TW201416396A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, polymer and compound - Google Patents

Abstract

A liquid crystal alignment agent is provided, which can provide a liquid crystal alignment film having excellent liquid crystal alignment property, transparency and rubbing resistance. The liquid crystal alignment agent is characterized in containing at least one polymer selected from a group consisting of a polyamic acid having a two valence group represented by the following formula (1) and an imidized polymer of the polyamic acid. In the formula (1), n1 is an integer of 1 to 3, a plurality of X independently represents an oxygen atom or a sulfer atom respectively; a plurality of Y independently represents -NH- or an oxygen atom respectively; R1 both independently represents a single bond, methylene group or alkylene group having 2 to 6 carbon respectively; R2 independently represents two valence organic group respectively when a plurality of R2 exist; ''*'' represents a connection bond respectively.

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer And compounds

The present invention relates to a liquid crystal alignment agent.

In particular, the present invention relates to a liquid crystal alignment agent which provides a liquid crystal alignment film which is excellent in liquid crystal alignment, transparency, and abrasion resistance.

The liquid crystal display element is displayed by a light switching function for enclosing liquid crystal between a pair of substrates arranged in opposite directions, and turning on/off (ON/OFF) of voltage application to cause alignment of liquid crystals Change to change the light.

Among the liquid crystal display elements, a twisted nematic liquid crystal display element (Twisted Nematic (TN) mode), a super twisted nematic liquid crystal display element (Super Twisted Nematic (STN) mode), and a transverse electric field In a horizontal alignment type liquid crystal display element such as a display type liquid crystal display element (In-Plane Switching (IPS) mode or a Fringe Field Switching (FFS) mode), it is necessary to align the liquid crystal in parallel with the substrate surface. Horizontal alignment technology. Among these modes, the function of aligning the liquid crystal is controlled by an organic film (liquid crystal alignment film) subjected to rubbing treatment. The rubbing treatment is a treatment of wiping the organic film on the substrate with a long cloth such as rayon or cotton, and imparts a liquid crystal alignment ability to the organic film in a direction rubbing with the cloth to form a liquid crystal alignment film.

By the rubbing treatment, there are scratches and flaking on the liquid crystal alignment film. In some cases, it may cause poor display. Therefore, there have been various proposals for obtaining a liquid crystal alignment film material excellent in abrasion resistance, and a certain result has been obtained (Patent Document 1 and Patent Document 2).

However, in recent years, with the high definition of liquid crystal display elements, one pixel The size becomes smaller than before, and thus the number of steps caused by the electronic parts on the substrate on which the liquid crystal alignment film is formed increases. Therefore, in recent years, the liquid crystal alignment film is subjected to higher stress than before due to the rubbing treatment, and thus it is likely to cause scratches, flaking, and the like. In addition to this, the requirement for high definition of the liquid crystal display element is not acceptable even in the case of display defects of a fine size, and therefore the requirements for the rubbing resistance of the liquid crystal alignment film are very strict.

It has not been known before that not only is it fully expressed as a liquid crystal alignment film, but of course A liquid crystal alignment film material which satisfies the requirements of the liquid crystal alignment property and transparency, and which satisfies the severe rubbing resistance as described above.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] International Patent Publication No. 2011/068127

[Patent Document 2] International Patent Publication No. 2004/053583

[Patent Document 3] International Patent Publication No. 2010/053128

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-97188

The present invention has been made in response to the above requirements.

An object of the present invention is to provide a liquid crystal alignment agent which provides a liquid crystal alignment film which is excellent in liquid crystal alignment, transparency, and abrasion resistance.

The above object and advantage of the present invention are attained by a liquid crystal alignment agent characterized by containing a polylysine selected from the group consisting of a divalent group represented by the following formula (1) and the polyamine At least one polymer of the group consisting of acid quinone imidized polymers.

In the formula (1), n1 is an integer of 1 to 3; a plurality of X are independently an oxygen atom or a sulfur atom; and a plurality of Y are independently -NH- or an oxygen atom; and two R are present ^{1 is} independently a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms, and R ² is independently a divalent organic group in the presence of a plurality of, and "*" represents a bond, respectively.

According to the present invention, there is provided a liquid crystal alignment agent which provides a liquid crystal alignment film which is excellent in liquid crystal alignment property and transparency and which can withstand severe rubbing treatment in recent years. The liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is suitable for a high-definition horizontal alignment type liquid crystal display element.

