CN105385455A - Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element - Google Patents

Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element Download PDF

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CN105385455A
CN105385455A CN201510440953.4A CN201510440953A CN105385455A CN 105385455 A CN105385455 A CN 105385455A CN 201510440953 A CN201510440953 A CN 201510440953A CN 105385455 A CN105385455 A CN 105385455A
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liquid crystal
compound
crystal aligning
aligning agent
base
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片桐宽
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JSR Corp
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Abstract

The invention provides a liquid crystal orientation agent, a liquid crystal orientation film and a liquid crystal display element. According to the invention, the liquid crystal orientation film good in rub resistance and high in external-pressure resistance is obtained. The liquid crystal orientation agent of the invention has at least one kind of compound (P) selected from groups formed by polyamide acid, polyamide acid ester and polyimide, and has organosilicon compounds in a nitrogen-containing structure expressed by the following formula (1a). In the formula (1a), *1 is bonded with a hydrogen atoms, a methylene hydrocarbyl key or a monovalent hydrocarbon key; Ra and Rb respectively and independently are bivalent organic bases; and *1 and *2 express bonds.

Description

Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
Technical field
The present invention relates to a kind of liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device.
Background technology
In the past, liquid crystal display device has developed the liquid crystal display device of electrode structure or the different multiple type of drive of the physical property, manufacturing step etc. of liquid crystal molecule that use, such as known twisted nematic (TwistedNematic, TN) type or STN Super TN (SuperTwistedNematic, STN) type, vertical orientated (VerticalAlignment, VA) type, coplanar switching (In-PlaneSwitching, IPS) type, fringing field switch the various liquid crystal display device such as (fringefieldswitching, FFS) type.These liquid crystal display device have the liquid crystal orientation film making liquid crystal molecular orientation.As the material of liquid crystal orientation film, with regard to thermotolerance or physical strength, the aspect good with the various characteristic such as the affinity of liquid crystal, usually use polyamic acid or polyimide.
In recent years, smart mobile phone, personal digital assistant (PersonalDigitalAssistance, etc. PDA) the universal propelling of the display terminal that mobile terminal or dull and stereotyped PC (tabletPC) etc. are small-sized, improves further to the requirement of the high-precision refinement of liquid crystal panel.Based on this kind of background, propose the plurality of liquid crystals alignment agent (such as with reference to patent documentation 1) that can realize the display quality of liquid crystal panel or the raising of reliability.Patent Document 1 discloses: containing in liquid crystal aligning agent together with the component of polymer of the epoxy compound making to have ad hoc structure and polyamic acid or polyimide, use this liquid crystal aligning agent to form liquid crystal orientation film, in display element, improve liquid crystal aligning and reliability thus.In addition, in recent years, along with the increase in demand of panel type terminal or mobile terminal, the liquid-crystal display of touch panel mode increases.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2008-299318 publication
Summary of the invention
[inventing problem to be solved]
In the liquid-crystal display of touch panel mode, require: the patience for the external pressure such as pressing of the pointing devices such as finger, pen (pointingdevice) is high, that is, be also difficult to produce orientation when being endowed external pressure bad or bright spot is bad.In addition, in recent years, in panel type terminal or mobile terminal, lightweight and slimming advance, and in the panel sectional step when liquid-crystal display manufactures, easily produce the strain of panel, or easy counter plate inside stress application.The strain of this kind of panel or stress become the reason that alignment films is peeled off on substrate, also become and produce the reason that bright spot is bad or orientation is bad.Therefore, require to be difficult to produce strippable substrate to liquid crystal orientation film.
Particularly in recent years, along with the high-precision refinement of liquid crystal display device, the size of 1 pixel becomes little than ever, and on the substrate being formed with liquid crystal orientation film, the quantity of the jump caused because of the electronic component be equipped on this substrate increases.Therefore, liquid crystal orientation film in recent years can be said and easily be subject to higher stress by friction treatment, easily produces scar or film is peeled off.On the other hand, the scar that liquid crystal orientation film produces or stripping become the bad reason of display, and therefore liquid crystal orientation film requires that rub resistance is high.
The present invention is formed in view of described problem, and one of object is to provide a kind of liquid crystal aligning agent, and it can obtain the good liquid crystal orientation film of rub resistance, and can obtain the liquid crystal display device high to the patience of external pressure.
[technique means of dealing with problems]
The problem of solution prior art as above that present inventor etc. are artificial and active research, thus find, the silicon compound with ad hoc structure is made to contain in liquid crystal aligning agent, and obtain the improvement effect of the rub resistance of liquid crystal orientation film and the patience to external pressure of liquid crystal display device, thus complete the present invention.Specifically, following liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device is provided by the present invention.
An aspect of of the present present invention is for providing a kind of liquid crystal aligning agent, and it comprises: be selected from least one polymkeric substance (P) in the cohort be made up of polyamic acid, poly amic acid ester and polyimide; And the silicoorganic compound containing N structure (" * 1 " wherein, in following formula (1a) and hydrogen atom, methylene radical or monovalent hydrocarbon bond) had represented by following formula (1a).
[changing 1]
(in formula (1a), R aand R bit is separately divalent organic base; " * 1 " and " * 2 " represents associative key)
An aspect of of the present present invention is for providing a kind of liquid crystal aligning agent, and it comprises: be selected from least one polymkeric substance (P) in the cohort be made up of polyamic acid, poly amic acid ester and polyimide; And silicoorganic compound, its have represented by described formula (1a) containing N structure, and meet in molecule the R had in hydroxyl and described formula (1a) afor at least one in carbonyl.
In addition, another aspect of the invention is and provide a kind of and use described liquid crystal aligning agent and the liquid crystal orientation film formed and the liquid crystal display device comprising this liquid crystal orientation film.
[effect of invention]
By the described liquid crystal aligning agent comprising particular silicone compound, the liquid crystal orientation film that rub resistance is good can be obtained.In addition, the liquid crystal display device high to the patience of external pressure can be obtained.
Embodiment
Liquid crystal aligning agent of the present disclosure is the aqueous polymer composition that component of polymer is preferably dissolved or dispersed in organic solvent.Below, each composition contained in liquid crystal aligning agent of the present disclosure and other compositions of optionally and arbitrarily allocating are described.
< polymkeric substance (P) >
Liquid crystal aligning agent of the present disclosure contains at least one polymkeric substance (P) in the cohort being selected from and being made up of polyamic acid, polyimide and poly amic acid ester as component of polymer.
[polyamic acid]
Polyamic acid contained in liquid crystal aligning agent of the present disclosure such as obtains by making tetracarboxylic dianhydride and diamines carry out reacting.
(tetracarboxylic dianhydride)
The tetracarboxylic dianhydride used in the synthesis of polyamic acid include, for example aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.As the concrete example of these tetracarboxylic dianhydrides, aliphatics tetracarboxylic dianhydride include, for example: butane tetracarboxylic acid dianhydride etc.;
Ester ring type tetracarboxylic dianhydride include, for example: 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 5-(2, 5-dioxotetrahydro furans-3-base)-3a, 4, 5, 9b-tetrahydrochysene naphtho-[1, 2-c] furans-1, 3-diketone, 5-(2, 5-dioxotetrahydro furans-3-base)-8-methyl-3a, 4, 5, 9b-tetrahydrochysene naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-volution-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl group norbornane-2:3, 5:6-dianhydride, dicyclo [3.3.0] octane-2, 4, 6, 8-tetracarboxylic acid 2:4, 6:8-dianhydride, dicyclo [2.2.1] heptane-2, 3, 5, 6-tetracarboxylic acid 2:3, 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone, 1,2,4,5-cyclopentanetetracarboxylic's dianhydride, dicyclo [2.2.2] pungent-7-alkene-2,3,5,6-tetracarboxylic dianhydride, ethylenediamine tetraacetic acid (EDTA) dianhydride, pentamethylene tetracarboxylic dianhydride etc.,
Aromatic tetracarboxylic acid's dianhydride include, for example: pyromellitic acid anhydride, ethylene glycol bis (trimellitic anhydride ester), 1,3-PD two (trimellitic anhydride ester) etc.; In addition, the tetracarboxylic dianhydride recorded in Japanese Patent Laid-Open 2010-97188 publication can also be used.In addition, the one of these tetracarboxylic dianhydrides can be used alone or be used in combination of two or more by the tetracarboxylic dianhydride used in the synthesis of polyamic acid.
As tetracarboxylic dianhydride, just can make liquid crystal aligning and to regard to the aspect of the favorable solubility of solvent, preferably comprise and be selected from by dicyclo [2.2.1] heptane-2, 3, 5, 6-tetracarboxylic acid 2:3, 5:6-dianhydride, 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 5-(2, 5-dioxotetrahydro furans-3-base)-3a, 4, 5, 9b-tetrahydrochysene naphtho-[1, 2-c] furans-1, 3-diketone, 5-(2, 5-dioxotetrahydro furans-3-base)-8-methyl-3a, 4, 5, 9b-tetrahydrochysene naphtho-[1, 2-c] furans-1, 3-diketone, dicyclo [3.3.0] octane-2, 4, 6, 8-tetracarboxylic acid 2:4, 6:8-dianhydride, cyclopentanetetracarboxylic's dianhydride, 1, at least one compound in the cohort that ammediol two (trimellitic anhydride ester) and pyromellitic acid anhydride form.Relative to the total amount of the tetracarboxylic dianhydride used in the synthesis of polyamic acid, the usage quantity (being its total amount when using two or more) of these preferred compounds is preferably set to more than 5 % by mole, be more preferably and be set to more than 10 % by mole, be more preferably and be set to more than 20 % by mole.
