WO2011010619A1 - Composé de diamine, acide polyamique, polyimide et agent d'alignement des cristaux liquides - Google Patents

Composé de diamine, acide polyamique, polyimide et agent d'alignement des cristaux liquides Download PDF

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WO2011010619A1
WO2011010619A1 PCT/JP2010/062109 JP2010062109W WO2011010619A1 WO 2011010619 A1 WO2011010619 A1 WO 2011010619A1 JP 2010062109 W JP2010062109 W JP 2010062109W WO 2011010619 A1 WO2011010619 A1 WO 2011010619A1
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liquid crystal
polyamic acid
diamine compound
diamine
polyimide
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PCT/JP2010/062109
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English (en)
Japanese (ja)
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徳俊 三木
悟志 南
雅章 片山
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日産化学工業株式会社
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Priority to CN201080043007.1A priority Critical patent/CN102574811B/zh
Priority to JP2011523647A priority patent/JP5729299B2/ja
Priority to KR1020177026552A priority patent/KR102073458B1/ko
Publication of WO2011010619A1 publication Critical patent/WO2011010619A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/61—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms not forming part of a nitro radical, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/20—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Definitions

  • the present invention relates to a novel diamine compound useful as a raw material for a polymer used in a liquid crystal alignment film, a polyamic acid and a polyimide obtained using the same, and a liquid crystal alignment treatment agent. Furthermore, it is related with the liquid crystal display element which has a liquid crystal aligning film obtained from the said liquid-crystal aligning agent.
  • a liquid crystal alignment treatment agent (also referred to as a liquid crystal alignment agent) mainly composed of a polyimide precursor such as polyamic acid or a solution of soluble polyimide is applied to a glass substrate and fired.
  • a so-called polyimide-based liquid crystal alignment film is mainly used.
  • the liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal.
  • the liquid crystal alignment film used has a high voltage holding ratio and a direct current voltage has been applied due to demands for suppressing the decrease in contrast of the liquid crystal display elements and reducing the afterimage phenomenon.
  • the characteristic that the residual charge at the time is small and / or the residual charge accumulated by the DC voltage is quickly relaxed has become increasingly important.
  • a liquid crystal aligning agent containing a tertiary amine having a specific structure in addition to polyamic acid or an imide group-containing polyamic acid was used as a short time until the afterimage generated by direct current voltage disappears.
  • a liquid crystal aligning agent containing a soluble polyimide using a specific diamine compound having a pyridine skeleton as a raw material for example, see Patent Document 1.
  • a compound containing one carboxylic acid group in the molecule In addition to polyamic acid and its imidized polymer, a compound containing one carboxylic acid group in the molecule, assuming that the voltage holding ratio is high and the time until the afterimage generated by direct current voltage disappears is short , Using a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amine group in the molecule (for example, a patent Document 3) is known.
  • liquid crystal alignment film to be used has to be more reliable than conventional liquid crystal alignment films.
  • the electrical characteristics of the liquid crystal alignment film are not only good in initial characteristics but also, for example, at a high temperature for a long time. There is a need to maintain good properties even after exposure.
  • An object of the present invention is to provide a liquid crystal alignment treatment agent capable of obtaining a liquid crystal alignment film having a high voltage holding ratio and capable of quickly relieving residual charges accumulated by a DC voltage even after being exposed to a high temperature for a long time. It is in providing the diamine compound which can be used as a raw material of the polyamic acid and / or polyimide (henceforth also referred to as a polymer). Furthermore, an object of the present invention is to provide a liquid crystal alignment film having a high voltage holding ratio and capable of obtaining a liquid crystal alignment film in which residual charges accumulated by a DC voltage are quickly relaxed even after being exposed to a high temperature for a long time. It is an object of the present invention to provide a liquid crystal display device with high reliability that can withstand a long-term use in a treating agent and a severe use environment.
  • X 1 represents —CO— or —CONH—
  • X 2 represents an alkylene group having 1 to 5 carbon atoms or a non-aromatic heterocyclic ring containing a nitrogen atom
  • X 3 represents 1 to 5 carbon atoms
  • It represents a 5-membered or 6-membered aromatic heterocycle containing two nitrogen atoms, which may be substituted with 5 alkyl groups.