As described above, the liquid crystal alignment agent of the present invention contains a group selected from the group consisting of polyglycine having a divalent group represented by the above formula (1) and a ruthenium-based polymer of the polyglycolic acid. At least one polymer (hereinafter referred to as "specific polymer").

<Specific polymer>

The specific polymer contained in the liquid crystal alignment agent of the present invention has a divalent group represented by the above formula (1).

In terms of easiness of synthesis, two of R ¹ in the above formula (1) are preferably the same group. R ¹ is preferably a single bond, a methylene group or an alkylene group having 2 to 4 carbon atoms, more preferably a single bond, a methylene group or a 1,2-extended ethyl group.

R ² in the above formula (1) is preferably a hydrocarbon group having 1 to 30 carbon atoms or a halogenated hydrocarbon group, and more preferably, for example, 1,2-extended ethyl group, 1,6-extended hexyl group, 1,6-hexylene, The groups represented by the formulas, and the like.

[Chemical 2]

In the above formula, "+" represents a bond, respectively.

The bonding bond represented by "*" in the above formula (1) is preferably in a meta or para position with respect to other groups.

N1 in the above formula (1) is preferably 1.

Examples of the group represented by the above formula (1) include the following formula (1-1-1) to formula (1-1-5) and formula (1-2-1) to formula (1-2-). 5), formula (1-3-1) ~ formula (1-3-5), formula (1-4-1) ~ formula (1-4-5), formula (1-5-1) ~ formula ( 1-5-5), a group represented by the formula (1-6-1) to the formula (1-6-7) and the formula (1-7-1) to the formula (1-7-3).

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemistry 7]

[化8]

[Chemistry 9]

In the above formula, "*" represents a bond, respectively.

In the above formula (1), X is preferably an oxygen atom, and Y is preferably -NH-.

The specific polymer contained in the liquid crystal alignment agent of the present invention is composed of a ruthenium imidized polymer selected from the group consisting of polyglycolic acid having a divalent group represented by the above formula (1) and the polyglycolic acid. The one or more polymers in the group may be a polymer synthesized by any method.

The specific polymer is preferably one or more selected from the group consisting of the following polymers: a tetracarboxylic dianhydride having a divalent group represented by the above formula (1), or the tetracarboxylic dianhydride and others a polyamic acid obtained by reacting a mixture of tetracarboxylic dianhydride with a diamine; a ruthenium iodide polymer of the polyphthalic acid; and a tetracarboxylic dianhydride having 2 represented by the above formula (1) a polyamine obtained by reacting a valence diamine (hereinafter referred to as "specific diamine") or a mixture of a specific diamine and another diamine; The ruthenium iodide polymer of polyglycolic acid; more preferably one or more selected from the group consisting of a tetracarboxylic dianhydride and a specific diamine or a specific diamine and other diamines The polyaminic acid obtained by the reaction of the mixture; and the quinone imidized polymer of the poly-proline.

[tetracarboxylic dianhydride]

Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid which is a specific polymer of the present invention include aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and alicyclic tetracarboxylic dianhydride.

The above-mentioned aromatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride in which two acid anhydride groups are bonded to an aromatic ring, respectively.

The above-mentioned aliphatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride in which two acid anhydride groups are bonded to a non-aromatic and acyclic hydrocarbon group, respectively. Here, as long as the bond bonds of the two acid anhydride groups are bonded to the acyclic and non-aromatic hydrocarbon groups, the other portions in the molecule may have an alicyclic structure or an aromatic structure or These two structures.

The above-mentioned alicyclic tetracarboxylic dianhydride is a tetracarboxylic dianhydride in which at least one of the total of four bonding bonds of the two acid anhydride groups is bonded to an alicyclic hydrocarbon group. Preferably, the two bonding bonds of one of the two acid anhydride groups are bonded to the alicyclic hydrocarbon group. In this case, the other acid anhydride group is preferably bonded to a non-aromatic and acyclic hydrocarbon group or bonded to an alicyclic hydrocarbon group. The alicyclic tetracarboxylic dianhydride may have an aromatic structure in a portion other than the hydrocarbon group to which the acid anhydride group is bonded.

