JP3968823B2 - Liquid crystal alignment agent - Google Patents

Liquid crystal alignment agent Download PDF

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JP3968823B2
JP3968823B2 JP16654497A JP16654497A JP3968823B2 JP 3968823 B2 JP3968823 B2 JP 3968823B2 JP 16654497 A JP16654497 A JP 16654497A JP 16654497 A JP16654497 A JP 16654497A JP 3968823 B2 JP3968823 B2 JP 3968823B2
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Prior art keywords
liquid crystal
group
polyamic acid
dianhydride
epoxy
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JPH10338880A (en
Inventor
幸枝 三島
圭一 山本
雅之 木村
直樹 柳通
敬祐 栗山
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Jsr株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid crystal aligning agent. More specifically, the present invention relates to a liquid crystal alignment agent that can form a liquid crystal alignment film having a high voltage holding ratio and a low residual DC voltage in a liquid crystal display element.
[0002]
[Prior art]
Currently, as a liquid crystal display element, a liquid crystal alignment film made of polyamic acid, polyimide, or the like is formed on the surface of a substrate on which a transparent conductive film is provided to form a liquid crystal display element substrate, and the two sheets are arranged to face each other. A nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a sandwich cell, and the major axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other. A TN type liquid crystal display element having a so-called TN type (Twisted Nematic) liquid crystal cell is known. Recently, an STN (Super Twisted Nematic) type liquid crystal display element has been developed which has a higher contrast than the TN type liquid crystal display element and has less viewing angle dependency. This STN type liquid crystal display element uses nematic liquid crystal blended with a chiral agent which is an optically active substance as liquid crystal, and the major axis of the liquid crystal molecule is continuously twisted over 180 degrees between substrates. The birefringence effect produced by this is utilized. The alignment of the liquid crystal in these TN type liquid crystal display elements and STN type liquid crystal display elements is usually expressed by a liquid crystal alignment film subjected to rubbing treatment.
[0003]
[Problems to be solved by the invention]
When such a liquid crystal display element is driven at a constant frame period, it is desirable that the voltage holding ratio (voltage holding ratio between frame periods) in the liquid crystal display element is high in order to obtain a display with good contrast. .
In addition, from the viewpoint of preventing a decrease in contrast due to an afterimage and an image burn-in phenomenon, it is desirable that a DC voltage remaining after the applied voltage is released (hereinafter referred to as “residual DC voltage”) is as low as possible. .
However, as for the conventional liquid crystal alignment film, in the liquid crystal display element, there is currently no liquid crystal display element that sufficiently satisfies a high voltage holding ratio and a low residual DC voltage.
The present invention has been made based on the above circumstances, and an object of the present invention is to provide a liquid crystal aligning agent capable of producing a liquid crystal display element having a high voltage holding ratio and a low residual DC voltage. Is to provide.
[0004]
[Means for Solving the Problems]
  The above issues are (A) (a)At least one tetracarboxylic dianhydride selected from the group consisting of an alicyclic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride, an aromatic diamine, and the following formula (V)
Embedded image
(Wherein R 7 Represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R 8 Represents a monovalent organic group having a group selected from a steroid skeleton, a trifluoromethyl group and a fluoro group, or an alkyl group having 6 to 30 carbon atoms. )
Obtained by ring-opening polyaddition with at least one diamine selected from the group consisting of monosubstituted phenylenediaminesAt least one polymer selected from the group consisting of a polyamic acid and (b) a polymer having an imide structure obtained by dehydrating and ring-closing the polyamic acid (hereinafter also referred to as "imidized polymer")100 parts by weight, (B)A glycidyl group-containing compound containing a nitrogen atomEpoxy group-containing compound (hereinafter also referred to as “epoxy compound”)15 to 90 parts by weightAnd (C) a curing agent for the epoxy group-containing compound (hereinafter also referred to as “epoxy curing agent”)(B) 0.133 to 0.533 mol per mol of epoxy group in the epoxy group-containing compoundIt is solved by the liquid crystal aligning agent characterized by containing.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[Polymer (A)]
The polyamic acid (a) used in the present invention is obtained by ring-opening polyaddition of a tetracarboxylic dianhydride and a diamine compound.