(diamines)
The diamines used in the synthesis of polyamic acid include, for example aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc.As the concrete example of these diamines, aliphatie diamine include, for example: m-xylene diamine, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine, 1,3-two (amino methyl) hexanaphthenes etc.;
Ester ring type diamines include, for example: Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (cyclo-hexylamine) etc.;
Aromatic diamine include, for example: dodecyloxy diaminobenzene, tetradecyloxyaniline diaminobenzene, pentadecane oxygen base diaminobenzene, n-Hexadecane oxygen base diaminobenzene, octadecane oxygen base diaminobenzene, cholestane oxygen base diaminobenzene, cholestene oxygen base diaminobenzene, diaminobenzoic acid cholestane base ester, diaminobenzoic acid cholesteryl ester, diaminobenzoic acid lanostane base ester, two (the 4-amino benzoyl oxygen base) cholestane of 3,6-, two (4-amino-benzene oxygen) cholestane of 3,6-, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexane of 1,1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthene of 1,1-, N-(2,4-diamino-phenyl)-4-(4-heptyl cyclohexyl) benzamide, following formula (D-1)
[changing 2]
(in formula (D-1), X iand X iIbe separately singly-bound ,-O-,-COO-or-OCO-, R ifor alkane two base of carbon number 1 ~ 3, R iIfor alkane two base of singly-bound or carbon number 1 ~ 3, a be 0 or 1, b be the integer of 0 ~ 2, c is the integer of 1 ~ 20, and d is 0 or 1; Wherein, a and b can not become 0 simultaneously)
Represented compound, there is the diamines containing orientation base such as diamines of light orientation structure;
Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl amine, 4,4 '-diamino diphenyl sulfide, 4-aminophenyl-4 '-Aminobenzoate, 4,4 '-chrysoidine, two (4-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) heptane of 1,7-, two [2-(4-aminophenyl) ethyl] hexanodioic acid, two (4-aminophenyl) methylamine of N, N-, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 4,4 '-diamino-diphenyl ether, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-(to phenylenediisopropylidene) dianiline, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, DAP, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-tolidine, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid, 4,4 '-[4,4 '-propane-1,3-bis-base two (piperidines-Isosorbide-5-Nitrae-two base)] pentanoic, 4, other diamines such as 4 '-diamino triphenylamine etc.,
Diamino organo-siloxane include, for example: two (3-aminopropyl)-tetramethyl disiloxanes of 1,3-etc.; In addition, the diamines recorded in Japanese Patent Laid-Open 2010-97188 publication can also be used.
"-X in described formula (D-1) i-(R i-X iI) d-" represented by divalent radical be preferably alkane two base of carbon number 1 ~ 3, *-O-, *-COO-or *-O-C 2h 4-O-(wherein, with associative key and the diamino-phenyl bond of " * ").Group "-C ch 2c+1" include, for example: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc., these groups are preferably straight-chain.Two amino in diamino-phenyl are preferably positioned at 2 relative to other groups, 4-position or 3,5-position.
As the concrete example of the compound represented by described formula (D-1), include, for example the compound etc. represented by following formula (D-1-1) ~ formula (D-1-4) difference.
[changing 3]
In addition, the one of these compounds can be used alone or suitably select two or more use by the diamines used in the synthesis of polyamic acid.
When being applied to the liquid crystal aligning agent of TN type, STN type or vertical alignment-type liquid crystal display device, the group (orientation base) can giving liquid crystal aligning ability to film can be imported on the side chain of polyamic acid.This kind of orientation base include, for example there is linear chain structure group, there is the group of liquid crystal green bone frame and there is the group etc. of massive structure, specifically, include, for example the alkyl of carbon number 4 ~ 20, the fluoroalkyl of carbon number 4 ~ 20, alkoxyl group, the group with steroid skeleton of carbon number 17 ~ 51, multiple ring group etc. that the is direct or bond via concatenating group of carbon number 4 ~ 20.The polyamic acid with orientation base such as obtains by the polymerization containing the diamines containing orientation base in monomer composition.When using the diamines containing orientation base, with regard to the viewpoint making liquid crystal aligning good, relative to the whole diamines used in synthesis, the allotment ratio of the described diamines containing orientation base is preferably set to more than 3 % by mole, is more preferably and is set to 5 % by mole ~ 70 % by mole.
(synthesis of polyamic acid)
Polyamic acid, by making tetracarboxylic dianhydride as above and diamines, optionally carries out reacting and obtaining together with molecular weight adjusting agent.The usage ratio of the tetracarboxylic dianhydride and diamines that are supplied to the building-up reactions of polyamic acid is preferably amino 1 equivalent relative to diamines, and the anhydride group of tetracarboxylic dianhydride becomes the ratio of 0.2 equivalent ~ 2 equivalent, is more preferably the ratio becoming 0.3 equivalent ~ 1.2 equivalent.
Molecular weight adjusting agent include, for example: sour single acid anhydrides such as MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, itaconic anhydride; The monoamine compounds such as aniline, cyclo-hexylamine, n-butylamine, stearic amine; The monoisocyanate compound etc. such as phenyl isocyanate, isocyanic acid naphthyl ester.Relative to total 100 weight part of used tetracarboxylic dianhydride and diamines, the usage ratio of molecular weight adjusting agent is preferably set to below 20 weight parts, is more preferably and is set to below 10 weight parts.
The building-up reactions of polyamic acid is preferably carried out in organic solvent.Temperature of reaction is now preferably-20 DEG C ~ 150 DEG C, is more preferably 0 DEG C ~ 100 DEG C.In addition, the reaction times is preferably 0.1 hour ~ 24 hours, is more preferably 0.5 hour ~ 12 hours.
The organic solvent used in reaction include, for example aprotic polar solvent, phenol system solvent, alcohol, ketone, ester, ether, halon, hydrocarbon etc.In these organic solvents, be preferably more than one that use and be selected from the cohort (organic solvent of the first cohort) be made up of aprotic polar solvent and phenol system solvent, or be selected from more than one and more than one the mixture be selected from the cohort (organic solvent of the second cohort) that is made up of alcohol, ketone, ester, ether, halon and hydrocarbon in the organic solvent of the first cohort.In the latter case, relative to the total amount of the organic solvent of the first cohort and the organic solvent of the second cohort, the usage ratio of the organic solvent of the second cohort is preferably less than 50 % by weight, is more preferably less than 40 % by weight, is especially preferably less than 30 % by weight.
Particularly preferred organic solvent is preferably use and is selected from by METHYLPYRROLIDONE, N, N-N,N-DIMETHYLACETAMIDE, N, more than one in the cohort that dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA, meta-cresol, xylenol and halogenation phenol form as solvent, or use the mixture of more than one and other organic solvent of these organic solvents in the scope of described ratio.The usage quantity (a) of organic solvent is preferably set to the total amount (a+b) relative to reaction soln, and the total amount (b) of tetracarboxylic dianhydride and diamines becomes the amount of 0.1 % by weight ~ 50 % by weight.
In the manner, the reaction soln dissolved by polyamic acid is obtained.This reaction soln directly can be supplied to the preparation of liquid crystal aligning agent, also reoffer to the preparation of liquid crystal aligning agent after polyamic acid contained in reaction soln can being separated, or can also reoffer after the polyamic acid purifying of separation to the preparation of liquid crystal aligning agent.When making polyimide when carrying out dehydration closed-loop to polyamic acid, described reaction soln directly can be supplied to dehydration closed-loop reaction, also reoffer to dehydration closed-loop reaction after polyamic acid contained in reaction soln can being separated, or can also react reoffering after the polyamic acid purifying of separation to dehydration closed-loop.The separation of polyamic acid and purifying can carry out according to known method.
[poly amic acid ester]
Poly amic acid ester such as can utilize following methods to obtain: [I] makes the polyamic acid that obtained by described building-up reactions and esterifying agent carry out the method for reacting; [II] makes tetracarboxylic acid diester and diamines carry out the method for reacting; [III] makes tetracarboxylic acid diester dihalide and diamines carry out the method etc. of reacting.
In addition, in this specification sheets so-called " tetracarboxylic acid diester " refer to two in four carboxyls that tetracarboxylic acid has esterified, all the other two is the compound of carboxyl.So-called " tetracarboxylic acid diester dihalide " refer to two in four carboxyls that tetracarboxylic acid has esterified, all the other two compounds be halogenated.
The esterifying agent used in method [I] include, for example the compound of hydroxyl, acetal based compound, halogenide, compound etc. containing epoxy group(ing).As the concrete example of these compounds, the compound of hydroxyl include, for example: the alcohols such as methyl alcohol, ethanol, propyl alcohol, the phenols such as phenol, cresols etc.; Acetal based compound include, for example: DMF diethyl acetal, N, N-diethylformamide diethyl acetal etc.; Halogenide include, for example: methyl bromide, bromic ether, bromo-octadecane, methyl chloride, chlorooctadecane, 1,1,1-tri-fluoro-2-iodoethane etc.; Compound containing epoxy group(ing) include, for example: propylene oxide etc.
The tetracarboxylic acid diester used in method [II] is such as by using described alcohols, and in the synthesis to described polyamic acid, illustrative tetracarboxylic dianhydride carries out open loop and obtains.In addition, in method [II], the tetracarboxylic acid derivatives used can be only tetracarboxylic acid diester, also can be used together tetracarboxylic dianhydride.The diamines used in method [II] can enumerate illustrative diamines in the synthesis of polyamic acid.The reaction of method [II] is preferably in organic solvent, carries out under the existence of suitable dehydration catalyst.Organic solvent can enumerate the organic solvent and illustrative organic solvent that use in the synthesis as polyamic acid.Dehydration catalyst include, for example: 4-(4,6-dimethoxy-1,3,5-triazines-2-base)-4-methylmorpholine halogenide, carbonylic imidazole, phosphorus system condensing agent etc.
The tetracarboxylic acid diester dihalide used in method [III] such as obtains by making the suitable chlorizating agent such as the tetracarboxylic acid diester that obtains in this way and thionyl chloride carry out reacting.In addition, in method [III], the tetracarboxylic acid derivatives used can be only tetracarboxylic acid diester dihalide, also can be used together tetracarboxylic dianhydride.The diamines used in method [III] can enumerate illustrative diamines in the synthesis of polyamic acid.The reaction of method [III] is preferably in organic solvent, carries out under the existence of suitable alkali.Organic solvent can enumerate the organic solvent and illustrative organic solvent that use in the synthesis as polyamic acid.Alkali such as can preferably use the tertiary amine such as pyridine, triethylamine.