In the above, the acid anhydride group means a divalent group having a structure represented by the following formula.

In the above formula, "*" represents a bond.

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, and 4,4′-oxygen. An aromatic tetracarboxylic dianhydride described in Patent Document 4 (Japanese Patent Laid-Open Publication No. 2010-97188), which is preferably used, is preferably used, for example, in the case of phthalic anhydride (4,4'-oxydiphthalic anhydride). It is one or more selected from these compounds. Among these compounds, the aromatic tetracarboxylic dianhydride is preferably selected from the group consisting of pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, and 4,4'-oxydiphthalic anhydride. In the case of improving the liquid crystal alignment property of the liquid crystal alignment film to be formed, it is more preferable to use pyromellitic dianhydride.

The aliphatic tetracarboxylic dianhydride may, for example, be 1,2,3,4-butanetetracarboxylic dianhydride or the like. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic 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, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-( 2,5-dioxotetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethyl group Bornane-2:3,5:6-dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 4,9-dioxatricyclo[5.3 .1.0 ^2,6 ]undecane-3,5,8,10-tetraketone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, etc., except for patent document 4 (Japanese patent) In the alicyclic tetracarboxylic dianhydride described in JP-A-2010-97188, it is preferred to use one or more selected from the group consisting of these compounds.

The aliphatic tetracarboxylic dianhydride or the alicyclic tetracarboxylic dianhydride is preferably one selected from the above compounds from 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxyl group. Cyclopentyl acetic 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, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, cyclohexanetetracarboxylic acid One or more selected from the group consisting of an anhydride and a 1,2,3,4-butanetetracarboxylic dianhydride, and more preferably selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride, (1S, 2S, 4R, 5R)-cyclohexanetetracarboxylic dianhydride, (1R, 2S, 4S, 5R)-cyclohexane tetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentyl acetic acid One or more of the groups consisting of dianhydrides is particularly preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

By using one or more selected from the group consisting of aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride, the electric power of the obtained liquid crystal display element can be improved. Pressure retention. In particular, in the case where only a compound selected from the group consisting of aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride is used as the tetracarboxylic dianhydride for synthesizing polyglycine, voltage retention is employed. The rate of increase is maximized.

The tetracarboxylic dianhydride used for the synthesis of polyamic acid is preferably selected from the group consisting of only a compound in a group consisting of aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride, or a group selected from the group consisting of aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride One or more of them may be used in combination with one or more selected from the group consisting of aromatic tetracarboxylic dianhydrides.

Relying on the friction resistance of the formed liquid crystal alignment film and the resulting liquid crystal display From the viewpoint of high voltage retention in the element, a tetracarboxylic dianhydride for synthesizing polyamic acid is selected from the group consisting of aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride. The ratio of use of one or more of them is preferably 10% by mole or more, more preferably 30% by mole or more, particularly preferably 50% by mole or more, and particularly preferably 60% by mole or more. .

Will be selected from the group consisting of aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride When one or more of the constituent groups and the aromatic tetracarboxylic dianhydride are used as the tetracarboxylic dianhydride, the liquid crystal alignment property and the high voltage holding ratio in the obtained liquid crystal display device are considered. The use ratio of the tetracarboxylic dianhydride is preferably from 5 mol% to 50 mol%, more preferably from 10 mol% to 45 mol%, and particularly preferably from 20 mol% to 40 mol. ear%.

[diamine]

The diamine used to synthesize the specific polymer of the present invention, that is, poly-proline Diamine.

The specific diamine is a diamine having a divalent group represented by the above formula (1), and examples thereof include a compound represented by the following formula (2).

N1 (2) in the formula, X, Y, R ¹ and R ² are the same as the above-described formula (1), n1, X, Y, R ¹ and R ² meanings. The specific diamine is preferably one or more selected from the group consisting of the following formula (1-1-1) to formula (1-1-5) and formula (1-2-1) to (formula). 1-2-5), Formula (1-3-1)~Formula (1-3-5), Formula (1-4-1)~Formula (1-4-5), Formula (1-5-1) )~(1-5-5), (1-6-1)~(1-6-7), and (1-7-1)~(1-7-3) In the divalent group, the two bond bonds represented by "*" are each bonded to an amino group. The two amine groups are preferably located at the 4-position on the benzene ring with respect to the other groups.