  • the diamine component contains 0.01 to 99 mol of a diamine compound having a carboxyl group in the molecule with respect to 1 mol of the diamine according to any one of (1) to (3) above.
  • the polyamic acid according to the above (6) or (7), wherein the diamine compound having a carboxyl group in the molecule is a diamine represented by the following formula [2], or a polyimide obtained by imidizing the polyamic acid .
  • X 5 is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4.
  • (11) A liquid crystal alignment film obtained from the liquid crystal aligning agent according to (9) or (10).
  • (12) A liquid crystal display device having the liquid crystal alignment film according to (11).
  • the diamine compound of the present invention is a novel diamine containing a specific structure containing a 5-membered or 6-membered aromatic heterocycle containing two nitrogen atoms in the side chain (hereinafter also referred to as a specific diamine compound). And can be obtained by a relatively simple method.
  • the 5-membered or 6-membered aromatic heterocycle containing two nitrogen atoms in the specific diamine compound functions as an electron hopping site depending on the conjugated structure thereof, so that the polyamic acid and / or the specific acid using the specific diamine compound and / or
  • the liquid crystal alignment film obtained from the polyimide polymer imidized with the polyamic acid can promote the movement of electric charge in the liquid crystal alignment film, has a high voltage holding ratio, and is exposed to a high temperature for a long time. Even in such a case, the residual charge accumulated by the DC voltage can be relaxed quickly.
  • a liquid crystal display element having a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a polyamic acid and / or a polyimide polymer using the diamine compound of the present invention is excellent in reliability and has a large screen. Therefore, it can be suitably used for high-definition liquid crystal televisions.
  • the specific diamine compound of the present invention is represented by the following formula [1].
  • X 1 represents —CO— or —CONH—
  • X 2 represents an alkylene group having 1 to 5 carbon atoms or a non-aromatic heterocyclic ring containing a nitrogen atom
  • X 3 represents 1 to 5 carbon atoms.
  • the bonding position of the two amino groups (—NH 2 ) in the formula [1] is not limited. Specifically, with respect to the linking group (X 1 ) of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring Position, 3, 5 positions. Among these, taking into consideration the reactivity when synthesizing the polyamic acid and the ease of synthesizing the diamine compound, the bonding positions of the two amino groups are positions 2, 4 and 2, 5 , 3, 5 are particularly preferred. In the formula [1], X 1 is —CO— or —CONH—.
  • X 2 is an alkylene group having 1 to 5 carbon atoms or a non-aromatic heterocyclic ring containing a nitrogen atom.
  • the alkylene group may be linear or branched.
  • the alkylene group preferably has 1 to 3 carbon atoms.
  • X 2 is a non-aromatic heterocyclic ring containing a nitrogen atom
  • examples include a pyrrolidine ring, a piperidine ring, a piperazine ring, a pyrazolidine ring, a quinuclidine ring, and an imidazolidine ring.
  • a non-aromatic heterocyclic ring having a 5-membered ring or a 6-membered ring is preferable because good alignment can be obtained when a liquid crystal alignment film is used.
  • the non-aromatic heterocycle contains two nitrogen atoms
  • ionic impurities in the liquid crystal are adsorbed at the liquid crystal alignment film interface, and the liquid crystal display device has good electrical characteristics. It is desirable to keep.
  • a piperazine ring is particularly preferable as the non-aromatic heterocyclic ring containing a nitrogen atom.
  • X 3 is a 5-membered or 6-membered aromatic heterocyclic ring containing two nitrogen atoms, which may be substituted with an alkyl group having 1 to 5 carbon atoms.
  • 5-membered or 6-membered aromatic heterocycles containing two nitrogen atoms include imidazole ring, pyrazole ring, pyrazine ring, pyrimidine ring and pyridazine ring. Among them, imidazole ring and pyrazine A ring or a pyrimidine ring is preferred.
  • the aromatic heterocycle in X 3 is substituted with an alkyl group, the alkyl group preferably has 1 to 3 carbon atoms.
  • the specific diamine compound of the present invention can be obtained by synthesizing a dinitro compound represented by the formula [3], further reducing the nitro group of the dinitro compound and converting it to an amino group.
  • a dinitro compound represented by the formula [3] There is no particular limitation on the method for reducing the dinitro compound, and usually palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran, dioxane, There is a method in which hydrogen gas, hydrazine, hydrogen chloride, or the like is used in an alcohol-based solvent.