In addition, poly amic acid ester contained in liquid crystal aligning agent can only have amic acid esters structure, also can be amido acid structure and amic acid esters structure and the partial esterification thing deposited.
The reaction soln that poly amic acid ester dissolves directly can be supplied to the preparation of liquid crystal aligning agent, also reoffer to the preparation of liquid crystal aligning agent after poly amic acid ester contained in reaction soln can being separated, or can also reoffer after the poly amic acid ester purifying of separation to the preparation of liquid crystal aligning agent.The separation of poly amic acid ester and purifying can carry out according to known method.
[polyimide]
Such as by carrying out dehydration closed-loop to the polyamic acid synthesized in this way, imidization obtains polyimide.
Polyimide can be the complete imide compound that the amido acid structure had the polyamic acid as its precursor all carries out dehydration closed-loop, also can be only carry out dehydration closed-loop to a part for amido acid structure and make amido acid structure and imide ring structure and the part imide compound of depositing.The imide rate of the polyimide used in reaction is preferably more than 20%, is more preferably 30% ~ 99%, is especially preferably 40% ~ 99%.This imide rate is the total relative to the quantity of the amido acid structure of polyimide and the quantity of imide ring structure, represents the ratio shared by quantity of imide ring structure with percentage.Herein, a part for imide ring also can be different imide ring.
The dehydration closed-loop of polyamic acid preferably utilizes following methods to carry out: the method heated polyamic acid; Or polyamic acid is dissolved in organic solvent, in this solution, adds dewatering agent and dehydration closed-loop catalyzer, optionally carry out the method heated.Wherein preferably utilize the method for the latter.
Add in the method for dewatering agent and dehydration closed-loop catalyzer in the solution of polyamic acid, dewatering agent such as can use the acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.Relative to 1 mole of the amido acid structure of polyamic acid, the usage quantity of dewatering agent is preferably set to 0.01 mole ~ 20 moles.Dehydration closed-loop catalyzer such as can use the tertiary amine such as pyridine, collidine, two picolins, triethylamine.Relative to used dewatering agent 1 mole, the usage quantity of dehydration closed-loop catalyzer is preferably set to 0.01 mole ~ 10 moles.The organic solvent used in dehydration closed-loop reaction can enumerate the organic solvent and illustrative organic solvent that use in the synthesis as polyamic acid.The temperature of reaction of dehydration closed-loop reaction is preferably 0 DEG C ~ 180 DEG C, is more preferably 10 DEG C ~ 150 DEG C.Reaction times is preferably 1.0 hours ~ 120 hours, is more preferably 2.0 hours ~ 30 hours.
Obtain the reaction soln containing polyimide in this way.This reaction soln directly can be supplied to the preparation of liquid crystal aligning agent, also reoffer to the preparation of liquid crystal aligning agent after can removing dewatering agent and dehydration closed-loop catalyzer in autoreaction solution, also reoffer to the preparation of liquid crystal aligning agent after polyimide can being separated, or can also reoffer after the polyimide purifying of separation to the preparation of liquid crystal aligning agent.These purification process can be carried out according to known method.In addition, polyimide also can be obtained by the imidization of poly amic acid ester.
The polymkeric substance (P) obtained in this way is preferably when being made into concentration and being the solution of 15 % by weight, and have 20mPas ~ 1, the soltion viscosity person of 800mPas, is more preferably and has 50mPas ~ 1, the soltion viscosity person of 500mPas.In addition, the soltion viscosity (mPas) of polymkeric substance (P) be to the concentration using the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) of polymkeric substance (P) to prepare be 15 % by weight polymers soln, use E type rotational viscosimeter, measure at 25 DEG C and the value that obtains.
The weight average molecular weight (Mw) of the polystyrene conversion utilizing gel permeation chromatography (GelPermeationChromatography, GPC) to measure of polymkeric substance (P) is preferably 1,000 ~ 500,000, be more preferably 2,000 ~ 300,000.In addition, Mw is preferably less than 15 with the molecular weight distribution (Mw/Mn) represented by ratio of the number average molecular weight (Mn) of the polystyrene conversion utilizing GPC to measure, and is more preferably less than 10.By being in molecular weight ranges as above, good orientation and the stability of liquid crystal display device can be guaranteed.
< silicoorganic compound >
Liquid crystal aligning agent of the present disclosure, except containing except described polymkeric substance (P), is also used as additive containing the silicoorganic compound (hereinafter also referred to " specific silicidation compound ") containing N structure had represented by following formula (1a) simultaneously.
[changing 4]
(in formula (1a), R aand R bit is separately divalent organic base; " * 1 " and " * 2 " represents associative key)
In described formula (1a), R aand R bdivalent organic base include, for example carbonyl, bivalent hydrocarbon radical, heterocyclic radical etc.Herein, in this specification sheets, so-called " alkyl " is the implication comprising chain alkyl, ester ring type alkyl and aromatic hydrocarbyl.So-called " chain alkyl ", refers to and main chain does not comprise ring texture, but the straight-chain alkyl be only made up of chain-like structure and branch-like alkyl.Wherein, can be saturated, also can be unsaturated.So-called " ester ring type alkyl ", refers to that the structure only comprising ester ring type hydrocarbon is as ring structure, and not containing the alkyl of aromatic ring structure.Wherein, be not necessarily only made up of the structure of ester ring type hydrocarbon, also comprised the alkyl in its part with chain-like structure.So-called " aromatic hydrocarbyl ", refers to and comprises the alkyl of aromatic ring structure as ring structure.Wherein, be not necessarily only made up of aromatic ring structure, also can comprised the structure of chain-like structure or ester ring type hydrocarbon in its part.
Specific silicidation compound contained in liquid crystal aligning agent of the present disclosure and then be " * 1 " in described formula (1a) and hydrogen atom, methylene radical or monovalent hydrocarbon bond, or meet in molecule the R had in hydroxyl and described formula (1a) afor at least one compound in carbonyl.By making this kind of silicoorganic compound contain in liquid crystal aligning agent, rub resistance or the liquid crystal orientation film good to the patience of external pressure can be obtained.
Herein, when " * 1 " in described formula (1a) and methylene radical bond, this methylene radical can with the nitrogen-atoms in formula (1a) and R bform ring structure at least partially together.In addition, when specific silicidation compound for have represented by formula described at least one (1a) containing N structure and " * 1 " in described formula (1a) compound with hydrogen atom, methylene radical or monovalent hydrocarbon bond, also can be and then meet in molecule the R had in hydroxyl and described formula (1a) afor the compound of at least one in carbonyl.
Wherein, with regard to fully obtaining the viewpoint of effect of the present invention, specific silicidation compound is preferably selected from least one in the cohort be made up of the silicon compound containing N structure and hydroxyl had represented by described formula (1a) and the silicon compound with urea structure.
When specific silicidation compound is for having the silicon compound containing N structure and hydroxyl represented by described formula (1a), this compound include, for example: the amine compound making to have at least one (hereinafter also referred to " specific amino ") be selected from amino by one-level and that secondary is amino formed cohort, carries out reacting and the compound that obtains with the compound containing reactive base of the reactive base of at least one had in the cohort that is selected from and is made up of anhydride group, epoxy group(ing) and oxetanylmethoxy.
In addition, described amine compound and the described compound containing reactive base at least any one is the compound with Siliciumatom.In this situation, can be that only described amine compound and any one containing the compound in reactive base described have Siliciumatom, or also can be that described amine compound and the described compound containing reactive base all have Siliciumatom.
Concrete example when synthesizing specific silicidation compound as the reaction by described amine compound and the described compound containing reactive base, include, for example following [1] ~ [4]:
[1] use the silicon compound (s-1) with specific amino as described amine compound, and use the compound (t-1) with anhydride group as the described compound containing reactive base, make these compounds carry out the method for reacting;
[2] use the silicon compound (s-2) with anhydride group as the described compound containing reactive base, make itself and described amine compound carry out the method for reacting;
[3] use the silicon compound (s-3) with epoxy group(ing) or oxetanylmethoxy as the described compound containing reactive base, make itself and described amine compound carry out the method for reacting;
[4] use the silicon compound (s-1) with specific amino as described amine compound, and use the compound (e-1) with epoxy group(ing) or oxetanylmethoxy as the described compound containing reactive base, make these compounds carry out the method etc. of reacting.
The silicon compound (s-1) used in described [1] and [4] include, for example: 3-TSL 8330, APTES, 3-amino propyl methyl diethoxy silane, 3-amino propyl methyl dimethoxysilane, 3-ethyldimonium dimethoxysilane, 3-ethyldimonium diethoxy silane, 3-dimethyl Ethoxysilane, 3-aminopropyl diethylmethoxysilane, 3-aminopropyl diethylethoxysilane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-APTES, 4-aminobutyl dimethyl methoxy silane etc.One in these compounds can be used alone or be use mixing two or more by silicon compound (s-1).
The silicon compound (s-2) used in described formula [2] include, for example: trimethoxysilylpropyl Succinic anhydried, tri-ethoxy silylpropyl Succinic anhydried, methyl dimethoxysilane base propyl succinimide acid anhydrides, methyldiethoxysilane base propyl succinimide acid anhydrides etc.Silicon compound (s-2) can be used alone one or be use mixing two or more.
The silicon compound (s-3) with epoxy group(ing) or oxetanylmethoxy used in described [3] include, for example: 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl dimethyl methoxy silane, 3-glycidoxypropyl dimethylethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, 4-epoxycyclohexyl) ethyl triethoxysilane etc. is containing the silane compound of epoxy group(ing), following formula (s-3-1)
[changing 5]
The silane compound etc. of the oxygen heterocyclic ring butyl such as represented compound.Silicon compound (s-3) can be used alone one or be use mixing two or more.
