, use the liquid Brilliant unit obtains.
As an example of liquid crystal cells production method, the liquid crystal expression element of passive-matrix structure is carried out as an example Explanation.It should be noted that or being provided with TFT (thin film transistor (TFT) (Thin in each pixel portion for constituting image expression Film Transistor)) etc. the active matrix structure of switch elements liquid crystal indicate element.
Specifically, preparing the substrate of transparent glass system, public electrode is set on one substrate, on another substrate Segment electrode is set.These electrodes can for example form ITO electrode, the formation figure in a manner of it can carry out desired image and indicate Case.Then, on each substrate, insulating film is set in a manner of covering public electrode and segment electrode.Insulating film such as can be logical Cross the SiO of sol-gel method formation2-TiO2Film.
Then, liquid crystal orientation film is formed on each substrate, it is opposed with mutual liquid crystal alignment film surface on one substrate Mode is overlapped another substrate, and periphery is bonded with sealant.In sealant, for control base board gap, it is ordinarily incorporated into spacer, In addition, in the face inner part for being not provided with sealant it is also preferred that spreading the spacer of substrate gap control.The one of sealant Part setting can be by the opening portion of external filling liquid crystal.
Then, by being set to the opening portion of sealant, liquid is injected into the space surrounded by two pieces of substrates and sealant Then brilliant material seals the opening portion with bonding agent.Vacuum impregnation can be used in injection, also can be used sharp in an atmosphere With the method for capillarity.Positive type liquid crystal material, any one in negative type liquid crystal material can be used in liquid crystal material, still Preferably negative type liquid crystal material.Then, the setting of polarizer is carried out.Specifically, in two pieces of substrates being opposite with liquid crystal layer Paste a pair of of polarizer in the face of side.
It is residual caused by capable of being inhibited exchange driving as described above by using aligning agent for liquid crystal of the invention Shadow and have both sealant and underlying substrate adaptation liquid crystal orientation film.It is obtained especially for irradiation polarized radiation line To the liquid crystal orientation films of light orientation position logos be useful.
Embodiment
It is exemplified below out embodiment the present invention is described in more detail, but the present invention is not limited by them, explained.
The abbreviation of compound used in below and measuring method are as described below.
NMP:N- N-methyl-2-2-pyrrolidone N
BCS: butyl cellosolve
Bis- (4- amino-benzene oxygen) ethane of DA-1:1,2-
Bis- (4- amino-benzene oxygen) propane of DA-2:1,3-
DA-3: p-phenylenediamine
DA-6:4- (2- (methylamino) ethyl) aniline
[viscosity]
For the viscosity of poly amic acid ester and polyamic acid solution, E type viscosimeter TVE-22H (eastern machine industry strain formula is used Commercial firm's system), it is measured under conditions of sample size 1.1mL, taper shaft TE-1 (1 ° 34 ', R24), 25 DEG C of temperature.
[molecular weight]
The molecular weight of poly amic acid ester is measured using GPC (room temperature gel permeation chromatography) device, as polyethylene glycol, polycyclic Oxidative ethane scaled value calculates number-average molecular weight (hereinafter also referred to Mn) and weight average molecular weight (hereinafter also referred to Mw).
GPC device: Shodex corporation (GPC-101)
Column: Shodex corporation (series connection of KD803, KD805)
Column temperature: 50 DEG C
Eluent: n,N-Dimethylformamide is (as additive, lithium bromide monohydrate (LiBrH2It O) is 30 mmoles That/L, phosphoric acid anhydrous crystal (orthophosphoric acid) are 30 mMs/L, tetrahydrofuran (THF) is 10ml/L)
Flow velocity: 1.0ml/ minutes
Standard curve is made with standard sample: TOSOH CORPORATION TSK standard polyethylene oxide (Weight-average molecular Measure (Mw) about 900000,150000,100000,30000) and Polymer Laboratories Ltd. polyethylene glycol (peak It is worth molecular weight (Mp) about 12000,4000,1000).For measurement, in order to avoid overlap of peaks, measure 900000 respectively, 100000, 12000,1,000 four kinds of samples mixed and 150000,30000,4000 three kinds of samples mixed this two Kind sample.
[measurement of acid imide rate]
Polyimide powder 20mg is added in NMR sample cell (NMR samples pipe standards, φ 5 (wasteland section length of schooling)), is added Add deuterated dimethyl sulfoxide (DMSO-d6,0.05%TMS (tetramethylsilane) melange) (0.53ml), it is complete to apply ultrasonic wave Dissolution.For the solution, the proton of NMR analyzer (JNW-ECA500) (JEOL DATUM Ltd. system) measurement 500MHz is utilized NMR.It is for acid imide rate, the proton for being originated from the structure not changed before and after imidizate is true as reference proton It is fixed, the proton peak of the NH base from amic acid occurred using the peak accumulated value of the proton and near 9.5ppm~10.0ppm Accumulated value is found out by following formula.