The imidized polymer (b) used in the present invention can be obtained by dehydrating and ring-closing the polyamic acid (a).
[0006]
<Tetracarboxylic dianhydride>
  Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid (a) include1, 2,3,4-Cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetra Carboxylic dianhydride, 1, 3, 3a, 4, 5, 9 -Hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5 -Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5 -Ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7 -Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7 -Ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3 -Dione, 1,3,3a, 4,5,9b-Hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3 -Dione, 1,3,3a, 4,5,9b-Hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3 -Dione, 1,3,3a, 4,5,9b-Hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1 , 3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene -2,3,5,6-tetracarboxylic dianhydrideThingDoFatCyclic tetracarboxylic dianhydrides;
[0009]
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diph Nylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenyl Phosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether Dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4- Butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-o Fragrances such as kutandiol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), compounds represented by the following formulas (1) to (4) Group tetracarboxylic dianhydride. These may be used alone or in combination of two or more.
[0010]
[Chemical 2]
[0011]
  Out of these1, 2,3,4-Cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, 1 , 3,3a, 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a , 4,5,9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a , 4,5,9b-Hexahydro-5,8-dimethyl-5- (tetrahydro-2, 5-Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic Acid dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1 , 4,5,8-Naphthalenetetracarboxylic dianhydrideThing isFrom the viewpoint of exhibiting good liquid crystal alignment, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4 are particularly preferable. -Cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] furan-1,3-dioneandPyromellitic dianhydrideThingsCan be mentioned.
[0013]
<Diamine compound>
Examples of the diamine compound used for the synthesis of the polyamic acid (a) include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and 4,4′-diamino. Diphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene 3,3-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) ) -1,3,3-trimethylindane, 3,4′-diaminodiphenyl ether, 3,3′-diaminobenzophenone, , 4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexa Fluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1 , 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9 , 9-bis (4-aminophenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4 ′ Diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4 ′-(p-phenyleneisopropyl Ridene) bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'- Aromatic diamines such as diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;
[0020]
  Mono-substituted phenylenediamine represented by the following formula (V)N
[0021]
[Chemical 6]
[0022]
(Wherein R7Represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R8Represents a monovalent organic group having a group selected from a steroid skeleton, a trifluoromethyl group and a fluoro group, or an alkyl group having 6 to 30 carbon atoms. )
[0025]
NaCan be mentioned. These diamine compounds can be used alone or in combination of two or more.
[0028]
  Of these, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2 , 2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisanilineNOf the compounds represented by the formula (V), compounds represented by the following formulas (16) to (21) are preferable.
[0029]
[Chemical 9]
[0030]
<Synthesis of polyamic acid (a)>
The ratio of tetracarboxylic dianhydride and diamine compound used for the synthesis reaction of polyamic acid (a) is such that the acid anhydride group of tetracarboxylic dianhydride is equivalent to 1 equivalent of amino group contained in the diamine compound. Is preferably a ratio of 0.2 to 2 equivalents, more preferably a ratio of 0.3 to 1.2 equivalents.
The synthesis reaction of the polyamic acid (a) is usually carried out in an organic solvent under a temperature condition of -20 to 150 ° C, preferably 0 to 100 ° C. The organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid (a). For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide And aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. The amount of organic solvent used (α) is usually such that the total amount (β) of tetracarboxylic dianhydride and diamine compound is 0.1 to 30% by weight based on the total amount (α + β) of the reaction solution. It is preferable that the amount is small.
[0031]
In addition, in the said organic solvent, the polyamic acid which produces | generates the alcohols, ketones, ester, ethers, halogenated hydrocarbons, hydrocarbons etc. which are poor solvents of polyamic acid (a) does not precipitate Can be used together. Specific examples of such a poor solvent include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate , Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n- Chill ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1 , 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like.