  • X 1 , X 2 , and X 3 in the formula [ 3 ] have the same definition as in the formula [1].
  • Dinitro compound represented by the formula [3] via the X 1 against dinitrobenzene -X 2 -X 3 can be obtained by a method of attaching, for example, X 1 is an amide bond (-CONH- ), A method of reacting dinitrobenzene chloride with an amino compound containing X 2 and X 3 in the presence of alkali.
  • X 1 is a reverse amide bond (—HNCO—)
  • a method of reacting an amino group-containing nitrobenzene and an acid chloride containing X 2 and X 3 in the presence of an alkali can be mentioned.
  • Examples of the dinitrobenzene acid chloride include 3,5-dinitrobenzoic acid chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 3,5-dinitrobenzyl chloride, and 2,4-dinitrobenzyl chloride.
  • Examples of the amino group-containing nitrobenzene include 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline and the like. In consideration of availability of raw materials and reaction, one or more kinds can be selected and used.
  • the polymer of the present invention is a polyamic acid obtained by reaction of a diamine component containing a specific diamine compound and tetracarboxylic dianhydride and a polyimide obtained by dehydrating and ring-closing this polyamic acid. Any of these polyamic acids and polyimides are useful as a polymer for obtaining a liquid crystal alignment film.
  • the liquid crystal alignment film obtained using the polymer of the present invention has a higher voltage holding ratio as the content ratio of the specific diamine compound in the diamine component increases, and even after being exposed to a high temperature for a long time, The residual charge accumulated by the DC voltage is alleviated faster.
  • the diamine component is the specific diamine compound. Furthermore, it is preferable that 5 mol% or more of a diamine component is a specific diamine compound, More preferably, it is 10 mol% or more. Although 100 mol% of the diamine component may be a specific diamine compound, the specific diamine compound is preferably 80 mol% or less of the diamine component, more preferably, from the viewpoint of uniform coatability when applying the liquid crystal aligning agent. It is 40 mol% or less.
  • ⁇ Diamine compound having a carboxyl group in the molecule when a diamine compound having a carboxyl group in the molecule is used together with the specific diamine compound as the diamine component, an aromatic heterocyclic ring having two nitrogen atoms of the specific diamine compound is present in the molecule.
  • the carboxyl group of the diamine compound having a carboxyl group is linked with an electrostatic interaction such as salt formation or hydrogen bond, charge transfer occurs between the carboxyl group and the nitrogen-containing aromatic heterocycle. Therefore, the charge transferred to the nitrogen-containing aromatic heterocyclic moiety can efficiently move within and between the molecules of the copolymer, and as a result, the liquid crystal alignment treatment agent obtained in this case is a liquid crystal alignment film.
  • the voltage holding ratio is high, and even after being exposed to a high temperature for a long time, there is an effect that the residual charge accumulated by the DC voltage is relaxed and faster.
  • the specific structure of the diamine compound having a carboxyl group in the molecule is not particularly limited, but a compound represented by the formula [2] is preferable.
  • X 5 is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4. If the formula [2] is specifically shown, the structures of the following formulas [3] to [7] can be mentioned.
  • m1 is an integer of 1 to 4
  • X 6 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, — CF 2 —, —C (CF 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 — , -COO-, -OCO-, -CON (CH 3 )-, or -N (CH 3 ) CO-
  • m2 and m3 are each an integer of 0 to 4
  • m2 + m3 is an integer of 1 to 4
  • m4 and m5 are each an integer of 1 to 5
  • X 7 is a linear or branched alkyl group having 1 to 5 carbon atoms, and m6
  • X 8 is a single bond, -CH 2 -, - C 2 H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3 2 -, - O -, - CO -, - NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH2 -, - COO -, - OCO -, - CON (CH 3 ) — or —N (CH 3 ) CO—, and m7 represents an integer of 1 to 4.
  • X 6 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, or —
  • X 8 is a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—, wherein m7 is an integer of 1 to 2.
  • diamine compound represented by the formulas [3] to [7] include the compounds of the following formulas [8] to [18].
  • X 9 is a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO.
  • X 10 is a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O —, —OCH 2 —, —COO—, or —OCO—.