Acid imide rate (%)=(1- α x/y) × 100
In above-mentioned formula, x is for peak accumulated value, the α that proton peak accumulated value, the y of the NH base from amic acid are benchmark proton The number ratio of NH matrix son 1 reference proton relative to amic acid when polyamic acid (acid imide rate is 0%).
[anisotropy of alignment films]
Use liquid crystal orientation film evaluation system " LayScan-Labo H " (LYS- of MORITEX Corporation LH30S-1A it) is measured.Ultraviolet light is irradiated by polarizer for the polyimide film of film thickness 100nm, is measured for gained The anisotropic size of the differently- oriented directivity of the alignment films arrived.
[production of liquid crystal cells]
Production, which has boundary electric field switching (Fringe Field Switching:FFS) mode liquid crystal, indicates the knot of element The liquid crystal cells of structure.
Prepare electroded substrate first.The 1st layer of shape is used as on the glass substrate for indulging 30mm, horizontal 0mm, thickness 0.7mm At the ITO electrode for having the pattern of shape on the spot for constituting opposite electrode.On the 1st layer of opposite electrode, as the 2nd layer, shape At SiN (silicon nitride) film using CVD method film forming.The film thickness of 2nd layer of SiN film is 500nm, plays function as interlayer dielectric Energy.On the 2nd layer of SiN film, as the 3rd layer, ito film is patterned the pixel electrode for the comb teeth-shaped to be formed by configuration, forms the 1st Pixel and the 2nd pixel both pixels.The size of each pixel is vertical 10mm, horizontal about 5mm.1st layer of opposite electrode and the 3rd at this time The pixel electrode of layer is electrically insulated by the effect of the 2nd layer of SiN film.
3rd layer of pixel electrode has the multiple comb teeth being arranged to make up of electrode member of the curved く word shape of center portion The shape of shape.The width of the width direction of each electrode member between 3 μm, electrode member between be divided into 6 μm.Form each pixel Pixel electrode, which is that the electrode member of the curved く word shape of center portion is multiple, to be arranged to make up, therefore the shape of each pixel is not grown Square shape has the shape similar to " く word " of the curved too word of center portion in the same manner as electrode member.And each pixel will The bending part in its center is divided into up and down as boundary line, the 1st region of the upside with bending part and the 2nd region of downside.
The formation side of the electrode member of their pixel electrode is constituted if the 1st region of more each pixel and the 2nd region To difference.That is, in the case that the frictional direction of aftermentioned liquid crystal orientation film is as benchmark, in the 1st region of pixel, with pixel electricity The mode that the electrode member of pole forms+10 ° of angle (rotating clockwise) is formed, in the 2nd region of pixel, with pixel electrode The mode that electrode member forms -10 ° of angle (rotating clockwise) is formed.That is, in the 1st region of each pixel and the 2nd region, with The spinning movement applied in the real estate of the liquid crystal induced by the voltage between pixel electrode and opposite electrode is (coplanar to open Close) direction be mutual opposite direction mode constitute.
Then by after 1.0 μm of the filter filtering of obtained aligning agent for liquid crystal, using spin application in being prepared The glass substrate of above-mentioned electroded substrate and the columnar spacer with 4 μm of height for the ito film that overleaf forms a film.At 80 DEG C Heating plate on it is dry after five minutes, be burnt within 20 minutes using 230 DEG C of heated air circulation type baking ovens, form film thickness 100nm's Film.For the coated surface by the ultraviolet light of the wavelength 254nm of the linear polarization of polarizer irradiation extinction ratio 10:1 or more.It will The substrate is impregnated in selected from least one of water and organic solvent solvent 3 minutes, is then impregnated in pure water 1 minute, at 150 DEG C It is heated 5 minutes in~300 DEG C of heating plate, obtains the substrate with liquid crystal orientation film.Using above-mentioned 2 pieces of substrates as one group, in base Printing and sealing agent on plate, make 0 ° of liquid crystal alignment film surface relative orientation direction making sealant cures after being bonded another substrate and Make dummy cell.Decompression injection method injection liquid crystal MLC-7026-100 (Merck Ltd. system), sealing note are utilized to the dummy cell Entrance obtains FFS driving liquid crystal cells.Then obtained liquid crystal cells are heated 1 hour at 110 DEG C, after placing a Dinner For each evaluation.
[the ghost evaluation caused by exchanging driving for a long time]
Prepare the liquid crystal cells with liquid crystal cells same structure used in the evaluation of above-mentioned ghost.
Using the liquid crystal cells, with alternating voltage 120 hours of frequency 60Hz application ± 5V under 60 DEG C of isoperibol. Then, state short-circuit between the pixel electrode of liquid crystal cells and opposite electrode is formed, is directly placed one day at room temperature.