[0032]
As described above, a reaction solution obtained by dissolving the polyamic acid (a) is obtained. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain the polyamic acid (a). Further, the polyamic acid (a) can be purified by performing the step of dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent once or several times.
[0033]
<Synthesis of imidized polymer (b)>
The imidized polymer (b) constituting the liquid crystal aligning agent of the present invention can be synthesized by dehydrating and ring-closing the polyamic acid (a). The dehydration ring closure of the polyamic acid (a) is carried out by (i) a method of heating the polyamic acid (a) or (ii) dissolving the polyamic acid (a) in an organic solvent, and the dehydrating agent and dehydration ring closure catalyst in this solution. Is added and heated as necessary. Further, the imidized polymer (b) used in the present invention has a partially dehydrated ring-closed imidization ratio (a ratio of repeating units formed with imide rings in all repeating units in the polymer). May be contained in an imidized polymer of less than 100%.
The reaction temperature in the method (i) of heating the polyamic acid (a) is usually 50 to 200 ° C., preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer (b) obtained may decrease.
On the other hand, in the above method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid (a) solution, examples of the dehydrating agent include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. Can be used. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the repeating unit of the polyamic acid (a). Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. In addition, as an organic solvent used for dehydration ring closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid (a) can be mentioned. And the reaction temperature of dehydration ring closure reaction is 0-180 degreeC normally, Preferably it is 10-150 degreeC. In addition, the imidized polymer (b) can be purified by performing the same operation as the method for purifying the polyamic acid (a) on the reaction solution thus obtained.
[0034]
<End-modified polymer>
The polymer (A) (polyamic acid (a) and imidized polymer (b)) may be a terminal-modified type having a controlled molecular weight. By using this terminal-modified polymer, the coating characteristics of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. Such a terminal-modified type can be synthesized by adding an acid monoanhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system when the polyamic acid (a) is synthesized. Here, as the acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride , N-hexadecyl succinic anhydride and the like. Examples of monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and n-undecylamine. N-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, etc. Can do. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
[0035]
<Logarithmic viscosity of polymer (A)>
The polymer (A) obtained as described above has a logarithmic viscosity (ηln) Is usually 0.05 to 10 dl / g, preferably 0.05 to 5 dl / g.
Logarithmic viscosity (ηlnThe value of) is obtained from the following formula (i) by measuring the viscosity at 30 ° C. of a solution having a concentration of 0.5 g / 100 ml using N-methyl-2-pyrrolidone as a solvent.
[0036]
[Expression 1]
[0037]
[Epoxy compound (B)]
  Epoxy compound (B) Is N, N, N ', N'−Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'−Tetraglycidyl-4,Glycidyl group-containing compounds containing nitrogen atoms such as 4'-diaminodiphenylmethane, N, N, N ', N'-tetraglycidyl-p-phenylenediamineIs. As content of the epoxy compound (B) in the liquid crystal aligning agent of this invention, with respect to a total of 100 weight part of a polymer (A).15It is made -90 weight part, Preferably it is 15-50 weight part. When the content of the epoxy compound (B) is too small, the “residual DC voltage reduction effect” and “voltage holding ratio improvement effect” cannot be sufficiently achieved in the produced liquid crystal display device. There is. On the other hand, when the epoxy compound (B) is added excessively, the liquid crystal alignment property of the liquid crystal alignment film to be formed may be lowered.