  • examples of the diamine side chain include diamine compounds having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and a cyclic substituent composed thereof.
  • Specific examples of the diamine compound include diamine compounds represented by the following formulas [DA1] to [DA26].
  • R 1 is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
  • R 2 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—.
  • R 3 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
  • R 4 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
  • R 5 represents 1 carbon atom.
  • R 6 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH. 2 — or —CH 2 —, wherein R 7 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.
  • R 8 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH. 2 —, —CH 2 —, —O—, or —NH—, wherein R 9 is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group. is there.
  • diaminosiloxane represented by the following formula [DA27] and the like are also included.
  • m is an integer of 1 to 10.
  • Other diamine compounds may be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
  • tetracarboxylic dianhydride The tetracarboxylic dianhydride reacted with the diamine component to obtain the polyamic acid of the present invention is not particularly limited.
  • the preferable specific example is given below.
  • the tetracarboxylic dianhydride can be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
  • a known synthesis method can be used.
  • tetracarboxylic dianhydride and a diamine component are reacted in an organic solvent.
  • the reaction between the tetracarboxylic dianhydride and the diamine component is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.
  • the organic solvent used for the reaction between the tetracarboxylic dianhydride and the diamine component is not particularly limited as long as the produced polyamic acid dissolves. Specific examples are given below.
  • a method of adding by dispersing or dissolving a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and alternately adding a tetracarboxylic dianhydride and a diamine component. Any of these methods may be used.
  • the tetracarboxylic dianhydride or diamine component consists of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed to form a high molecular weight product.
  • the polymerization temperature at that time can be selected from -20 ° C. to 150 ° C., but is preferably in the range of ⁇ 5 ° C. to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the total concentration of the tetracarboxylic dianhydride and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
  • the ratio of the total number of moles of tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably 0.8 to 1.2. Similar to the normal polymerization reaction, the molecular weight of the polyamic acid produced increases as the molar ratio approaches 1.0.
  • the polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the above polyamic acid, and is useful as a polymer for obtaining a liquid crystal alignment film.
  • the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
  • Examples of the method for imidizing the polyamic acid include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
  • the temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
  • the catalytic imidation of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to the polyamic acid solution and stirring at -20 ° C to 250 ° C, preferably 0 ° C to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is easy.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the reaction solution may be poured into a poor solvent and precipitated.
  • the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
  • the polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.
  • the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
  • the molecular weight of the polyamic acid and the polyimide contained in the liquid crystal aligning agent of the present invention is determined by considering the strength of the coating film obtained therefrom, the workability when forming the coating film, and the uniformity of the coating film.
  • the weight average molecular weight measured by the Permeation Chromatography method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
  • the liquid crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a solution in which a polymer component for forming a polymer film is dissolved in a solvent.
  • the polymer component includes at least one polymer of the polymer of the present invention described above.
  • the content of the polymer component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass in the liquid crystal aligning agent.
  • all of the above polymer components may be the polymer of the present invention, and may contain other polymers as long as the effects of the present invention are not impaired.
  • the content thereof is preferably 0.05 to 4 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 1 part by mass of the polymer of the present invention. It is.
  • the other polymer examples include a polyamic acid obtained by using a diamine compound other than the specific diamine compound as a diamine component to be reacted with a tetracarboxylic dianhydride component, or a polyimide obtained by imidizing the polyamic acid.
  • the solvent used in the liquid crystal aligning agent of the present invention is preferably an organic solvent that dissolves the polymer component, and specific examples thereof are given below.
  • the liquid crystal aligning agent of this invention may contain components other than the above.
  • examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate.
  • examples of the solvent that improves the uniformity of the film thickness and the surface smoothness include poor solvents that have low solubility in the polymer component in the liquid crystal aligning agent. Specific examples of the poor solvent include the following.
  • the poor solvent may be used alone or in combination.
  • the poor solvent is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal aligning agent.
  • the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.
  • F-top EF301, EF303, EF352 manufactured by Tochem Products
  • MegaFuck F171, F173, R-30 manufactured by Dainippon Ink
  • Florard FC430, FC431 manufactured by Sumitomo 3M
  • Asahi Guard AG710 Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.).
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. is there.