After placement, liquid crystal cells are set between the 2 pieces of polarizers configured in the orthogonal mode of polarizing axis, not apply Alive state is by backlight lighting, with the arrangement angles through the brightness least way of light adjustment liquid crystal cells.Then Rotation angle when will rotate liquid crystal cells until the most dark angle in the 1st region by the most dark angle in the 2nd region of the 1st pixel Degree is calculated as angle delta.2nd region is similarly compared for the 2nd pixel and the 1st region calculates same angle delta.
[evaluation (contrast) of the bright spot of liquid crystal cells]
Carry out the evaluation of the bright spot of the liquid crystal cells of above-mentioned production.The evaluation of the bright spot of liquid crystal cells, by for liquid crystal Unit is observed to carry out using petrographic microscope (ECLIPSE E600WPOL) (NIKONCORPORATION system).It is specific and Liquid crystal cells are arranged with Nicol crossed in speech, are 5 times of polarized light microscope observing liquid crystal cells with multiplying power, for really The bright spot number recognized is counted, and bright spot number is less than 10 as " good ", 10 or more as " bad ".
<synthesis example 1>
DA-1 0.81g (3.30 mMs), DA-2 are taken in the 50mL four-neck flask with agitating device and nitrogen ingress pipe NMP is added in 0.57g (2.20 mMs), DA-3 0.36g (3.30 mMs), DA-4 0.88g (2.20 mMs) 29.99g is stirred, dissolves while being sent into nitrogen.Dimethyl -1,2 1,3- are added while by diamine solution stirring, 3,4- cyclobutane tetracarboxylic dianhydride 2.35g (10.51 mMs), and then so that solid component concentration is 12 mass % to be added NMP 6.40g stirs 24 hours at room temperature, obtains polyamic acid solution (A).It is viscous at 25 DEG C of the temperature of the polyamic acid solution Degree is 316mPas.In addition, the molecular weight of the polyamic acid is Mn=13230, Mw=29550.
<synthesis example 2>
DA-1 0.54g (2.20 mMs), DA-2 are taken in the 50mL four-neck flask with agitating device and nitrogen ingress pipe NMP is added in 0.85g (3.30 mMs), DA-3 0.36g (3.30 mMs), DA-4 0.88g (2.20 mMs) 30.17g is stirred, dissolves while being sent into nitrogen.Dimethyl -1,2 1,3- are added while by diamine solution stirring, 3,4- cyclobutane tetracarboxylic dianhydride 2.35g (10.51 mMs), and then so that solid component concentration is 12 mass % to be added NMP 6.34g stirs 24 hours at room temperature, obtains polyamic acid solution (B).It is viscous at 25 DEG C of the temperature of the polyamic acid solution Degree is 356mPas.In addition, the molecular weight of the polyamic acid is Mn=14120, Mw=31210.
<synthesis example 3>
DA-1 0.88g (3.60 mMs), DA-2 are taken in the 50mL four-neck flask with agitating device and nitrogen ingress pipe NMP is added in 0.31g (1.20 mMs), DA-3 0.52g (4.80 mMs), DA-4 0.96g (2.40 mMs) 30.64g is stirred, dissolves while being sent into nitrogen.Dimethyl -1,2 1,3- are added while by diamine solution stirring, 3,4- cyclobutane tetracarboxylic dianhydride 2.57g (11.46 mMs), and then so that solid component concentration is 12 mass % to be added NMP 7.74g stirs 24 hours at room temperature, obtains polyamic acid solution (C).It is viscous at 25 DEG C of the temperature of the polyamic acid solution Degree is 336mPas.In addition, the molecular weight of the polyamic acid is Mn=13410, Mw=30110.
<synthesis example 4>
DA-1 0.54g (2.20 mMs), DA-2 are taken in the 50mL four-neck flask with agitating device and nitrogen ingress pipe NMP is added in 0.57g (2.20 mMs), DA-3 0.48g (4.40 mMs), DA-4 0.88g (2.20 mMs) 28.27g is stirred, dissolves while being sent into nitrogen.Dimethyl -1,2 1,3- are added while by diamine solution stirring, 3,4- cyclobutane tetracarboxylic dianhydride 2.35g (10.51 mMs), and then so that solid component concentration is 12 mass % to be added NMP 7.03g stirs 24 hours at room temperature, obtains polyamic acid solution (D).It is viscous at 25 DEG C of the temperature of the polyamic acid solution Degree is 366mPas.In addition, the molecular weight of the polyamic acid is Mn=14530, Mw=36150.
<synthesis example 5>
DA-1 0.95g (3.90 mMs), DA-2 are taken in the 50mL four-neck flask with agitating device and nitrogen ingress pipe NMP 26.76g is added in 0.67g (2.60 mMs), DA-3 0.70g (6.50 mMs), is stirred while being sent into nitrogen It mixes, dissolve.1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride 2.78g is added while by diamine solution stirring (12.42 mMs), and then so that solid component concentration is 12 mass % NMP 10.71g is added, stirring 24 is small at room temperature When, obtain polyamic acid solution (E).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 301mPas.In addition, this is poly- The molecular weight of amic acid is Mn=11990, Mw=25310.