The compound (t-1) with anhydride group used in described [1] as long as have at least one anhydride group in a part, then there is no particular restriction.Specifically, the compound in a part with an anhydride group include, for example: MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, itaconic anhydride, 2, Niacin Nicitinic Acid acid anhydride etc.; The compound in a part with plural anhydride group include, for example the tetracarboxylic dianhydride and illustrative compound etc. that use in the synthesis as described polyamic acid.The one of these compounds can be used alone or be use mixing two or more by the compound (t-1) with anhydride group.
Described [2] and [3] as long as the middle amine compound used has at least one specific amino in a part, then there is no particular restriction.Specifically, the compound having an one-level amino in a part include, for example: aniline, cyclo-hexylamine, propyl group amine, butylamine, amylamine, hexyl amine etc.; The compound in a part with a secondary amino include, for example: dimethyl amine, diethylamide, dipropylamine, dibutylamine, ten dimethylene imines, piperidines, tetramethyleneimine, hexamethylene imine, heptamethylene imines, dicyclohexylamine, N-methyl-benzyl amine, two-(2-ethylhexyl) amine, diallyl amine, morpholines etc.;
The compound in a part with plural one-level amino include, for example the diamines and illustrative compound etc. that use in the synthesis as described polyamic acid; The compound in a part with plural secondary amino include, for example piperazine etc.The one of these compounds can be used alone or be used in combination of two or more by described amine compound.
The compound (e-1) with epoxy group(ing) or oxetanylmethoxy used in described [4] include, for example: ethylene glycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-aminomethyl cyclohexane, N, N-diglycidyl-cyclo-hexylamine etc.The one of these compounds can be used alone or be used in combination of two or more by described compound (e-1).
Be supplied to the amine compound in the building-up reactions of specific silicidation compound and be preferably specific amino 1 equivalent relative to amine compound containing the usage ratio of the compound of reactive base, reactive base containing the compound of reactive base becomes the ratio of 0.2 equivalent ~ 2.5 equivalent, is more preferably the ratio becoming 0.3 equivalent ~ 2.2 equivalent.
Amine compound preferably carries out with the reaction of the compound containing reactive base in organic solvent.As long as the organic solvent used in reaction for amine compound and containing reactive base compound for be inertia, and by the solvent of these compound dissolutions, METHYLPYRROLIDONE etc. can be include, for example.Temperature of reaction is preferably 0 DEG C ~ 80 DEG C, is more preferably 10 DEG C ~ 70 DEG C.Reaction times is preferably 1 hour ~ 60 hours, is more preferably 10 hours ~ 30 hours.
As the concrete example of the specific silicidation compound obtained by described reaction, include, for example the compound etc. represented by following formula (1).
[changing 6]
(in formula (1), R 19for hydrogen atom or monovalent hydrocarbon or intramolecular two R 19the bivalent hydrocarbon radical that bond is formed; R 20for trivalent organic radical, R 21for divalent organic base, R 22and R 23be separately monovalent hydrocarbon, R 24for (h+i) valency organic radical; A 1for singly-bound or carbonyl, A 2for alkane two base of singly-bound, carbonyl or carbon number 1 ~ 3, B 1and B 2it is separately alkane two base of carbonyl or carbon number 1 ~ 3; E, f, g and i are separately the integer of 0 ~ 4, e+f+g>=1 and e+i>=1; H is the integer of 1 ~ 4, and j is the integer of 1 ~ 3; Wherein, at R 20, R 22, R 23, A 1, A 2, B 1and B 2when existing multiple respectively, multiple R 20, R 22, R 23, A 1, A 2, B 1and B 2there is described definition independently)
In described formula (1), R 19monovalent hydrocarbon include, for example: the alkyl of the straight-chain such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl or branch-like; The cycloalkyl such as cyclohexyl; The aryl such as phenyl, tolyl; The aralkyl etc. such as benzyl.In these groups, R 19be preferably the alkyl of hydrogen atom or carbon number 1 ~ 5, be more preferably the alkyl of hydrogen atom or carbon number 1 ~ 3.
In addition, in R 19there is plural situation in a part under, intramolecular two R 19can bond and form the part of ring mutually.In this situation, by the "-R in formula (1) 19-nitrogen-atoms-B 2-R 24-B 2-nitrogen-atoms-R 19-" form ring.Pass through R 19bond and the ring formed is the nitrogen heterocyclic ring with two nitrogen-atoms, include, for example piperazine ring etc.
R 20trivalent organic radical include, for example the alkyl of carbon number 1 ~ 10, be preferably the chain alkyl of carbon number 1 ~ 3.R 21the methylene radical of divalent organic base alkane two base or this alkane two base that include, for example carbon number 1 ~ 6 be substituted divalent radical etc. into-O-.
R 22and R 23monovalent hydrocarbon can enumerate as R 19monovalent hydrocarbon and illustrative group.Be preferably the alkyl of carbon number 1 ~ 5, be more preferably the alkyl of carbon number 1 ~ 3.R 24include, for example: the group etc. that the group that the methylene radical of the alkyl of carbon number 1 ~ 20, this alkyl replaces through-O-,-CO-,-COO-,-NH-,-NHCO-etc., the hydrogen atom of alkyl replace through halogen atom (being preferably fluorine atom) etc.
When e=0, be preferably B 1and B 2at least any one is carbonyl, and A 1for carbonyl.In this situation, specific silicidation compound have hydroxyl that specific silicidation compound has and containing N structure respectively with the structure of carbonyl bond.In addition, when hydroxyl and carbonyl bond, specific silicidation compound has carboxyl, and when containing N structure and carbonyl bond, specific silicidation compound has amido linkage (-CO-NR-).Wherein, specific silicidation compound also can have more hydroxyl in addition except carboxyl, in addition, also except amido linkage, also can have more-NR-in addition.
As the concrete example of the compound represented by described formula (1), include, for example the compound etc. represented by following formula (1-1) ~ formula (1-5) difference.
[changing 7]
(in formula (1-1), R 1for quadrivalent organic radical, R 2for divalent organic base, R 3and R 4be separately monovalent hydrocarbon, a is the integer of 1 ~ 3; Wherein, multiple R 2can be identical, also can be different; At R 3and R 4when existing multiple respectively, multiple R 3and multiple R 4can be identical, also can be different)
[changing 8]
(in formula (1-2), R 5and R 7be separately divalent organic base, R 6for trivalent organic radical, R 8and R 9be separately monovalent hydrocarbon, b is the integer of 1 ~ 3; Wherein, multiple R 6can be identical, also can be different; At R 8and R 9when existing multiple respectively, multiple R 8and multiple R 9can be identical, also can be different)
[changing 9]
(in formula (1-3), R 10and R 11be separately divalent organic base, R 12and R 13be separately monovalent hydrocarbon, c is the integer of 1 ~ 3; Wherein, at R 12and R 13when existing multiple respectively, multiple R 12and multiple R 13can be identical, also can be different)
[changing 10]
(in formula (1-4), R 14for any monovalent organic radical, R 15for trivalent organic radical, R 16for bivalent hydrocarbon radical, R 17and R 18be separately monovalent hydrocarbon, d is the integer of 1 ~ 3; Wherein, at R 17and R 18when existing multiple respectively, multiple R 17and multiple R 18can be identical, also can be different)
[changing 11]
(in formula (1-5), R 25for hydrogen atom or monovalent hydrocarbon or intramolecular two R 25the bivalent hydrocarbon radical that bond is formed; R 26for divalent organic base, R 27for trivalent organic radical, R 30for divalent organic base, R 28and R 29be separately monovalent hydrocarbon, k is the integer of 1 ~ 3; A 3for alkane two base of singly-bound, carbonyl or carbon number 1 ~ 3; Wherein, molecular memory multiple R 25, R 27, R 30and A 3each other can be identical, also can be different; At R 28and R 29when existing multiple respectively, multiple R 28and multiple R 29can be identical, also can be different)
Compound represented by described formula (1-1) can utilize the method for described [1] to synthesize, specifically, by using containing amino silane compound as silicon compound (s-1) and tetracarboxylic dianhydride as the compound (t-1) with anhydride group, these compounds are made to carry out reacting and obtaining.
Herein, in described formula (1-1), R 1quadrivalent organic radical be the tetravalence base come by tetracarboxylic dianhydride; R 2divalent organic base be by the divalent radical come containing amino silane compound, include, for example: alkane two base of carbon number 1 ~ 6, there is between the C-C of this alkane two base the divalent radical etc. of-NH-.
R 3and R 4monovalent hydrocarbon can enumerate as the R in described formula (1) 19monovalent hydrocarbon and illustrative group.Be preferably the alkyl of carbon number 1 ~ 5, be more preferably the alkyl of carbon number 1 ~ 3.
Compound represented by described formula (1-2) can utilize the method for described [2] to synthesize, specifically, by using silane compound containing anhydride group as silicon compound (s-2) and diamines as described amine compound, these compounds are made to carry out reacting and obtaining.
Herein, in described formula (1-2), R 5divalent organic base be the divalent radical come by diamines.R 7divalent organic base be by the divalent organic base come containing the silane compound of anhydride group, include, for example alkane two base etc. of carbon number 1 ~ 6.R 6trivalent organic radical include, for example the chain alkyl etc. of carbon number 1 ~ 5.R 8and R 9monovalent hydrocarbon can enumerate as the R in described formula (1) 19monovalent hydrocarbon and illustrative group.Be preferably the alkyl of carbon number 1 ~ 5, be more preferably the alkyl of carbon number 1 ~ 3.
Compound represented by described formula (1-3) can utilize the method for described [1] to synthesize, specifically, by using containing amino silane compound as silicon compound (s-1) and sour single acid anhydride as the compound (t-1) with anhydride group, these compounds are made to carry out reacting and obtaining.
Herein, in described formula (1-3), R 10divalent organic base be the divalent radical come by acid list acid anhydride, include, for example the bivalent hydrocarbon radical etc. of carbon number 2 ~ 20.R 11divalent organic base be by the divalent radical come containing amino silane compound, include, for example alkane two base of carbon number 1 ~ 6, there is the divalent radical etc. of-NH-between the C-C of this alkane two base.