A specific diamine can be synthesized by appropriately combining a common method of organic chemistry. For example, in the above formula (2), a compound in which n1 is 1, X is an oxygen atom, and Y is -NH- can be, for example, made by the formula OCN-R ² -NCO (wherein R ² is the same as the above formula (2) The equivalent of R ^{2 in the} same meaning) is 1 equivalent of the diisocyanate and 2 equivalents of the diamine represented by the following formula, and is preferably synthesized by reacting in a suitable solvent (for example, tetrahydrofuran).

[化12]

In the above formula, R ¹ has the same meaning as R ¹ in the above formula (2). Here, when R ¹ is a single bond, the reactivity of the two amine groups in the above diamine is equal; when R ¹ is a methylene group or a C 2 to 6 alkyl group, since it is bonded to R ¹ Since the amine group is more reactive, for example, the above formula (2) can be obtained in a high yield by, for example, dissolving a predetermined amount of a diamine in a suitable solvent and adding the above isocyanate little by little. The desired compound is represented.

In the above formula (2), a compound wherein n1 is 1, X is an oxygen atom, Y on the R ¹ side is an oxygen atom, and Y on the R ² side is -NH- can be, for example, made by the formula OCN-R ² -NCO (this) Wherein R ² is 1 equivalent of the diisocyanate represented by the formula (2) and 2 equivalents of the compound represented by the following formula, and preferably after reacting in a suitable solvent (for example, toluene), The nitro group is reduced and synthesized.

In the above formula, R ¹ has the same meaning as R ¹ in the above formula (2).

The diamine used for the synthesis of the polyamic acid may be a compound represented by the above formula (2), or another diamine may be used in combination with the compound represented by the above formula (2).

Other diamines which can be used herein include, for example, a diamine having a pretilt performance and a diamine having no pretilt expression.

Examples of the above diamine having a pretilt performance include, for example, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, and pentadecyloxy-2. , 4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diamine Benzobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecyloxy-2,5-diaminobenzene, eighteen Alkoxy-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2 , 4-diaminobenzene, cholesteneoxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid cholestene Base ester, 3,5-diaminobenzoic acid lanthanum alkyl ester, 3,6-bis(4-aminobenzylideneoxy)cholestane, 3,6-bis(4-aminophenoxyl) A choline, a compound represented by the following formula (A-1), and a diamine or the like described in Patent Document 4 (Japanese Patent Laid-Open Publication No. 2010-97188) can be used. the above.

In the formula (A-1), X ^I and X ^II are a single bond, ^* -O-, ^* -COO- or ^* -OCO-, respectively (wherein the bond bond marked with "*" is oriented toward the left of the formula (AI) Direction)), R ^I is a single bond, a methylene group or an alkylene group having 2 or 3 carbon atoms, a is 0 or 1, and b is an integer of 0 to 2, wherein a and b are not simultaneously 0, and c is An integer from 1 to 20.

Specific examples of the group C _c H _2c+1 - in the above formula (A-1) include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and the like. N-octyl, n-decyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-ten Octaalkyl, n-nonadecyl, n-icosyl and the like.

The divalent group represented by X ^I -R ^I -X ^II - in the above formula (A-1) is preferably a methylene group, an alkylene group having 2 or 3 carbon atoms, ^* -O-, ^* -COO- Or ^* -O-CH ₂ CH ₂ -O- (wherein the bond labeled "*" is bonded to the diaminophenyl group). The two amine groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to other groups.

Specific examples of the compound represented by the above formula (A-1) are preferably, for example, the following formula (A-1-1-1), formula (A-1-1-2), and formula (A-1-2), respectively. The compound represented.

[化15]

In the above formula, nC ₅ H ₁₁ and nC ₇ H ₁₅ each represent a linear pentyl group and a linear heptyl group.

The diamine having no pretilt-expressing group may, for example, be an aliphatic diamine, an alicyclic diamine, a diamine-based organodecane or an aromatic diamine having no pretilt-expressing group, and is preferably One or more selected from the group consisting of these compounds are used.