[0038]
[Epoxy curing agent (C)]
  Examples of the epoxy curing agent (C) used in the present invention include diamine compounds, acid monoanhydrides, boron complexes, imidazoles, hydrazides, and dicyandiamide. As a diamine compound, the diamine compound used for the synthesis | combination of the polyamic acid (a) mentioned above can be used, Aromatic diamines, such as diaminodiphenylmethane, diaminodiphenyl ether, and diaminodiphenyl sulfide, can be mentioned as a preferable thing. As the acid monoanhydride, acid monoanhydrides such as the above-mentioned acid monoanhydrides, succinic anhydrides, maleic anhydrides, phthalic anhydrides, etc. used in the synthesis of the terminal-modified polymer can be used. Examples of boron complexes include boron trifluoride acetic acid complex, boron trifluoride diethyl etherate, boron trifluoride butyl methyl etherate, boron trifluoride dibutyl etherate, boron trifluoride ethylamine complex, trifluoride Boron methanol complex, boron trifluoride methyl sulfide complex, boron trifluoride phenol complex, boron trifluoride phosphate complex, boron trifluoride propanol complex, boron trifluoride tetrahydrofuran complex, boron trifluoride aniline complex, trifluoride Examples thereof include boron diaminodiphenylmethane complex, boron trifluoride phenylenediamine complex, and boron trifluoride dimethylaniline complex. Examples of imidazoles include imidazole, imidazole metal derivatives, 4-imidazole acetic acid, urocanic acid, 2-imidazole carboxaldehyde, 4-imidazole carboxyl acid, imidazole carbonitrile, 5-imidazolethiocarboxylate, 4-imidazole methanol, 2- Imidazolethiol, 4- (imidazol-1-yl) acetophenone, 4- (imidazol-1-yl) phenol, 1-phenylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-benzyl-2-ethyl-imidazole, 1 -Methyl-2-ethyl-imidazole, 1-benzyl-2-phenyl-imidazole and the like. Examples of hydrazides include acetohydrazide, methanesulfonyl hydrazide, trifluoromethanesulfonyl hydrazide, P-toluenesulfonyl hydrazide and the like. As content of the epoxy curing agent (C) in the liquid crystal aligning agent of this invention, with respect to 1 mol of epoxy groups in an epoxy compound (B).0.133 to 0.533Mole, preferably0.133-0.5 mol. When the content of the epoxy curing agent (C) is too small, the “residual DC voltage reduction effect” and “voltage holding ratio improvement effect” cannot be sufficiently achieved in the liquid crystal display device to be produced. There is a case. On the other hand, if the epoxy curing agent (C) is added excessively, the liquid crystal alignment property of the liquid crystal alignment film to be formed may be deteriorated.
[0039]
[Liquid crystal aligning agent]
The liquid crystal aligning agent of the present invention is usually composed of a polyamic acid (a) and / or an imidized polymer (b), an epoxy compound (B) and an epoxy curing agent (C) dissolved in an organic solvent. The The epoxy compound (B) contained in the liquid crystal aligning agent is usually crosslinked in the presence of the epoxy curing agent (C) by a treatment such as heating when a liquid crystal aligning agent is applied on the substrate to form a thin film. And a high molecular compound.
As an organic solvent which comprises the liquid crystal aligning agent of this invention, the solvent illustrated as what is used for the synthesis reaction of a polyamic acid (a) can be mentioned. Moreover, the poor solvent illustrated as what can be used together in the case of the synthesis reaction of polyamic acid (a) can also be selected suitably, and can be used together.
The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., but is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the coating film thickness is When the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive. Moreover, the viscosity of the liquid crystal aligning agent may increase, resulting in poor coating characteristics.
[0040]
The liquid crystal aligning agent of the present invention may contain a functional silane-containing compound from the viewpoint of improving the adhesion to the substrate surface. Examples of such functional silane-containing compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- , 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N -Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. can be mentioned. The compounding ratio of these functional silane-containing compounds is usually 40 parts by weight or less, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer.
[0041]
[Liquid crystal display element]
The liquid crystal display element obtained using the liquid crystal aligning agent of this invention can be manufactured, for example with the following method.