<synthesis example 6>
DA-1 0.81g (3.30 mMs), DA-2 are taken in the 50mL four-neck flask with agitating device and nitrogen ingress pipe NMP is added in 0.57g (2.20 mMs), DA-3 0.36g (3.30 mMs), DA-5 0.75g (2.20 mMs) 28.55g is stirred, dissolves while being sent into nitrogen.Dimethyl -1,2 1,3- are added while by diamine solution stirring, 3,4- cyclobutane tetracarboxylic dianhydride 2.35g (10.51 mMs), and then so that solid component concentration is 12 mass % to be added NMP 6.93g stirs 24 hours at room temperature, obtains polyamic acid solution (F).It is viscous at 25 DEG C of the temperature of the polyamic acid solution Degree is 350mPas.In addition, the molecular weight of the polyamic acid is Mn=15220, Mw=31850.
<synthesis example 7>
DA-1 0.88g (3.60 mMs), DA-3 are taken in the 50mL four-neck flask with agitating device and nitrogen ingress pipe NMP 28.57g is added in 0.65g (6.00 mMs), DA-4 0.96g (2.40 mMs), is stirred while being sent into nitrogen It mixes, dissolve.1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride 2.57g is added while by diamine solution stirring (11.46 mMs), and then so that solid component concentration is that NMP 8.49g is added in 12 mass %, it stirs 24 hours at room temperature, Obtain polyamic acid solution (G).Viscosity at 25 DEG C of the temperature of the polyamic acid solution is 386mPas.In addition, the polyamide The molecular weight of acid is Mn=16530, Mw=37220.
<synthesis example 8>
DA-1 1.59g (6.50 mMs), DA-3 are taken in the 50mL four-neck flask with agitating device and nitrogen ingress pipe NMP 26.34g is added in 0.70g (6.50 mMs), is stirred, dissolves while being sent into nitrogen.The diamine solution is stirred While add 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride 2.78g (12.42 mMs), and then so that solid Constituent concentration is 12 mass % NMP 10.86g is added, and stirs 24 hours at room temperature, obtains polyamic acid solution (H).This is poly- Viscosity at 25 DEG C of the temperature of amide acid solution is 310mPas.In addition, the molecular weight of the polyamic acid is Mn=13310, Mw =26210.
<synthesis example 9>
DA-2 1.68g (6.50 mMs), DA-3 are taken in the 50mL four-neck flask with agitating device and nitrogen ingress pipe NMP 27.39g is added in 0.70g (6.50 mMs), is stirred, dissolves while being sent into nitrogen.The diamine solution is stirred While add 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride 2.78g (12.42 mMs), and then so that solid Constituent concentration is 12 mass % NMP 10.48g is added, and stirs 24 hours at room temperature, obtains polyamic acid solution (I).This is poly- Viscosity at 25 DEG C of the temperature of amide acid solution is 322mPas.In addition, the molecular weight of the polyamic acid is Mn=14430, Mw =29950.
<synthesis example 10>
DA-3 1.46g (13.50 mMs), DA-6 are taken in the 50mL four-neck flask with agitating device and nitrogen ingress pipe NMP 20.88g is added in 0.36g (1.50 mMs), is stirred, dissolves while being sent into nitrogen.The diamine solution is stirred While add 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride 3.21g (14.33 mMs), and then so that solid Constituent concentration is 12 mass % NMP 15.98g is added, and stirs 24 hours at room temperature, obtains polyamic acid solution (J).This is poly- Viscosity at 25 DEG C of the temperature of amide acid solution is 344mPas.In addition, the molecular weight of the polyamic acid is Mn=14430, Mw =34850.
<synthesis example 11>
It takes DA-1 2.69g (11.00 mMs), is added in the 50mL four-neck flask with agitating device and nitrogen ingress pipe NMP 30.90g is stirred, dissolves while being sent into nitrogen.1,3- dimethyl-is added while by diamine solution stirring 1,2,3,4- cyclobutane tetracarboxylic dianhydride 2.35g (10.51 mMs), and then so that solid component concentration is 12 mass % to add Enter NMP 6.07g, stirs 24 hours at room temperature, obtain polyamic acid solution (K).At 25 DEG C of the temperature of the polyamic acid solution Viscosity is 367mPas.In addition, the molecular weight of the polyamic acid is Mn=17110, Mw=33310.
<embodiment 1>
Polyamic acid solution (A) 15.00g of 12 mass % obtained in synthesis example 1 is taken at 100ml conical flask, is added NMP 9.00g, BCS 6.00g mix 8 hours at 25 DEG C, obtain aligning agent for liquid crystal (1).The aligning agent for liquid crystal does not find muddy Turbid, precipitation etc. is abnormal, is confirmed as uniform solution.
<embodiment 2~6>
Using polyamic acid solution (B)~(F) of the 12 mass % respectively obtained in synthesis example 2~6, in addition to this with reality It applies example 1 similarly to implement, thus obtains aligning agent for liquid crystal (2)~(6).The all muddy, precipitations without discovery of these aligning agent for liquid crystal Deng exception, it is confirmed as uniform solution.