The aliphatic diamine having no pretilt-expressing group may, for example, be 1,1-meta-xylylenediamine, 1,3-propanediamine or tetramethylene An amine, pentamethylenediamine, hexamethylenediamine or the like; the alicyclic diamine having no pretilt-expressing group, for example, 1,4-diaminocyclohexane, 4, 4 '-methylene bis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane or the like; the diamine-based organodecane having no pretilt-expressing group, for example, may be exemplified by 1 , 3-bis(3-aminopropyl)-tetramethyldioxane, and the like; Examples of the aromatic diamine having no pretilt-expressing group include phenylendiamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4 , 4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino -2,2'-bis(trifluoromethyl)biphenyl, 2,7-diaminopurine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-amine Phenyloxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2 ,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediisopropylidene)diphenylamine, 4,4'-(inter)phenyldiisopropylidene Diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4 -diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N, N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis-(4-aminophenyl)-piperazine, 3,5 -diaminobenzoic acid, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoro Methyl benzhydryloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butyl ring Hexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)) Phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2,4-Diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1-(2,4-diaminophenyl)piperazine- 4-carboxylic acid, 4-(morpholin-4-yl)benzene-1,3-diamine, 1,3-bis(N-(4-aminophenyl)piperidinyl)propane, α-amino group -ω-aminophenylalkylene, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, etc.; other than this, Patent Document 4 (Japan) In the diamine described in JP-A-2010-97188, one or more selected from the group consisting of these compounds can be used.

The diamine for synthesizing the polyglycolic acid of the present invention preferably contains 10 mol% or more of the specific diamine as described above with respect to the total amount of the diamine, and more preferably contains 20 mol% to 90 mol. %, particularly preferably from 30 mol% to 70 mol%.

The diamine for synthesizing poly-proline may contain a diamine having a pretilt performance as described above in a range of 40 mol% or less with respect to the total amount of the diamine, which has a pretilt expression The content ratio of the amine is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably a diamine having no pretilt performance.

[Molecular weight regulator]

When synthesizing a specific polymer, that is, poly-proline, a terminal-modified polymer can be synthesized together with the above tetracarboxylic dianhydride and a diamine using an appropriate molecular weight modifier. By making the poly-proline acid into the terminal-modified polymer, the coating property (printability) of the obtained liquid crystal alignment agent can be further improved without impairing the effects of the present invention.

Examples of the molecular weight modifier include a monoanhydride, a monoamine compound, and a monoisocyanate compound.

Examples of the above monoacid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, and positive ten Hexaalkyl succinic anhydride;

Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine. Examples of the monoisocyanate compound include phenyl isocyanate and isocyanide. Naphthyl ester and the like.

The use ratio of the molecular weight modifier is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the total of the tetracarboxylic dianhydride and the diamine to be used.

[Synthesis method of polylysine]

The specific polymer of the present invention, polylysine, can be synthesized by reacting a tetracarboxylic dianhydride with a diamine in a solvent. The ratio of the tetracarboxylic dianhydride to the diamine used in the synthesis reaction of the polyamic acid is preferably 1 equivalent to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 equivalent to 2 equivalents. More preferably, it is a ratio of 0.3 equivalent to 1.2 equivalent.

The solvent used to synthesize the poly-proline is preferably an organic solvent. Examples of the organic solvent include an aprotic polar solvent, phenol and a derivative thereof, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. Specific examples of such an organic solvent include the above-mentioned aprotic polar solvent: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. , dimethyl hydrazine, γ-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N , N-dimethylpropionamide, etc.; examples of the above phenol and its derivative include phenol, m-cresol, xylenol, halogenated phenol, and the like; Examples of the above-mentioned alcohol include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, and ethylene glycol monomethyl ether; and the above ketones include, for example, : acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; examples of the above esters include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, and methoxy group. Methyl propionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, etc.; examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, and ethylene Alcohol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc.; the halogenated hydrocarbons mentioned above may, for example, be dichloro Methane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, etc.; examples of the above hydrocarbons include hexane, heptane, octane, and benzene. Toluene, Toluene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether and the like, may be more of these organic solvents selected from one kind.

Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and phenol and a derivative thereof (an organic solvent of the first group) or a first group selected from the above group is preferably used. One or more kinds of the organic solvent may be one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (organic solvents of the second group). In the latter case, relative to the first The total ratio of the organic solvent of the second group to the organic solvent of the second group is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably It is 30% by mass or less.