[0042]
(1) The liquid crystal aligning agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film by a method such as a roll coater method, a spinner method, or a printing method, and then the coated surface is heated. Thus, a coating film is formed. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used. As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO2), an ITO film made of indium oxide-tin oxide (In2 O3-SnO2), or the like can be used. In order to pattern these transparent conductive films, a photo-etching method or a method using a mask in advance is used. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane-containing compound, a functional titanium-containing compound, or the like is previously applied to the surface of the substrate. You can also The heating temperature after application of the liquid crystal aligning agent is 80 to 300 ° C, preferably 120 to 250 ° C. In addition, the liquid crystal aligning agent of this invention containing a polyamic acid formed the coating film used as an alignment film by removing an organic solvent after application | coating, but also advanced dehydration ring closure by heating and was imidized. It can also be set as a coating film. The film thickness of the coating film to be formed is usually 0.001 to 1 μm, preferably 0.005 to 0.5 μm.
[0043]
(2) A rubbing process is performed in which the formed coating film surface is rubbed in a certain direction with a roll wound with a cloth made of a fiber such as nylon, rayon, or cotton. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.
Further, by partially irradiating the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention with ultraviolet rays as disclosed in, for example, JP-A-6-222366 and JP-A-6-281937. A resist film is partially formed on the surface of the liquid crystal alignment film that has been subjected to a treatment for changing the pretilt angle or a rubbing treatment as disclosed in JP-A-5-107544, which is different from the previous rubbing treatment. The visibility characteristics of the liquid crystal display element can be improved by removing the resist film after performing the rubbing treatment in the direction and changing the liquid crystal alignment ability of the liquid crystal alignment film.
[0044]
(3) Two substrates on which the liquid crystal alignment film is formed as described above are manufactured, and the two substrates are separated by a gap (cell gap) so that the rubbing directions in the respective liquid crystal alignment films are orthogonal or antiparallel. ), And the periphery of the two substrates are bonded together using a sealant, and liquid crystal is injected and filled in the cell gap defined by the substrate surface and the sealant, and the injection hole is sealed. A liquid crystal cell is constructed. A polarizing plate is disposed on the outer surface of the liquid crystal cell, that is, on the other surface side of each substrate constituting the liquid crystal cell, and the polarization direction thereof coincides with or is orthogonal to the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate. A liquid crystal display element is obtained by pasting together.
[0045]
Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable. For example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal. Liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, for these liquid crystals, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck). Etc. can also be used. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.
Further, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film in which a polarizing film called an H film that absorbs iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between cellulose acetate protective films. The polarizing plate which consists of itself can be mentioned.
[0046]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the measuring method and evaluation method about the liquid crystal aligning agent prepared by the following Examples and comparative examples and the produced liquid crystal display element are as follows.
[Orientation of liquid crystal]
The presence or absence of an abnormal domain when the voltage was turned on / off of the liquid crystal display element was observed with a polarizing microscope, and the case where there was no abnormal domain was determined as “good”.
[Residual DC voltage]
A 30 Hz, 2.0 V rectangular wave with 1.0 V DC superimposed on the liquid crystal display element is applied at an ambient temperature of 70 ° C. for 1 hour, and the voltage remaining in the liquid crystal cell immediately after the DC voltage is turned off is flicker-erased. To determine the residual DC voltage.
[Voltage holding ratio]
When a voltage of 5 V, an application time of 60 microseconds, and a span of 167 milliseconds were applied to the liquid crystal display element, a holding voltage after 167 milliseconds after the release of 5 V was applied using VHR-1 manufactured by Toyo Corporation. Measurements were made to determine the voltage holding ratio.
[0047]
[Synthesis Example 1]
2,3,5-tricarboxycyclopentylacetic acid dianhydride 22.4 g (100 mmol) as tetracarboxylic dianhydride, 5.23 g (10 mmol) and 4 of the diamine represented by the above chemical formula (17) as the diamine compound , 4′-diaminodiphenylmethane (17.8 g, 90 mmol) was dissolved in 450 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it is washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to give a polyamic acid having a logarithmic viscosity of 0.95 dl / g and an imidization ratio of 0% (this is referred to as “polyamic acid (a1)”). 40.8 g was obtained.