  • the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
  • the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, More preferably, it is 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
  • the liquid crystal alignment treatment agent of the present invention is a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. A substance, and further, a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.
  • the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without applying an alignment treatment after being applied and baked on a substrate and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
  • a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process.
  • an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
  • the method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and ink jet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
  • Firing after applying the liquid crystal aligning agent on the substrate is performed at 50 ° C. to 300 ° C., preferably 80 ° C. to 250 ° C. by a heating means such as a hot plate, and the solvent is evaporated to form a coating film. Can do. If the thickness of the coating film formed after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. The thickness is preferably 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
  • the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
  • liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spread a spacer on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure, or a method in which the substrate is attached to the surface after the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed, and the like is sealed.
  • the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.
  • the molecular weight of polyimide in the synthesis example was measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Showa Denko KK and a column (KD-803, KD-805) manufactured by Shodex. .
  • GPC normal temperature gel permeation chromatography
  • the imidation ratio of polyimide in the synthesis example was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard ⁇ 5 manufactured by Kusano Kagaku Co., Ltd.) and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture). The solution was completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum.
  • JNW-ECA500 JNW-ECA500
  • the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is a proton peak integrated value derived from NH group of amic acid
  • y is a peak integrated value of reference proton
  • ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
  • Example 4 BODA (3.24 g, 13.0 mmol), p-PDA (0.65 g, 6.01 mmol), PCH7DAB (3.30 g, 8.67 mmol), and the diamine compound (4) obtained in Example 1 (0) .68 g, 2.62 mmol) were mixed in NMP (14.5 g) and reacted at 80 ° C. for 5 hours, and then CBDA (0.85 g, 4.34 mmol) and NMP (11.9 g) were added.
  • the polyamic acid solution (A) (concentration: 24.8% by mass) was obtained by reacting at 6 ° C. for 6 hours.
  • the number average molecular weight of this polyamic acid was 22,800, and the weight average molecular weight was 53,900.
  • NMP was added to the polyamic acid solution (A) (20.0 g) obtained in Example 4 to dilute the polyamic acid concentration to 6% by mass, and then acetic anhydride (2.65 g) and pyridine ( 2.07 g) was added and reacted at 80 ° C. for 2 hours.
  • This reaction solution was put into methanol (350 ml), and the resulting precipitate was separated by filtration.
  • This deposit was wash
  • Example 6 BODA (3.25 g, 13.0 mmol), DBA (0.52 g, 3.42 mmol), PCH7DAB (3.30 g, 8.67 mmol), and the diamine compound (4) obtained in Example 1 (1.36 g) , 5.24 mmol) in NMP (15.5 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.85 g, 4.34 mmol) and NMP (12.7 g) were added, and Reaction was performed for 6 hours to obtain a polyamic acid solution (C) (concentration: 24.8% by mass). The number average molecular weight of this polyamic acid was 24,100, and the weight average molecular weight was 55,500.
  • C polyamic acid solution
  • Example 7 After adding NMP to the polyamic acid solution (C) (20.1 g) obtained in Example 6 and diluting the polyamic acid concentration to 6% by mass, acetic anhydride (2.66 g) and pyridine ( 2.07 g) was added and reacted at 80 ° C. for 2 hours. This reaction solution was put into methanol (350 ml), and the resulting precipitate was separated by filtration. This deposit was wash
  • Example 8 BODA (3.15 g, 12.6 mmol), p-PDA (1.01 g, 9.34 mmol), AP18 (1.25 g, 3.32 mmol), and the diamine compound (7) obtained in Example 2 (1) .10 g, 4.28 mmol) were mixed in NMP (8.35 g) and reacted at 80 ° C. for 5 hours, and then CBDA (0.85 g, 4.34 mmol) and NMP (6.83 g) were added. The polyamic acid solution was obtained by reacting at 6 ° C. for 6 hours. The number average molecular weight of this polyamic acid was 21,500, and the weight average molecular weight was 52,400.
  • Example 9 BODA (3.22 g, 12.9 mmol), DBA (0.79 g, 5.19 mmol), PCH7DAB (3.22 g, 8.46 mmol), and the diamine compound (7) obtained in Example 2 (0.92 g) , 3.58 mmol) in NMP (13.5 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.85 g, 4.34 mmol) and NMP (11.0 g) were added, and Reaction was performed for 6 hours to obtain a polyamic acid solution.