R 12and R 13monovalent hydrocarbon can enumerate as the R in described formula (1) 19monovalent hydrocarbon and illustrative group.Be preferably the alkyl of carbon number 1 ~ 5, be more preferably the alkyl of carbon number 1 ~ 3.
Compound represented by described formula (1-4) can utilize the method for described [2] to synthesize, specifically, by using silane compound containing anhydride group as silicon compound (s-2) and monoamine as described amine compound, these compounds are made to carry out reacting and obtaining.
Herein, in described formula (1-4), R 14any monovalent organic radical be the monad radical come by monoamine.R 15trivalent organic radical include, for example the chain alkyl etc. of carbon number 1 ~ 5.R 16divalent organic base be by the divalent organic base come containing the silane compound of anhydride group, include, for example alkane two base etc. of carbon number 1 ~ 6.R 17and R 18monovalent hydrocarbon can enumerate as the R in described formula (1) 19monovalent hydrocarbon and illustrative group.Be preferably the alkyl of carbon number 1 ~ 5, be more preferably the alkyl of carbon number 1 ~ 3.
Compound represented by described formula (1-5) can utilize the method for described [3] to synthesize, specifically, by using containing the silane compound of epoxy group(ing) or the silane compound of oxygen heterocyclic ring butyl as silicon compound (s-3) and described illustrative compound as described amine compound, these compounds are made to carry out reacting and obtaining.
Herein, in described formula (1-5), R 26divalent organic base be the divalent radical come by amine compound.R 27trivalent organic radical include, for example the chain alkyl etc. of carbon number 1 ~ 5.R 30divalent organic base be by the divalent radical come containing the silane compound of epoxy group(ing) or the silane compound of oxygen heterocyclic ring butyl, include, for example alkane two base of carbon number 1 ~ 5 or there is the divalent radical etc. of-O-between the C-C of this alkane two base.R 25, R 28and R 29monovalent hydrocarbon can enumerate as the R in described formula (1) 19monovalent hydrocarbon and illustrative group.Be preferably the alkyl of carbon number 1 ~ 5, be more preferably the alkyl of carbon number 1 ~ 3.A 3be preferably alkane two base of singly-bound or carbon number 1 ~ 3.
As the preferred concrete example when specific silicidation compound is the silicon compound with urea structure, include, for example the compound represented by following formula (2).
[changing 12]
(in formula (2), R 31and R 32be separately monovalent hydrocarbon, R 33for divalent organic base, R 34for any monovalent organic radical; T is the integer of 1 ~ 3; Wherein, at R 31, R 32when existing multiple, multiple R 31, R 32there is described definition independently)
In described formula (2), R 31and R 32be preferably methyl or ethyl.R 33the methylene radical of alkane two base or this alkane two base that include, for example carbon number 1 ~ 6 is substituted the divalent radical etc. into-O-.R 34include, for example monovalent hydrocarbon, monovalence ester ring type base etc.
As the concrete example of the compound represented by described formula (2), include, for example: 1-(pyridine-2-base)-3-(3-triethoxysilicane alkyl) propyl group) urea, 1-(pyridine-2-base)-3-(3-Trimethoxy silane base) propyl group) urea, 1-(pyridine-2-base)-3-(3-methyldiethoxysilane base) propyl group) urea etc.In addition, the silicon compound with urea structure can be used alone one or be used in combination of two or more.
In described compound, specific silicidation compound contained in liquid crystal aligning agent of the present disclosure particularly preferably can use at least one be selected from cohort that the compound represented by described formula (1) and the compound represented by described formula (2) form.In addition, specific silicidation compound can be used alone one or be used in combination of two or more.
Relative to total 100 weight part of the component of polymer of liquid crystal aligning agent, the allotment ratio of specific silicidation compound is preferably 0.01 weight part ~ 50 weight part.Its reason is: if be less than 0.01 weight part, be then difficult to obtain the improvement effect brought because of the interpolation of silicoorganic compound, if more than 50 weight parts, then there is the tendency that liquid crystal aligning declines.Be more preferably 0.05 weight part ~ 40 weight part, be especially preferably 0.1 weight part ~ 35 weight part, be particularly preferably 0.1 weight part ~ 30 weight part.In addition, the one of described compound can be used alone or be used in combination of two or more by specific silicidation compound.
Other compositions of < >
Liquid crystal aligning agent of the present disclosure also can optionally and containing other compositions beyond polymkeric substance (P) and specific silicidation compound.These other compositions include, for example: other polymkeric substance beyond polyamic acid, polyimide and poly amic acid ester, have other functional silanes compounds etc. beyond the compound (hereinafter referred to as " compound containing epoxy group(ing) ") of at least one epoxy group(ing), specific silicidation compound in molecule.
[other polymkeric substance]
Other polymkeric substance described can be used for improving solution properties or electrical characteristic.Other polymkeric substance described include, for example the polymkeric substance etc. in main framing with organopolysiloxane, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative, poly-(methyl) acrylate etc.
When other polymkeric substance are made an addition in liquid crystal aligning agent, relative to total 100 weight part of polymkeric substance contained in liquid crystal aligning agent, the allotment ratio of other polymkeric substance described is preferably set to below 50 weight parts, be more preferably and be set to 0.1 weight part ~ 40 weight part, be especially preferably set to below 0.1 weight part ~ 30 weight part.
[compound containing epoxy group(ing)]
Compound containing epoxy group(ing) can be used for improving liquid crystal orientation film with the cementability of substrate surface or electrical characteristic.This kind include, for example following compound as preferred person containing the compound of epoxy group(ing): ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidylether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-aminomethyl cyclohexane, N, N-diglycidyl-cyclo-hexylamine etc.In addition, containing the organopolysiloxane containing epoxy group(ing) that the example of the compound of epoxy group(ing) can use No. 2009/096598th, International Publication to record.
When the compound containing epoxy group(ing) is made an addition in liquid crystal aligning agent, relative to total 100 weight part of polymkeric substance contained in liquid crystal aligning agent, the allotment ratio of the described compound containing epoxy group(ing) is preferably set to below 40 weight parts, is more preferably and is set to 0.1 weight part ~ 30 weight part.
[other functional silanes compound]
Other functional silanes compound can use for the object of the printing of raising liquid crystal aligning agent.This kind of functional silanes compound include, for example: 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-tri-ethoxy silylpropyl diethylenetriamine, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-Trimethoxy silane base-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-phenyl-3-TSL 8330, glycidoxypropyl methyltrimethoxy silane, 2-glycidoxypropyl ethyl trimethoxy silane, 3-glycidoxypropyltrimewasxysilane etc.
When other functional silanes compound is made an addition in liquid crystal aligning agent, relative to total 100 weight part of polymkeric substance contained in liquid crystal aligning agent, other the allotment ratio of functional silanes compound described is preferably set to below 2 weight parts, is more preferably and is set to 0.02 weight part ~ 0.2 weight part.
In addition, other compositions, except described compound, also can be enumerated: compound or antioxidant, meal chelate compounds, hardening accelerator, tensio-active agent, weighting agent, dispersion agent, the sensitizing agent etc. in molecule with at least one oxetanylmethoxy.
< solvent >
Liquid crystal aligning agent of the present disclosure is prepared into and polymkeric substance (P), specific silicidation compound and other compositions of optionally using preferably is disperseed or are dissolved in the liquid composition in suitable solvent.
The organic solvent used include, for example: METHYLPYRROLIDONE, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, methyl methoxypropionate, ethyl ethoxy-c acid esters, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (ethylene glycol butyl ether), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, Texacar PC etc.These organic solvents can be used alone or are use mixing two or more.
Solid component concentration (ratio of total weight shared by the gross weight of liquid crystal aligning agent of the composition beyond the solvent of liquid crystal aligning agent) in liquid crystal aligning agent can be considered viscosity, volatility etc. and suitably select, and is preferably the scope of 1 % by weight ~ 10 % by weight.That is, liquid crystal aligning agent is by coating substrate surface in aftermentioned mode, preferably heats, and formed as liquid crystal orientation film film or become the film of liquid crystal orientation film.Now, when solid component concentration is less than 1 % by weight, the thickness of film becomes too small and is difficult to obtain good liquid crystal orientation film.On the other hand, when solid component concentration is more than 10 % by weight, the thickness of film becomes excessive and is difficult to obtain good liquid crystal orientation film, and in addition, the viscosity that there is liquid crystal aligning agent increases and the tendency of coating decline.
The scope of particularly preferred solid component concentration is different according to the method on substrate during coating of liquid crystalline alignment agent.Such as when utilizing turner method to coat on substrate, solid component concentration (ratios of total weight shared by the gross weight of liquid crystal aligning agent of the whole compositions beyond the solvent in liquid crystal aligning agent) is particularly preferably the scope of 1.5 % by weight ~ 4.5 % by weight.When utilizing print process, being particularly preferably scope solid component concentration being set to 3 % by weight ~ 9 % by weight, thus soltion viscosity being set to the scope of 12mPas ~ 50mPas.When utilizing ink jet method, being particularly preferably scope solid component concentration being set to 1 % by weight ~ 5 % by weight, thus soltion viscosity being set to the scope of 3mPas ~ 15mPas.Temperature when preparing liquid crystal aligning agent is preferably 10 DEG C ~ 50 DEG C, is more preferably 20 DEG C ~ 30 DEG C.
< liquid crystal display device >
Liquid crystal display device of the present disclosure comprises the liquid crystal orientation film using the liquid crystal aligning agent of described explanation to be formed.The operating mode of liquid crystal display device is not particularly limited, such as can be applicable to TN type, STN type, VA type (comprise vertical orientated-multidomain vertical orientation (VerticalAlignment-MultidomainVerticalAlignment, VA-MVA) type, the vertical orientated (VerticalAlignment-PatternedVerticalAlignment of vertical orientated-pattern, VA-PVA) type etc.), IPS type, FFS type, the multiple operation mode such as optical compensation curved (OpticallyCompensatedBend, OCB) type.
Liquid crystal display device such as can utilize and comprise the following steps that the method for (1) ~ step (3) manufactures.Step (1) uses different substrates according to required operating mode.Step (2) and step (3) share in each operating mode.