[Synthesis Example 2]
25.0 g of polyamic acid (a1) obtained in Synthesis Example 1 is dissolved in 450 g of N-methyl-2-pyrrolidone, 7.0 g of pyridine and 9.1 g of acetic anhydride are added, and dehydration ring closure is performed at 100 ° C. for 3 hours. Reaction was performed. Next, the reaction solution was precipitated, washed, and dried in the same manner as in Synthesis Example 1 to obtain an imidized polymer having a logarithmic viscosity of 0.93 dl / g and an imidization ratio of 70% (this is referred to as “imidized polymer (b1)”). 19.0 g was obtained.
[Synthesis Example 3]
In Synthesis Example 2, an imidized polymer having a logarithmic viscosity of 0.85 dl / g and an imidization rate of 100% (this is referred to as “1”) except that 23.4 g of pyridine and 18.1 g of acetic anhydride were used. 17.5 g of imidized polymer (b2) ”was obtained.
[0048]
[Synthesis Example 4]
In Synthesis Example 1, the logarithmic viscosity was the same as in Synthesis Example 1 except that 5.24 g (10 mmol) of the diamine represented by the chemical formula (16) was used instead of the diamine represented by the chemical formula (17). Was 0.95 dl / g, and 40.8 g of a polyamic acid (hereinafter referred to as “polyamic acid (a2)”) having an imidization ratio of 0% was obtained.
[Synthesis Example 5]
25.0 g of polyamic acid (a2) obtained in Synthesis Example 4 is dissolved in 450 g of N-methyl-2-pyrrolidone, 7.2 g of pyridine and 9.2 g of acetic anhydride are added, and dehydration ring closure is performed at 100 ° C. for 3 hours. Reaction was performed. Next, the reaction solution was precipitated, washed and dried in the same manner as in Synthesis Example 1 to obtain an imidized polymer having a logarithmic viscosity of 0.93 dl / g and an imidization ratio of 70% (this is referred to as “imidized polymer (b3)”). 19.5 g was obtained.
[0049]
[Synthesis Example 6]
A polyamic acid having a logarithmic viscosity of 1.50 dl / g in the same manner as in Synthesis Example 1 except that 21.8 g (100 mmol) of pyromellitic dianhydride was used as the tetracarboxylic dianhydride in Synthesis Example 1. (This is referred to as “polyamic acid (a3).”) 37.8 g was obtained.
[0050]
[Example 1]
(1) Preparation of liquid crystal aligning agent:
4 g of polyamic acid (a1) obtained in Synthesis Example 1, 0.8 g of N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane (B1) and 4,4′-diaminodiphenylmethane (C1) ) 0.2 g was dissolved in a mixed solvent of 20 g of 4-hydroxy-4-methyl-2-pentanone and 76 g of γ-butyrolactone to obtain a solution having a solid content concentration of 4% by weight. This solution was filtered through a filter having a pore diameter of 1 μm to prepare the liquid crystal aligning agent of the present invention.
(2) Production of liquid crystal display element:
(1) The liquid crystal aligning agent of the present invention prepared as described above was applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm using a spinner at 180 ° C. By drying for 1 hour, a coating film having a dry film thickness of 800 mm was formed.
(2) A liquid crystal alignment film was prepared by subjecting the formed coating surface to a rubbing treatment using a rubbing machine having a roll wound with a nylon cloth. Here, the rubbing treatment conditions were a roll rotation speed of 500 rpm, a stage moving speed of 1 cm / sec, and a hair foot pushing length of 0.4 mm.
(3) Two substrates on which a liquid crystal alignment film is formed as described above are prepared, and an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 17 μm is applied to the outer edge of each substrate by a screen printing method. After that, the two substrates were placed facing each other through a gap so that the rubbing directions in the respective liquid crystal alignment films were antiparallel, and the outer edge portions were brought into contact with each other to be pressure-bonded to cure the adhesive.