  • the number average molecular weight of this polyamic acid was 23,700, and the weight average molecular weight was 54,000.
  • Example 10 ⁇ Example 10> BODA (2.97 g, 11.9 mmol), p-PDA (0.70 g, 6.47 mmol), PCH7DAB (3.06 g, 8.04 mmol), and the diamine compound (10) obtained in Example 3 (0 .51 g, 1.71 mmol) were mixed in NMP (12.6 g) and reacted at 80 ° C. for 5 hours, and then CBDA (0.85 g, 4.34 mmol) and NMP (10.3 g) were added. The reaction was carried out at 6 ° C. for 6 hours to obtain a polyamic acid solution (G) (concentration: 26.1% by mass). The number average molecular weight of this polyamic acid was 21,200, and the weight average molecular weight was 52,100.
  • G polyamic acid solution
  • Example 11 After adding NMP to the polyamic acid solution (G) (20.0 g) obtained in Example 10 and diluting the polyamic acid concentration to 6% by mass, acetic anhydride (2.67 g) and pyridine ( 2.05 g) was added and reacted at 80 ° C. for 2 hours. This reaction solution was poured into methanol (360 ml), and the resulting precipitate was filtered off. This deposit was wash
  • Tables 3 and 4 collectively show reaction conditions (moles of each component) and imidation ratios of Examples 4 to 11 and Synthesis Examples 3 to 6 (synthesis of polyamic acid and polyimide).
  • Example 12 NMP (10.2 g) and BCS (20.0 g) were added to the polyamic acid solution [A] (10.0 g) obtained in Example 4, and the mixture was stirred at 25 ° C. for 2 hours, thereby liquid crystal alignment treatment.
  • Agent [1] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the polymer component was uniformly dissolved.
  • [Production of liquid crystal cell] The liquid crystal alignment treatment agent [1] obtained above is spin-coated on the ITO surface of the substrate with 3 cm ⁇ 4 cm (vertical ⁇ horizontal) ITO electrodes, and baked in a hot air circulation oven at 80 ° C. for 5 minutes and 210 ° C. for 1 hour. A polyimide coating film having a thickness of 100 nm was prepared.
  • This substrate with a liquid crystal alignment film is subjected to a rubbing treatment with a roll diameter 120 mm, a rayon cloth rubbing device under the conditions of a rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.3 mm.
  • a rubbing treatment with a roll diameter 120 mm, a rayon cloth rubbing device under the conditions of a rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.3 mm.
  • Two substrates with this liquid crystal alignment film were prepared, and a 6 ⁇ m bead spacer was sprayed on the surface of one liquid crystal alignment film, and then a sealant was printed thereon.
  • the other prepared substrate was bonded so that the liquid crystal alignment film surface was on the inside and the rubbing direction was reversed, and then the sealing agent was cured to produce an empty cell.
  • Liquid crystal MLC-6608 (manufactured by Merck Japan Ltd.) was injected into this empty cell by a reduced pressure injection method to obtain an antiparallel aligned nematic liquid crystal cell.
  • [Evaluation of voltage holding ratio] A voltage of 4 V is applied to the liquid crystal cell obtained above at a temperature of 80 ° C. for 60 ⁇ s, the voltage after 16.67 ms and 1667 ms is measured, and the voltage holding ratio (%) As calculated. The results are shown in Table 5.
  • [Evaluation of relaxation of residual charge] A DC voltage of 10 V was applied to the liquid crystal cell after measuring the voltage holding ratio for 30 minutes and short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds.
  • liquid crystal aligning agents obtained in the following Examples 13 to 19 and Comparative Examples 1 to 4, as in Example 12, liquid crystal cells were prepared using these liquid crystal aligning agents, and each liquid crystal The cell was evaluated. The results are summarized in Table 5 and Table 6.
  • Example 13 NMP (36.3 g) was added to the polyimide powder [B] (5.1 g) obtained in Example 5, and dissolved by stirring at 70 ° C. for 40 hours. NMP (18.1 g) and BCS (25.6 g) were added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent [2]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the polymer component was uniformly dissolved.