[step (1): the formation of film]
First, on substrate, coating of liquid crystalline alignment agent, heats coated face then, forms film thus on substrate.
(1-A) when Production Example is as TN type, STN type or VA type liquid crystal display device, first, using two pieces of substrates being provided with patterned nesa coating as a pair, preferably utilize flexographic printing process, method of spin coating, roll-coater method or ink jet printing method, difference coating of liquid crystalline alignment agent in each transparent conductive film forming surface of described substrate.Substrate such as can use: the glass such as float glass, soda glass; Comprise the transparency carrier of the plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene).The wherein nesa coating of one side being arranged at substrate can use and comprise stannic oxide (SnO 2) nesa (NESA) film (PPG company of the U.S., registered trademark), comprise indium oxide-tin oxide (In 2o 3-SnO 2) tin indium oxide (IndiumTinOxide, ITO) film etc.In order to obtain patterned nesa coating, such as, can utilize following methods: after forming patternless nesa coating, being formed the method for pattern by photoetch; The method etc. with the mask of required pattern is used when forming nesa coating.During coating of liquid crystalline alignment agent, in order to make the cementability of substrate surface and nesa coating and film better, also to the face forming film in substrate surface, the pre-treatment being coated with functional silanes compound, functionality titanium compound etc. in advance can be implemented.
After coating of liquid crystalline alignment agent, for the object such as sagging preventing be coated with liquid crystal aligning agent, be preferably enforcement and preheat (prebake conditions).Prebake conditions temperature is preferably 30 DEG C ~ 200 DEG C, is more preferably 40 DEG C ~ 150 DEG C, is particularly preferably 40 DEG C ~ 100 DEG C.The prebake conditions time is preferably 0.25 minute ~ 10 minutes, is more preferably 0.5 minute ~ 5 minutes.Then, remove completely for by solvent, optionally the amido acid structure be present in polymkeric substance is carried out to the object of hot-imide, and implement calcining (toasting afterwards) step.Calcining temperature (rear storing temperature) is now preferably 80 DEG C ~ 300 DEG C, is more preferably 120 DEG C ~ 250 DEG C.Post-bake times is preferably 5 minutes ~ 200 minutes, is more preferably 10 minutes ~ 100 minutes.The thickness of the film formed in this way is preferably 0.001 μm ~ 1 μm, is more preferably 0.005 μm ~ 0.5 μm.
(1-B) when manufacturing IPS type or FFS type liquid crystal display device, be provided with comprise the patterned substrate for the nesa coating of interdigitated electrode structure or the electrode of metallic membrane electrode forming surface, with the one side of subtend substrate that electrode is not set, coating of liquid crystalline alignment agent respectively, then each coated face is heated, form film thus.The patterning method of heating condition, nesa coating or metallic membrane after now used substrate and the material of nesa coating, coating process, coating, the pre-treatment of substrate and the preferred thickness of film formed identical with described (1-A).Metallic membrane can use the film such as comprising the metals such as chromium.
In any one situation of described (1-A) and (1-B), all by after coating of liquid crystalline alignment agent on substrate, remove organic solvent and form liquid crystal orientation film or become the film of liquid crystal orientation film.Now, also the polyamic acid of allotment in liquid crystal aligning agent, poly amic acid ester and polyimide can be made to carry out dehydration closed-loop reaction by heating further after film is formed, thus be formed further through the film of imidization.
[step (2): alignment capability gives process]
When manufacturing TN type, STN type, IPS type or FFS type liquid crystal display device, implement the process of the film formed in described step (1) being given to liquid crystal aligning ability.Thus, the alignment capability of liquid crystal molecule is imparted to film and becomes liquid crystal orientation film.Alignment capability gives process can enumerate friction treatment, light orientation process etc.: described friction treatment is by utilizing the roller being wound with the cloth comprising the fibers such as such as nylon, artificial silk, cotton, carrying out wiping to film to certain orientation; Described smooth orientation process is radioactive rays film being irradiated to polarisation or non-polarized.The rub resistance of the liquid crystal orientation film particularly formed by described liquid crystal aligning agent is high, when adopting friction treatment to give process as alignment capability, is also difficult to produce scar or film stripping.On the other hand, when manufacturing VA type liquid crystal display device, the film formed directly can be used as liquid crystal orientation film, also can give process to this film implementation orientation ability in described step (1).
In addition, also can carry out following process further to the liquid crystal orientation film after friction treatment, in each region, there is different liquid crystal aligning abilities to make liquid crystal orientation film: make by a part of irradiation ultraviolet radiation to liquid crystal orientation film the process that the tilt angle in a part of region of liquid crystal orientation film changes; Or after a part on liquid crystal orientation film surface forms resist film, after friction treatment is carried out in the direction different from friction treatment just now, by the process that resist film is removed.In this situation, the visual field characteristic of the liquid crystal display device of gained can be improved.The liquid crystal orientation film being suitable for VA type liquid crystal display device also can be suitable for the liquid crystal display device of polymer stabilizing orientation (Polymersustainedalignment, PSA) type.
[step (3): constructing of liquid crystal cells]
Prepare the substrate that two pieces are formed with liquid crystal orientation film in this way, between two pieces of substrates of subtend configuration, configure liquid crystal, manufacture liquid crystal cells thus.In order to manufacture liquid crystal cells, include, for example two kinds of following methods.First method is in the past known method.First, in the mode of each liquid crystal orientation film subtend, via gap (cell gap) by two pieces of substrate subtend configurations, sealing agent is used to be fitted by the periphery of two pieces of substrates, inject filling liquid crystal in the cell gap divided by substrate surface and sealing agent after, filling orifice is sealed, can liquid crystal cells be manufactured thus.In addition, the second method is for being called the method for liquid crystal drip-injection (OneDropFill, ODF) mode.Specified location on wherein one piece of substrate in the two pieces of substrates being formed with liquid crystal orientation film, the such as sealing agent of coated UV photo-hardening, and then after the set several positions on liquid crystal aligning face drip liquid crystal, to fit another block substrate in the mode of liquid crystal orientation film subtend, and liquid crystal is spread out on whole of substrate, then, whole irradiating ultraviolet light of substrate is cured the sealant, can liquid crystal cells be manufactured thus.When utilizing any one method, be all desirably the liquid crystal cells to manufacturing in this way, and then be heated to till used liquid crystal obtains the temperature of isotropic phase, then slowly be cooled to room temperature, eliminate flow orientation when liquid crystal is filled thus.
As sealing agent, such as, can use the epoxy resin etc. containing stiffening agent and the alumina balls as spacer (spacer).
Liquid crystal can enumerate nematic liquid crystal and disc-like liquid crystal, wherein be preferably nematic liquid crystal, such as, can use: schiff bases (Schiffbase) is liquid crystal, azoxy (azoxy) is liquid crystal, biphenyl system liquid crystal, Santosol 360 system liquid crystal, ester system liquid crystal, terphenyl system liquid crystal, xenyl hexamethylene methane series liquid crystal, pyrimidine system liquid crystal, diox system liquid crystal, double-octane system liquid crystal, cubane (cubane) are liquid crystal etc.In addition, also can add following material to use in these liquid crystal: the cholesteryl liquid crystals (cholestericliquidcrystal) such as such as cholesteryl chloride (cholesterylchloride), cholesteryl nonanoate (cholesterylnonanoate), cholesteryl carbonate; With the chiral agent that trade(brand)name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company) are sold; To oxygen base α-tolylene-to ferroelectric liquid crystals etc. such as amino-2-methyl butyl laurates in the last of the ten Heavenly stems.
Then, liquid crystal display device is obtained by the outer surface laminating Polarizer at liquid crystal cells.The Polarizer fitting in the outside surface of liquid crystal cells can be enumerated: be called as the Polarizer of the light polarizing film of " H film " with the clamping of rhodia protective membrane or comprise itself Polarizer of H film, and described " H film " is polyvinyl alcohol is extended film that orientation absorbs iodine.
Liquid crystal display device of the present disclosure can be effectively applied to multiple device, such as can be used for: the various display unit of clock and watch, pocket game machine, word processor, notes type PC, auto-navigation system, video camera, personal digital assistant (PersonalDigitalAssistance, PDA), digital camera, mobile phone, smart mobile phone, dull and stereotyped PC, various watch-dog, LCD TV, information display etc.
[embodiment]
Below, by embodiment, the present invention is specifically described further, but the present invention is not limited to these embodiments.
In following synthesis example, utilize following methods to the soltion viscosity of the weight average molecular weight Mw and imide rate and polymers soln that measure polymkeric substance.In addition, below, sometimes by the compound represented by formula X referred to as " compounds X ".
[the weight average molecular weight Mw of polymkeric substance]
Mw is the polystyrene conversion value utilizing the GPC under following condition to measure.
Tubing string: eastern Cao (Tosoh) (stock) manufactures, TSKgelGRCXLII
Solvent: tetrahydrofuran (THF)
Temperature: 40 DEG C
Pressure: 68kgf/cm 2
[the imide rate of polymkeric substance]
Solution containing polyimide is fed in pure water, the precipitation of gained, at room temperature fully after drying under reduced pressure, is dissolved in deuterodimethylsulfoxide, using tetramethylsilane as primary standard, at room temperature measures 1h-nucleus magnetic resonance ( 1h-NuclearMagneticResonance, 1h-NMR).According to gained 1h-NMR spectrum, uses following numerical expression (1) to obtain imide rate.
Imide rate (%)=(1-A 1/ A 2× α) × 100... (1)
(in numerical expression (1), A 1for the peak area come by the proton of NH base occurred near chemical shift 10ppm, A 2for the peak area come by other protons, α is the number ratios of other protons relative to a proton of the NH base in the precursor (polyamic acid) of polymkeric substance)
[soltion viscosity of polymers soln]
The soltion viscosity (mPas) of polymers soln uses E type rotational viscosimeter, measures at 25 DEG C.