(4) Nematic liquid crystal “MLC-2001” (manufactured by Merck) is injected and filled into the cell gap defined by the adhesive on the surface and outer edge of the substrate, and then the injection hole is sealed with an epoxy adhesive. A liquid crystal cell was constructed. Thereafter, a polarizing plate was bonded to the outer surface of the liquid crystal cell so that the polarization direction coincided with the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate, thereby producing a liquid crystal display element.
(5) With respect to the liquid crystal display device produced as described above, the voltage holding ratio and the residual DC voltage were measured to evaluate the orientation of the liquid crystal. The results are shown in Table 1.
[0051]
[Example 210]
  In accordance with the formulation shown in Table 1 below, each of the examples obtained by using 100 parts by weight of the polymers obtained in Synthesis Examples 1 to 6, 20 parts by weight of the epoxy compound (B), and each of the epoxy curing agent (C). The liquid crystal aligning agent of this invention was prepared like 1. Next, a liquid crystal display device was produced in the same manner as in Example 1 using each of the liquid crystal aligning agents thus prepared. Each of the manufactured liquid crystal display elements was evaluated in the same manner as in Example 1. The results are also shown in Table 1.
[Comparative Examples 1-5]
  According to the formulation shown in Table 1 below, the liquid crystal aligning agent of the present invention was prepared in the same manner as in Example 1 using 100 parts by weight of each of the polymers obtained in Synthesis Examples 1-6. Next, a liquid crystal display device was produced in the same manner as in Example 1 using each of the liquid crystal aligning agents thus prepared. Each of the manufactured liquid crystal display elements was evaluated in the same manner as in Example 1. The results are also shown in Table 1.
[0052]
[Table 1]
[0053]
  In Table 1, the types of the epoxy compound and the epoxy curing agent are as follows.
(Epoxy compound)
B1: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane
B2: N, N, N ', N'−Tetraglycidyl-m-xylylenediamine
B3: 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane
B4: N, N, N ', N'−Tetraglycidyl-p-phenylenediamineN
(Epoxy curing agent)
C1: 4,4'-diaminodiphenylmethane
C2: 4,4 '-(p-phenylenediisopropylidene) bisaniline
C3: Phthalic anhydride
C4: Boron trifluoride ethylamine complexbody
C6: p-ToluenesulfonylhydrazideDo
【The invention's effect】
  According to the present invention, it is possible to provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film having a high voltage holding ratio and a low afterimage type. The liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention is suitable for constituting various liquid crystal display elements such as SH (Super Homeotropic) type liquid crystal display elements as well as TN type liquid crystal display elements and STN type liquid crystal display elements. Can be used for In addition, the liquid crystal display element provided with the liquid crystal alignment film is excellent in the alignment and reliability of the liquid crystal, and can be effectively used in various devices. It can be suitably used as a display device such as a personal computer or a liquid crystal television.

Claims (1)

  1. (A) (a) at least one tetracarboxylic dianhydride selected from the group consisting of an alicyclic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride, an aromatic diamine and the following formula (V)
    (Wherein R 7 represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R 8 represents a steroid skeleton, A monovalent organic group having a group selected from a fluoromethyl group and a fluoro group or an alkyl group having 6 to 30 carbon atoms is shown.)
    A polyamic acid obtained by ring-opening polyaddition with at least one diamine selected from the group consisting of mono-substituted phenylenediamines represented by the formula (b) and a polyamic acid having an imide structure obtained by dehydrating and ring-closing the polyamic acid. 100 parts by weight of at least one polymer selected from the group consisting of a combination, (B) 15 to 90 parts by weight of an epoxy group-containing compound that is a glycidyl group-containing compound containing a nitrogen atom, and (C) of the epoxy group-containing compound The liquid crystal aligning agent characterized by including 0.133-0.533 mol of hardening | curing agents with respect to 1 mol of epoxy groups in the (B) epoxy-group containing compound .
JP16654497A 1997-06-09 1997-06-09 Liquid crystal alignment agent Expired - Lifetime JP3968823B2 (en)

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