  • Example 14 NMP (10.2 g) and BCS (20.0 g) were added to the polyamic acid solution [C] (10.0 g) obtained in Example 6, and the mixture was stirred at 25 ° C. for 2 hours, thereby liquid crystal alignment treatment. Agent [3] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the polymer component was uniformly dissolved.
  • Example 15 NMP (30.3 g) was added to the polyimide powder [D] (5.0 g) obtained in Example 7 and dissolved by stirring at 70 ° C. for 40 hours. NMP (14.8g) and BCS (33.8g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained liquid-crystal aligning agent [4]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the polymer component was uniformly dissolved.
  • NMP 33.0 g was added to the polyimide powder [E] (5.1 g) obtained in Example 8, and dissolved by stirring at 70 ° C. for 40 hours.
  • Example 17 NMP (34.5 g) was added to the polyimide powder [F] (5.2 g) obtained in Example 9, and dissolved by stirring at 70 ° C. for 40 hours. NMP (16.5g) and BCS (30.3g) were added to this solution, and the liquid-crystal aligning agent [6] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the polymer component was uniformly dissolved.
  • Example 18 NMP (15.6 g) and BCS (17.1 g) were added to the polyamic acid solution [G] (10.0 g) obtained in Example 10, and the mixture was stirred at 25 ° C. for 2 hours, thereby liquid crystal alignment treatment. Agent [7] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the polymer component was uniformly dissolved.
  • Example 19 NMP (35.5 g) was added to the polyimide powder [H] (5.0 g) obtained in Example 11, and dissolved by stirring at 70 ° C. for 40 hours. NMP (17.8g) and BCS (25.1g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained liquid-crystal aligning agent [8]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the polymer component was uniformly dissolved.
  • NMP (34.5 g) was added to the polyimide powder [L] (4.5 g) obtained in Synthesis Example 6 and dissolved by stirring at 70 ° C. for 40 hours.
  • NMP (17.2g) and BCS (18.8g) were added to this solution, and the liquid-crystal aligning agent [12] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the polymer component was uniformly dissolved.
  • the liquid crystal aligning agent containing the diamine compound of the present invention has a high voltage holding ratio when it is formed into a liquid crystal alignment film, and alleviates charges accumulated by direct current voltage even after being exposed to a high temperature for a long time. Can be obtained. Furthermore, a highly reliable liquid crystal display element that can withstand long-term use in a severe use environment can be provided. As a result, it is useful for TN elements, STN elements, TFT liquid crystal elements, and liquid crystal display elements of vertical alignment type and horizontal alignment type (IPS).
  • IPS vertical alignment type and horizontal alignment type

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Abstract

La présente invention concerne un nouveau composé de diamine utile en tant que matière première pour un acide polyamique et/ou un polyimide. L'acide polyamique ou le polyimide préparé en utilisant le composé de diamine peut constituer un agent d'alignement des cristaux liquides capable de former un film d'alignement des cristaux liquides qui présente un rapport de tenue de tension élevé et qui, même après une exposition à long terme à une température élevée, atteint un relâchement rapide d'une charge résiduelle accumulée par tension DC. L'invention concerne spécifiquement un nouveau composé de diamine représenté par la formule générale [1] et un agent d'alignement des cristaux liquides qui contient un acide polyamique et/ou un polyimide préparé en utilisant le composé de diamine. Dans la formule générale [1], X1 représente –CO- ou –CONH- ; X2 représente un groupe alkylène en C1 à C5 ou un hétérocycle non aromatique contenant de l'azote ; et X3 représente un hétérocycle aromatique à cinq ou six chaînons qui contient deux atomes d'azote et qui peut être substitué par un groupe alkyle en C1 à C5.
PCT/JP2010/062109 2009-07-21 2010-07-16 Composé de diamine, acide polyamique, polyimide et agent d'alignement des cristaux liquides WO2011010619A1 (fr)

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JP2012027429A (ja) * 2010-07-21 2012-02-09 Daxin Material Corp 芳香族ジアミン化合物、それを用いて調製されたポリアミック酸とポリイミド、および液晶配向剤
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CN102574811B (zh) 2015-09-09
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JP5729299B2 (ja) 2015-06-03
CN102574811A (zh) 2012-07-11
KR20120037493A (ko) 2012-04-19
KR20170110172A (ko) 2017-10-10
KR102073458B1 (ko) 2020-02-04

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