The synthesis > of < silicoorganic compound
[synthesis example 1-1: the synthesis of compound (Si-1)]
By APTES (3-aminopropyltriethoxysilane, and 1 APTES), 2,3,4-tetramethylene tetracarboxylic dianhydride (1,2,3,4-cyclobutanetetracarboxylicdianhydride, CB), make an addition to METHYLPYRROLIDONE (N-methyl-2-pyrrolidone with the allotment ratio of APTES: CB=2: 1 (mol ratio), NMP) in, stir, at 25 DEG C, carry out reaction in 6 hours, obtain containing the solution of compound (Si-1) as silicoorganic compound.
[synthesis example 1-2 ~ synthesis example 1-6]
Except the compound (precursor) used in reaction and their allotment ratio are changed to as described in Table 1, by the operation identical with synthesis example 1-1, obtain respectively containing the solution of compound (Si-2) ~ compound (Si-6) as silicoorganic compound.
[table 1]
In table 1, the abbreviation of precursor as described below.
(precursor 1: silane compound)
C-1:3-aminopropyltriethoxywerene werene (APTES)
C-2:3-trimethoxysilylpropyl Succinic anhydried
C-3:3-glycidyloxypropyl Trimethoxy silane
(precursor 2: other compounds)
AN-1: pyromellitic acid anhydride
AN-2:1,2,3,4-tetramethylene tetracarboxylic dianhydride (CB)
DA-1: Ursol D
B-1: MALEIC ANHYDRIDE
B-2:2,3-pyridine dicarboxylic acid acid anhydride
B-3: piperazine
The synthesis > of < polymkeric substance
[synthesis example 2-1: the synthesis of polymkeric substance (PAA-1)]
Using two [2-(4-aminophenyl) ethyl] hexanodioic acids of the pyromellitic acid anhydride of 100 molar part as tetracarboxylic dianhydride and 100 molar part as diamines, be dissolved in METHYLPYRROLIDONE (NMP), at 60 DEG C, carry out reaction in 6 hours, obtain the polyamic acid solution that solid component concentration is 15 % by weight.The polyamic acid solution of gained is divided and takes a morsel, measure and the soltion viscosity that obtains is 420mPas.
[synthesis example 2-2 ~ synthesis example 2-7]
Except in described synthesis example 2-1, beyond the kind of the tetracarboxylic dianhydride that uses and amine (diamines and monoamine) in reaction and quantitative change are more as described in following table 2, obtain polyamic acid in the mode identical with synthesis example 2-1.In addition, about synthesis example 2-2 ~ synthesis example 2-7, the usage ratio (molar part) of the numeric representation in table 2 for total amount 100 molar part of the tetracarboxylic dianhydride used in reaction.
Tetracarboxylic dianhydride in table 2 and the abbreviation of diamines are as described below.
(tetracarboxylic dianhydride)
AN-1: pyromellitic acid anhydride
AN-2:1,2,3,4-tetramethylene tetracarboxylic dianhydride
AN-3:2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride
AN-4: dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride
AN-5:5-(2,5-dioxotetrahydro furans-3-base)-8-methyl-3a, 4,5,9b-tetrahydrochysene naphtho-[1,2-c] furans-1,3-diketone
AN-6:1, ammediol two (trimellitic anhydride ester)
AN-7: two (chloroformyl) tetramethylene-2, the 4-carboxylicesters of dimethyl-1,3-
AN-8: two (chloroformyl) pentamethylene-2, the 4-carboxylicesters of dimethyl-1,3-
[changing 13]
(diamines)
DA-1: Ursol D
DA-2:4,4 '-diaminodiphenyl-methane
DA-3:4,4 '-diamino-diphenyl amine
Two (4-amino-benzene oxygen) pentane of DA-4:1,5-
DA-5:4-aminophenyl-4 '-Aminobenzoate
DA-6: two [2-(4-aminophenyl) ethyl] hexanodioic acid
DA-7:2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine
DA-8:4,4 '-diamino triphenylamine
DA-9: the compound represented by following formula (DA-9)
DA-10:4-(tetradecyloxyaniline) benzene-1,3-diamines
DA-11: stearic amine
Two (3-the aminopropyl)-tetramethyl disiloxane of DA-12:1,3-
Two (the 4-amino benzoyl oxygen base) cholestane of DA-13:3,6-
DA-14: the compound represented by following formula (DA-14)
DA-15: the compound represented by following formula (DA-15)
[changing 14]
[synthesis example 2-8: the synthesis of polymkeric substance (PI-8)]
Using 2 of 100 molar part as tetracarboxylic dianhydride, 3,5-tricarboxylic cyclopentyl acetic acid dianhydride and as the Ursol D of 80 molar part of diamines, 4 of 10 molar part, 2 of 4 '-diaminodiphenyl-methane and 10 molar part, 2 '-bis-(trifluoromethyl)-4,4 '-benzidine is dissolved in NMP, at room temperature carries out reaction in 6 hours, obtains the polyamic acid solution that solid component concentration is 15 % by weight.In this polyamic acid solution, add NMP and make solid component concentration become 10 % by weight, relative to total 100 molar part of tetracarboxylic dianhydride, and to add respectively be respectively pyridine and the diacetyl oxide of 200 molar part, carries out dehydration closed-loop reaction in 4 hours at 110 DEG C.After dehydration closed-loop reaction, utilize new NMP to carry out solvent exchange to intrasystem solvent, obtain and contain the solution that imide rate is the polyimide (polymkeric substance (PI-8)) of 75%.Be adjusted to 15 % by weight and the measured in solution viscosity obtained for the polymkeric substance utilizing NMP by gained (PI-8), result is 520mPas.
[synthesis example 2-9: the synthesis of polymkeric substance (PI-9)]
Except in described synthesis example 2-8, by the quantitative change of the kind of the tetracarboxylic dianhydride that uses and diamines in reaction and amount and pyridine and diacetyl oxide more as described in as described in table 2 beyond, carry out the operation identical with synthesis example 2-9, obtain polyimide (polymkeric substance (PI-9)) thus.In addition, about synthesis example 2-9, the usage ratio (molar part) of the numeric representation in table 2 for total amount 100 molar part of the tetracarboxylic dianhydride used in reaction.Be adjusted to 15 % by weight and the measured in solution viscosity obtained for the polymkeric substance utilizing NMP by gained (PI-9), result is 520mPas.
[synthesis example 2-10: the synthesis of polymkeric substance (PAE-10)]
Add as the Ursol D (being 80 molar part for total amount 100 molar part of the diamines used in synthesis) of the 6.92g of diamines and 4, the 4 '-diaminodiphenyl-methane of 3.17g (being 20 molar part for total amount 100 molar part of the diamines used in synthesis) and the pyridine of 15ml and the METHYLPYRROLIDONE (NMP) of 505ml and dissolve.While this solution is carried out water-cooled stirring, while add the dimethyl-1 of 2.975g (being 97 molar part for total amount 100 molar part of the diamines used in synthesis), two (chloroformyl) tetramethylene-2 of 3-, 4-carboxylicesters, and then add NMP in the mode that solid component concentration becomes 5 % by weight, carry out water-cooled and stir 4 hours.This solution is injected in the water of 250g, polymkeric substance is separated out, carry out leaching polymkeric substance by suction filtration, after again washing with the water of 250g, utilize the methyl alcohol of 63g to wash 3 times, at 40 DEG C, carry out drying under reduced pressure, obtain the poly amic acid ester powder of 28g thus.The weight average molecular weight of this poly amic acid ester (polymkeric substance (PAE-10)) is Mw=27,000.In addition, about synthesis example 2-10, numerical value in table 2 is represent the usage ratio (molar part) for total amount 100 molar part of the tetracarboxylic acid derivatives used in reaction for tetracarboxylic acid derivatives, is represent the usage ratio (molar part) for total amount 100 molar part of the diamines used in reaction for diamines.
[synthesis example 2-11: the synthesis of polymkeric substance (PAE-11)]
Except in described synthesis example 2-10, by the quantitative change of the kind of the tetracarboxylic acid diester dihalide that uses and diamines in reaction and amount and pyridine and diacetyl oxide more as described in as described in table 2 beyond, carry out the operation identical with synthesis example 2-10, obtain poly amic acid ester (polymkeric substance (PAE-11)) thus.In addition, about synthesis example 2-11, the numerical value in table 2 and described synthesis example 2-10 are identical meanings.
The preparation of < liquid crystal aligning agent and evaluation >
[embodiment 1]
(1) preparation of liquid crystal aligning agent
Using the polymkeric substance (PAA-1) obtained in the synthesis example 2-1 of 100 weight parts as polymkeric substance and the compound (Si-1) obtained in the synthesis example 1-1 of 2 weight parts of silicoorganic compound, be dissolved in and comprise gamma-butyrolactone (γ-butyrolactone, GBL), NMP and diethylene glycol diethyl ether (diethyleneglycoldiethylether, DEDG), in mixed solvent (GBL: NMP: DEDG=55: 30: 15 (weight ratio)), the solution that solid component concentration is 6.0 % by weight is made.Utilize aperture to be that this solution filters by the strainer of 0.2 μm, prepare liquid crystal aligning agent thus.
(2) rub resistance evaluation
Use the liquid crystal aligning agent of preparation in described (1), form film on a quartz substrate, then use the friction gear possessing the roller being wound with artificial silk cloth, utilize two conditions (condition (A) and condition (B)) recorded in following table 3 to carry out friction treatment.Utilize Virahol to wash the film (liquid crystal orientation film) after friction treatment, confirm the stripping of alignment films on substrate and the presence or absence of friction scar with visual.Now, being rub resistance " good (zero) " by any one all unobservable average evaluation of the stripping of liquid crystal orientation film and friction scar, is " bad (×) " by least any one the average evaluation observing the stripping of liquid crystal orientation film and friction scar.Its result is, in this embodiment, under arbitrary condition of condition (A) and condition (B), all do not observe stripping and the friction scar of liquid crystal orientation film, be the result of rub resistance " well ".