<the Comparative Examples 1 to 5>
Using polyamic acid solution (G)~(K) of the 12 mass % respectively obtained in synthesis example 7~11, in addition to this with Embodiment 1 is similarly implemented, and aligning agent for liquid crystal (7)~(11) are thus obtained.The all muddy, analysis without discovery of these aligning agent for liquid crystal It is equal abnormal out, it is confirmed as uniform solution.
(embodiment 7)
After aligning agent for liquid crystal obtained in embodiment 1 (1) 1.0 μm of filter filtering, using spin application in The ito substrate of 30mm × 40mm.In 80 DEG C of heating plate after drying 2 minutes, 230 DEG C of heated air circulation type baking ovens is utilized to carry out It is burnt within 14 minutes, forms the film of film thickness 100nm.For the coated surface by the linear polarization of polarizer irradiation extinction ratio 26:1 Wavelength 254nm ultraviolet light, measure the anisotropic height for differently- oriented directivity of obtained liquid crystal orientation film.It is above-mentioned Ultraviolet irradiation amount is 100mJ/cm2When anisotropic value be 1.31,150mJ/cm2When anisotropic value be 3.10、200mJ/cm2When anisotropic value be 2.25.The highest above-mentioned ultraviolet irradiation amount of anisotropy is 150mJ/ cm2, as the most suitable irradiation condition in light orientation processing.
(embodiment 8)
After aligning agent for liquid crystal obtained in embodiment 2 (2) 1.0 μm of filter filtering, using spin application in The ito substrate of 30mm × 40mm.In 80 DEG C of heating plate after drying 2 minutes, 230 DEG C of heated air circulation type baking ovens is utilized to carry out It is burnt within 14 minutes, forms the film of film thickness 100nm.For the coated surface by the linear polarization of polarizer irradiation extinction ratio 26:1 Wavelength 254nm ultraviolet light, measure the anisotropic height for differently- oriented directivity of obtained liquid crystal orientation film.It is above-mentioned Ultraviolet irradiation amount is 50mJ/cm2When anisotropic value be 0.43,100mJ/cm2When anisotropic value be 3.53、150mJ/cm2When anisotropic value be 3.26.The highest above-mentioned ultraviolet irradiation amount of anisotropy is 150mJ/ cm2, as the most suitable irradiation condition in light orientation processing.
(embodiment 9)
After aligning agent for liquid crystal obtained in embodiment 3 (3) 1.0 μm of filter filtering, using spin application in The ito substrate of 30mm × 40mm.In 80 DEG C of heating plate after drying 2 minutes, 230 DEG C of heated air circulation type baking ovens is utilized to carry out It is burnt within 14 minutes, forms the film of film thickness 100nm.For the coated surface by the linear polarization of polarizer irradiation extinction ratio 26:1 Wavelength 254nm ultraviolet light, measure the anisotropic height for differently- oriented directivity of obtained liquid crystal orientation film.It is above-mentioned Ultraviolet irradiation amount is 200mJ/cm2When anisotropic value be 2.24,300mJ/cm2When anisotropic value be 3.41、400mJ/cm2When anisotropic value be 1.51.The highest above-mentioned ultraviolet irradiation amount of anisotropy is 300mJ/ cm2, as the most suitable irradiation condition in light orientation processing.
(embodiment 10)
After aligning agent for liquid crystal obtained in embodiment 4 (4) 1.0 μm of filter filtering, using spin application in The ito substrate of 30mm × 40mm.In 80 DEG C of heating plate after drying 2 minutes, 230 DEG C of heated air circulation type baking ovens is utilized to carry out It is burnt within 14 minutes, forms the film of film thickness 100nm.For the coated surface by the linear polarization of polarizer irradiation extinction ratio 26:1 Wavelength 254nm ultraviolet light, measure the anisotropic height for differently- oriented directivity of obtained liquid crystal orientation film.It is above-mentioned Ultraviolet irradiation amount is 100mJ/cm2When anisotropic value be 1.15,200mJ/cm2When anisotropic value be 2.30、300mJ/cm2When anisotropic value be 2.26.The highest above-mentioned ultraviolet irradiation amount of anisotropy is 200mJ/ cm2, as the most suitable irradiation condition in light orientation processing.
(embodiment 11)
After aligning agent for liquid crystal obtained in embodiment 5 (5) 1.0 μm of filter filtering, using spin application in The ito substrate of 30mm × 40mm.In 80 DEG C of heating plate after drying 2 minutes, 230 DEG C of heated air circulation type baking ovens is utilized to carry out It is burnt within 14 minutes, forms the film of film thickness 100nm.For the coated surface by the linear polarization of polarizer irradiation extinction ratio 26:1 Wavelength 254nm ultraviolet light, measure the anisotropic height for differently- oriented directivity of obtained liquid crystal orientation film.It is above-mentioned Ultraviolet irradiation amount is 100mJ/cm2When anisotropic value be 4.29,150mJ/cm2When anisotropic value be 5.23、200mJ/cm2When anisotropic value be 3.00.The highest above-mentioned ultraviolet irradiation amount of anisotropy is 150mJ/ cm2, as the most suitable irradiation condition in light orientation processing.