[table 3]
Condition (A) Condition (B)
Hair press-in length [mm] 0.5 0.5
Roller revolution [rpm] 1000 1000
Platform movement speed [cm/sec] 20 20
Rubbing number [secondary] 2 10
(3) manufacture of liquid crystal cells
Use liquid crystal orientation film printing press (Japan's description printing (stock) manufactures), it is on the electrode surface of the glass substrate of 1mm that the liquid crystal aligning agent prepared in described (1) is coated the thickness with the ITO electrode being set to comb teeth-shaped, the hot plate of 80 DEG C heats (prebake conditions) 1 minute and after removing solvent, the hot plate of 200 DEG C heats (toasting afterwards) 10 minutes, form the film that average film thickness is 0.06 μm.For this film, utilize and there is the friction machine of the roller being wound with artificial silk cloth, revolve several 500rpm with roller, platform movement speed 3cm/ second, hair press-in length 0.4mm carry out friction treatment, give liquid crystal aligning ability.Then, in ultrapure water, carry out 1 minute ultrasonic washing, in 100 DEG C of cleaning ovens dry 10 minutes then, obtain the substrate with liquid crystal orientation film thus.In addition, be highly 5 μm for being dispersed with area occupation ratio 0.1%, diameter be the thickness without electrode of the circular photosensitivity spacer (photospacer) of 5 μm is the glass substrate of 1mm, also repeat described operation, obtain the substrate that a pair (two pieces) have liquid crystal orientation film.
Then, for the wherein one piece of substrate in described a pair substrate, after the outer rim coating in the face with liquid crystal orientation film adds and has diameter to be the epoxy resin adhesive of the alumina balls of 5.5 μm, in the relative mode of liquid crystal aligning face by the crimping of a pair substrate overlap, make adhesive hardens.Then, from liquid crystal injecting port to after filling nematic liquid crystal (Merck (Merck) company manufactures, MLC-2042) between a pair substrate, utilize acrylic acid series ray hardening type adhesive to be sealed by liquid crystal injecting port, manufacture liquid crystal cells thus.
(4) evaluation that the bright spot of liquid crystal cells is bad
Use pull and push dynamometer (pushpullgauge) (happy motor (Imada) (stock) manufactures), to the central part of the liquid crystal cells manufactured in described (3), apply pressure 5 seconds in the mode becoming 40N.Repeated 100 times, the average evaluation of bright spot is not observed for " good (zero) " by utilizing polarizing microscope, being " can (△) " by the average evaluation of observing 1 ~ 9 bright spots, be " bad (×) " by the average evaluation of the bright spot observing more than 10.Its result is, does not observe bright spot in this embodiment, is the result of " well ".
(5) the evaluation A of liquid crystal aligning
For the liquid crystal cells manufactured in described (3), utilize polarizing microscope to observe the presence or absence of the flow orientation of liquid crystal, and utilizing polarizing microscope to observe the presence or absence of the abnormal area in the light and shade change when repeating on-off (applying to remove) 5V voltage, evaluating liquid crystal orientation thus.Evaluate as follows: be liquid crystal aligning " good (zero) " by the average evaluation that flow orientation and abnormal area are not all observed, though will not find flow orientation, but the average evaluation observing abnormal area is " can (△) ", be " bad (×) " by the average evaluation finding flow orientation.Its result is, the liquid crystal aligning of this embodiment is the evaluation of " well ".
(6) the evaluation B (the resistance to image retention under high temperature) of liquid crystal aligning
The method of described (3) is utilized to prepare two liquid crystal cells, respectively under backlight, at 60 DEG C, one of them (element A) is applied to the voltage of alternating current 20 hours of 10V, another (element B) is applied to the voltage of alternating current 20 hours of 1V.Then, representing the luminance difference when voltage being applied element A and the element B observed when being converted to the volts DS of 2.5V with 256 gradients, evaluating the resistance to image retention under hot environment according to luminance difference.Average evaluation luminance difference being less than 5 is resistance to image retention " well ", by more than 5 and the average evaluation being less than 10 is resistance to image retention "available", is resistance to image retention " bad " by the average evaluation more than 10.Its result is, is the evaluation of resistance to image retention " well " in this embodiment.
(7) electrical characteristic evaluation (voltage retention)
For the liquid crystal cells utilizing the method for described (3) to manufacture, apply the voltage of 5V with the application time of 60 microseconds, the span of 167 milliseconds at 40 DEG C after, measure the voltage retention (VHR) after 167 milliseconds from applying to remove.In addition, determinator is the VHR-1 using Dongyang Te Kenika (ToyoTechnica) (stock) to manufacture.The evaluation of the electrical characteristic of liquid crystal cells be by voltage retention be more than 98% situation be set to " well ", by more than 95% and the situation being less than 98% is set to "available", the situation of less than 95% is set to " bad ".Its result is, this embodiment is the evaluation of electrical characteristic " well ".
[embodiment 2 ~ embodiment 12 and comparative example 1 ~ comparative example 5]
Except in described embodiment 1, the kind of used polymkeric substance and additive and amount are set to beyond as shown in following table 4, carry out the preparation of liquid crystal aligning agent and the manufacture of liquid crystal cells in the same manner as example 1, carry out various evaluation.Evaluation result is shown in following table 4.
In table 4, the abbreviation of additive as described below.
Add-1:N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane
Add-2:3-glycidyloxypropyl Trimethoxy silane
Add-3:3-aminopropyltriethoxywerene werene
Si-7: the compound represented by following formula (si-7)
[changing 15]
As shown in table 4, in the liquid crystal aligning agent of the embodiment 1 ~ embodiment 12 containing the silicoorganic compound containing N structure had represented by described formula (1a), the rub resistance of the liquid crystal orientation film using it to be formed is good.In addition, be the result of " well " or "available" in resistance to image retention under the evaluation (flow orientation of liquid crystal and the presence or absence of abnormal area), high temperature of the bad generation difficulty of bright spot, liquid crystal aligning of the liquid crystal cells of embodiment 1 ~ embodiment 12 and electrical characteristic, and obtain the balance of various characteristic.On the other hand, in comparative example, at least either side of the generation difficulty that the bright spot in the rub resistance and liquid crystal cells of liquid crystal orientation film is bad and liquid crystal aligning, all poor than embodiment.

Claims (10)

1. a liquid crystal aligning agent, it comprises:
Be selected from least one polymkeric substance (P) in the cohort be made up of polyamic acid, poly amic acid ester and polyimide; And
There are the silicoorganic compound containing N structure represented by following formula (1a), wherein, " * 1 " in following formula (1a) and hydrogen atom, methylene radical or monovalent hydrocarbon bond;
In formula (1a), R aand R bit is separately divalent organic base; " * 1 " and " * 2 " represents associative key.
2. liquid crystal aligning agent according to claim 1, wherein said silicoorganic compound are and then meet in molecule the R had in hydroxyl and described formula (1a) afor the compound of at least one in carbonyl.
3. a liquid crystal aligning agent, it comprises: be selected from least one polymkeric substance (P) in the cohort be made up of polyamic acid, poly amic acid ester and polyimide; And
Have represented by following formula (1a) containing N structure, and meet in molecule the R had in hydroxyl and described formula (1a) afor the silicoorganic compound of at least one in carbonyl;
In formula (1a), R aand R bit is separately divalent organic base; " * 1 " and " * 2 " represents associative key.
4. liquid crystal aligning agent according to any one of claim 1 to 3, wherein said silicoorganic compound are for being selected from by least one had in cohort that the described silicon compound containing N structure and hydroxyl and the silicon compound with urea structure form.
5. liquid crystal aligning agent according to any one of claim 1 to 3, wherein said silicoorganic compound are the amine compound making to have at least one be selected from amino by one-level and that secondary is amino formed cohort, carry out reacting with the compound containing reactive base of at least one had in the cohort that is selected from and is made up of anhydride group, epoxy group(ing) and oxetanylmethoxy and the compound that obtains, and
Described amine compound and the described compound containing reactive base at least any one is the compound with Siliciumatom.
6. liquid crystal aligning agent according to any one of claim 1 to 3, wherein said silicoorganic compound have hydroxyl, and
At least one and carbonyl bond of the hydroxyl that described silicoorganic compound have.
7. liquid crystal aligning agent according to any one of claim 1 to 3, wherein said silicoorganic compound are at least one in the cohort that is selected from the compound represented by following formula (1) and the compound represented by following formula (2) and forms
In formula (1), R 19for hydrogen atom or monovalent hydrocarbon or intramolecular two R 19the bivalent hydrocarbon radical that bond is formed; R 20for trivalent organic radical, R 21for divalent organic base, R 22and R 23be separately monovalent hydrocarbon, R 24for (h+i) valency organic radical; A 1for singly-bound or carbonyl, A 2for alkane two base of singly-bound, carbonyl or carbon number 1 ~ 3, B 1and B 2it is separately alkane two base of carbonyl or carbon number 1 ~ 3; E, f, g and i are separately the integer of 0 ~ 4, e+f+g>=1 and e+i>=1; H is the integer of 1 ~ 4, and j is the integer of 1 ~ 3; Wherein, at R 20, R 22, R 23, A 1, A 2, B 1and B 2when existing multiple respectively, multiple R 20, R 22, R 23, A 1, A 2, B 1and B 2there is described definition independently;
In formula (2), R 31and R 32be separately monovalent hydrocarbon, R 33for divalent organic base, R 34for any monovalent organic radical; T is the integer of 1 ~ 3; Wherein, at R 31, R 32when existing multiple, multiple R 31, R 32there is described definition independently.
8. liquid crystal aligning agent according to any one of claim 1 to 3, wherein relative to the described polymkeric substance (P) of 100 weight parts, the allotment ratio of described silicoorganic compound is 0.1 weight part ~ 30 weight part.
9. a liquid crystal orientation film, it uses liquid crystal aligning agent according to any one of claim 1 to 8 and is formed.
10. a liquid crystal display device, it comprises liquid crystal orientation film according to claim 9.
CN201510440953.4A 2014-08-29 2015-07-24 Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element Pending CN105385455A (en)

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