(embodiment 12)
After aligning agent for liquid crystal obtained in embodiment 6 (6) 1.0 μm of filter filtering, using spin application in The ito substrate of 30mm × 40mm.In 80 DEG C of heating plate after drying 2 minutes, 230 DEG C of heated air circulation type baking ovens is utilized to carry out It is burnt within 14 minutes, forms the film of film thickness 100nm.For the coated surface by the linear polarization of polarizer irradiation extinction ratio 26:1 Wavelength 254nm ultraviolet light, measure the anisotropic height for differently- oriented directivity of obtained liquid crystal orientation film.It is above-mentioned Ultraviolet irradiation amount is 100mJ/cm2When anisotropic value be 2.76,150mJ/cm2When anisotropic value be 4.87、200mJ/cm2When anisotropic value be 4.01.The highest above-mentioned ultraviolet irradiation amount of anisotropy is 150mJ/ cm2, as the most suitable irradiation condition in light orientation processing.
(comparative example 6)
After aligning agent for liquid crystal obtained in comparative example 1 (7) 1.0 μm of filter filtering, using spin application in The ito substrate of 30mm × 40mm.In 80 DEG C of heating plate after drying 2 minutes, 230 DEG C of heated air circulation type baking ovens is utilized to carry out It is burnt within 14 minutes, forms the film of film thickness 100nm.For the coated surface by the linear polarization of polarizer irradiation extinction ratio 26:1 Wavelength 254nm ultraviolet light, measure the anisotropic height for differently- oriented directivity of obtained liquid crystal orientation film.It is above-mentioned Ultraviolet irradiation amount is 100mJ/cm2When anisotropic value be 2.02,200mJ/cm2When anisotropic value be 2.87、300mJ/cm2When anisotropic value be 2.51.The maximum above-mentioned ultraviolet irradiation amount of anisotropy is 200mJ/ cm2, as the most suitable irradiation condition in light orientation processing.
(comparative example 7)
After aligning agent for liquid crystal obtained in comparative example 2 (8) 1.0 μm of filter filtering, using spin application in The ito substrate of 30mm × 40mm.In 80 DEG C of heating plate after drying 2 minutes, 230 DEG C of heated air circulation type baking ovens is utilized to carry out It is burnt within 14 minutes, forms the film of film thickness 100nm.For the coated surface by the linear polarization of polarizer irradiation extinction ratio 26:1 Wavelength 254nm ultraviolet light, measure the anisotropic height for differently- oriented directivity of obtained liquid crystal orientation film.It is above-mentioned Ultraviolet irradiation amount is 100mJ/cm2When anisotropic value be 5.02,150mJ/cm2When anisotropic value be 7.37、200mJ/cm2When anisotropic value be 6.40.The maximum above-mentioned ultraviolet irradiation amount of anisotropy is 150mJ/ cm2, as the most suitable irradiation condition in light orientation processing.
(comparative example 8)
After aligning agent for liquid crystal obtained in comparative example 3 (9) 1.0 μm of filter filtering, using spin application in The ito substrate of 30mm × 40mm.In 80 DEG C of heating plate after drying 2 minutes, 230 DEG C of heated air circulation type baking ovens is utilized to carry out It is burnt within 14 minutes, forms the film of film thickness 100nm.For the coated surface by the linear polarization of polarizer irradiation extinction ratio 26:1 Wavelength 254nm ultraviolet light, measure the anisotropic height for differently- oriented directivity of obtained liquid crystal orientation film.It is above-mentioned Ultraviolet irradiation amount is 50mJ/cm2When anisotropic value be 4.11,100mJ/cm2When anisotropic value be 5.78、150mJ/cm2When anisotropic value be 4.55.The maximum above-mentioned ultraviolet irradiation amount of anisotropy is 100mJ/ cm2, as the most suitable irradiation condition in light orientation processing.
(comparative example 9)
After aligning agent for liquid crystal obtained in comparative example 4 (10) 1.0 μm of filter filtering, using spin application in The ito substrate of 30mm × 40mm.In 80 DEG C of heating plate after drying 2 minutes, 230 DEG C of heated air circulation type baking ovens is utilized to carry out It is burnt within 14 minutes, forms the film of film thickness 100nm.For the coated surface by the linear polarization of polarizer irradiation extinction ratio 26:1 Wavelength 254nm ultraviolet light, measure the anisotropic height for differently- oriented directivity of obtained liquid crystal orientation film.It is above-mentioned Ultraviolet irradiation amount is 400mJ/cm2When anisotropic value be 1.60,600mJ/cm2When anisotropic value be 1.78、800mJ/cm2When anisotropic value be 1.33.The maximum above-mentioned ultraviolet irradiation amount of anisotropy is 600mJ/ cm2, as the most suitable irradiation condition in light orientation processing.
(comparative example 10)
After aligning agent for liquid crystal obtained in comparative example 5 (11) 1.0 μm of filter filtering, using spin application in The ito substrate of 30mm × 40mm.In 80 DEG C of heating plate after drying 2 minutes, 230 DEG C of heated air circulation type baking ovens is utilized to carry out It is burnt within 14 minutes, forms the film of film thickness 100nm.For the coated surface by the linear polarization of polarizer irradiation extinction ratio 26:1 Wavelength 254nm ultraviolet light, measure the anisotropic height for differently- oriented directivity of obtained liquid crystal orientation film.It is above-mentioned Ultraviolet irradiation amount is 50mJ/cm2When anisotropic value be 5.54,100mJ/cm2When anisotropic value be 7.34、200mJ/cm2When anisotropic value be 6.40.The maximum above-mentioned ultraviolet irradiation amount of anisotropy is 100mJ/ cm2, as the most suitable irradiation condition in light orientation processing.
(embodiment 13)
After 1.0 μm of filter filtering of aligning agent for liquid crystal obtained in embodiment 1 (1), using spin application in institute The glass substrate of the columnar spacer with 4 μm of height of the above-mentioned electroded substrate and the ito film that overleaf forms a film that prepare. Drying after five minutes, utilizes 230 DEG C of heated air circulation type baking ovens be burnt within 20 minutes, forms film thickness in 80 DEG C of heating plate The film of 100nm.For the coated surface by the ultraviolet light of the wavelength 254nm of the linear polarization of polarizer irradiation extinction ratio 26:1 150mJ/cm2Afterwards, it is heated 14 minutes in 230 DEG C of heating plate, obtains the substrate with liquid crystal orientation film.By above-mentioned 2 pieces of substrates As one group, the printing and sealing agent on substrate makes 0 ° of liquid crystal alignment film surface relative orientation direction to make after being bonded another substrate Sealant cures and make dummy cell.Liquid crystal MLC-7026-100 (Merck is injected using decompression injection method to the dummy cell Ltd. make), inlet is sealed, FFS driving liquid crystal cells are obtained.Then obtained liquid crystal cells are heated to 1 at 110 DEG C small When, it places a Dinner and implements the ghost evaluation caused by exchanging driving for a long time.The liquid crystal cells after driving are exchanged for a long time The value of angle delta is 0.08 degree.In addition, carry out the bright spot observation in unit, as a result bright spot number less than 10, it is good.
(embodiment 14)
For aligning agent for liquid crystal obtained in embodiment 1 (1), after irradiating polarized UV rays, be impregnated in 2- propyl alcohol 3 minutes, Then it is impregnated in pure water 1 minute, in addition to this utilizes method production FFS driving liquid crystal cells identical with embodiment 13.For The FFS drives liquid crystal cells, implements the ghost evaluation caused by exchanging driving for a long time.The liquid crystal after long-term exchange driving The value of the angle delta of unit is 0.10 degree.In addition, carry out the bright spot observation in unit, as a result bright spot number less than 10, it is good.
(embodiment 15~19)
Respectively using aligning agent for liquid crystal (2)~(6) obtained in embodiment 2~6, in addition to this utilize and 13 phase of embodiment Same method forms each film of film thickness 100nm.For these each coated surfaces by polarizer respectively to be shone shown in following table 1 The amount of penetrating (unit: mJ/cm2) irradiation extinction ratio 26:1 linear polarization wavelength 254nm ultraviolet light, in addition to this with embodiment 13 similarly make the substrate with liquid crystal orientation film, then make each FFS driving liquid crystal cells, implement due to exchanging driving for a long time Caused ghost evaluation.The value of the angle delta of each liquid crystal cells after long-term exchange driving, the bright spot carried out in unit are observed The results are shown in Table 1.It is evaluated as it should be noted that bright spot number is evaluated as good, bright spot number less than 10 for 10 or more It is bad.
(comparative example 11~15)
Respectively using aligning agent for liquid crystal (7)~(11) obtained in the Comparative Examples 1 to 5, in addition to this utilize and embodiment 13 Identical method forms each film of film thickness 100nm.For these each coated surfaces by polarizer respectively shown in following table 1 Exposure (unit: mJ/cm2) irradiation extinction ratio 26:1 linear polarization wavelength 254nm ultraviolet light, in addition to this with implementation Example 13 similarly makes the substrate with liquid crystal orientation film, then makes each FFS driving liquid crystal cells, implements due to exchanging drive for a long time Ghost evaluation caused by moving.The value of the angle delta of each liquid crystal cells after long-term exchange driving, the bright spot carried out in unit are seen Examine that the results are shown in Table 1.It is evaluated it should be noted that bright spot number is evaluated as good, bright spot number less than 10 for 10 or more It is bad.
[table 1]
Industrial availability
Aligning agent for liquid crystal through the invention, it is available in the case where using negative type liquid crystal, will not generate by Bright spot caused by the decomposition product from liquid crystal orientation film generated when light orientation processing, the liquid with good image retention speciality Brilliant alignment films.The main reason for liquid crystal orientation film obtained as a result, by aligning agent for liquid crystal of the invention, degree reduces as a comparison Bright spot is few, and can reduce IPS driving method, FFS driving method liquid crystal indicate element in generate due to exchange drive Caused ghost obtains the excellent IPS driving method of image retention speciality, the liquid crystal of FFS driving method indicates element.It therefore can It is used in and the high liquid crystal for indicating quality is required to indicate element.

Claims (12)

1. a kind of aligning agent for liquid crystal, which is characterized in that it contains selected from as with knot shown in following formula (1) and following formula (2) The polymerization of at least one of the group that the polyimide precursor of structure unit and the imide amination polymer of the polyimide precursor form Object (A),
In formula (1), formula (2), X1And X2It is 4 valence organic groups, R each independently1And R2It is hydrogen atom or carbon number each independently 1~4 alkyl, A1、A2、A3、A4It is the alkyl of hydrogen atom or carbon number 1~4, Z each independently1、Z2、Z3And Z4It is respectively independent Ground is the alkyl of hydrogen atom, halogen atom and carbon number 1~4, the integer that n is 1~4.
2. aligning agent for liquid crystal according to claim 1, wherein the containing ratio phase of structural unit shown in the formula (1) 1 mole of entire infrastructure unit for the polymer (A) is 10~50 moles of %, structural unit shown in the formula (2) Containing ratio is 20~90 moles of % relative to 1 mole of entire infrastructure unit of the polymer (A).
3. aligning agent for liquid crystal according to claim 1 or 2, wherein in formula (1), formula (2) and formula (3), X1、X2And X3For At least one of group selected from the structure composition as shown in following formula (X1-1)~(X1-9),
In formula (X1-1), R3、R4、R5And R6It is hydrogen atom, halogen atom, the alkyl of carbon number 1~6, carbon number 2~6 each independently Alkenyl, alkynyl or phenyl, optionally it is identical or different.
4. aligning agent for liquid crystal described in any one of claim 1 to 3, wherein polymer (A) has following formula (3) institute The structural unit shown as the structural unit in addition to formula (1) and formula (2),
In formula (3), X3Each independently be selected from the structure composition as shown in the formula (X1-1)~(X1-9) group at least One kind, R3It is the alkyl of hydrogen atom or carbon number 1~4, Y1It is selected from the structure composition as shown in following formula [1d-1]~[1d-7] At least one of group,
In formula [1d-1]~formula [1d-7], D is tert-butoxymethoxy carbonyl, and n1~n5 is 1~5 integer each independently.
5. aligning agent for liquid crystal according to any one of claims 1 to 4, wherein structural unit shown in formula (3) contains Ratio is 10~50 moles of % relative to 1 mole of entire infrastructure unit of the polymer (A).
6. aligning agent for liquid crystal according to any one of claims 1 to 5, wherein in formula (1), formula (2) and formula (3), X1、 X2And X3For at least one of the group selected from the structure composition as shown in the formula (X1-1).
7. aligning agent for liquid crystal described according to claim 1~any one of 6, wherein in formula (1), formula (2) and formula (3), X1、 X2And X3For at least one of the group selected from the structure composition as shown in following formula (X1-10) and (X1-11),
8. aligning agent for liquid crystal according to any one of claims 1 to 7, wherein in formula (1), formula (2) and formula (3), X1、 X2And X3For the formula (X1-11).
9. a kind of liquid crystal orientation film, for by aligning agent for liquid crystal according to any one of claims 1 to 8 coating, firing and Obtained from obtained film irradiation polarized UV rays.
10. a kind of liquid crystal orientation film, to utilize ink-jet method using aligning agent for liquid crystal described in any one of claim 1~8 Obtained from.
11. a kind of liquid crystal indicates element, with liquid crystal orientation film described in any one of claim 9 and claim 10.
12. liquid crystal according to claim 11 indicates element, wherein liquid crystal is minus liquid crystal material.
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CN105659156A (en) * 2013-10-23 2016-06-08 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
CN105849630A (en) * 2013-10-23 2016-08-10 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114651207A (en) * 2019-11-14 2022-06-21 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same
CN114456378A (en) * 2020-11-09 2022-05-10 江苏三月科技股份有限公司 Polyimide for liquid crystal aligning agent and liquid crystal alignment film prepared from polyimide
CN114456378B (en) * 2020-11-09 2024-02-27 江苏三月科技股份有限公司 Polyimide for liquid crystal alignment agent and liquid crystal alignment film prepared from polyimide

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WO2018122936A1 (en) 2018-07-05

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