The solvent for synthesizing the poly-proline of the present invention is more preferably one or more selected from the group consisting of the above-mentioned first group of organic solvents, and it is particularly preferable to use one or more selected from the group consisting of aprotic polar solvents, particularly Preference is given to using N-methyl-2-pyrrolidone.

The ratio of use of the solvent is preferably a ratio of the total amount of the tetracarboxylic dianhydride to the diamine to be 0.1% by mass to 50% by mass based on the total amount of the reaction solution.

The synthesis of the specific polymer of the present invention, that is, poly-proline is preferably at a reaction temperature of from -20 ° C to 150 ° C, more preferably from 0 ° C to 100 ° C, preferably from 0.1 to 24 hours, more preferably 0.5 hour. ~12 hours of reaction time to carry out.

In the above manner, a reaction solution obtained by dissolving a specific polymer, that is, polylysine, was obtained.

The reaction solution can be directly used for preparing a liquid crystal alignment agent, and the polyamic acid contained in the reaction solution can be isolated and used for preparing a liquid crystal alignment agent. Alternatively, the isolated polylysine may be purified and used to prepare a liquid crystal alignment agent.

The isolation and purification of the above polylysine can be carried out according to a known method.

[Synthesis method of ruthenium iodide polymer]

The quinone imidized polymer which is a specific polymer contained in the liquid crystal alignment agent of the present invention can be obtained by subjecting the polylysine obtained in the above manner to dehydration ring closure and ruthenium imidization. In this case, the reaction of the above synthesized polylysine can be carried out. The solution is directly supplied to the dehydration ring closure reaction, and the polylysine contained in the reaction solution may be isolated and then supplied to the dehydration ring closure reaction, or the isolated polyamic acid may be purified and then supplied to the dehydration ring closure reaction.

The specific polymer of the present invention, i.e., the ruthenium iodide polymer, may be as The complete ruthenium imide of the proline acid structure of the precursor of the polyamic acid has a dehydration ring closure, and may also be a part of the structure of the proline structure, which is dehydrated and closed, the structure of the proline and the structure of the quinone ring. Coexisting part of the quinone imide. The oxime imidization ratio in the present invention is preferably 30% or more, more preferably 50% to 99%, and particularly preferably 65% to 99%. The ruthenium imidization ratio is a ratio of the number of quinone ring structures in terms of the total number of guanidine structures and the number of quinone ring structures in the polyimine. Here, even if a part of the imine ring is an isoindole ring, it can be calculated as a quinone ring.

The dehydration ring-closing reaction of poly-proline is preferably a method of heating poly-proline Alternatively, a dehydrating agent and a dehydration ring-closure catalyst may be added to a solution obtained by dissolving polylysine in an organic solvent, and heating may be carried out as needed; more preferably, the latter method is used.

Adding a dehydrating agent to the solution of the above polyamic acid and dehydration ring closure catalysis In the method of the agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The use ratio of the dehydrating agent is preferably set to 0.01 mol to 20 mol with respect to 1 mol of the proline structure of the polyglycolic acid. As the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, collidine, lutidine or triethylamine can be used. 1 mole relative to the dehydrating agent used, The use ratio of the dehydration ring-closure catalyst is preferably set to 0.01 mol to 10 mol. The organic solvent used for the dehydration ring-closure reaction is exemplified as the organic solvent exemplified above for the organic solvent for synthesizing polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably from 0 ° C to 180 ° C, more preferably from 10 ° C to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

A reaction solution containing a ruthenium iodide polymer was obtained in the above manner. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or the dehydration agent can be removed from the reaction solution, and the dehydration ring-closing catalyst can be supplied to the liquid crystal alignment agent, or the polyimine can be isolated and then supplied to the liquid crystal alignment. The preparation of the agent, or the isolated polyimine may also be purified and then supplied to the preparation of the liquid crystal alignment agent. These operations can be carried out in accordance with known methods.

[Solid viscosity of a specific polymer]

The specific polymer of the present invention obtained in the above manner (at least one selected from the group consisting of polylysine and sulfiminated polymers) is preferably prepared as a solution having a concentration of 10% by mass. When, it has 20mPa. s~800mPa. The solution viscosity of s is more preferably 30 mPa. s~500mPa. s solution viscosity. Here, the solution viscosity (mPa.s) of the specific polymer is a specific polymer solution having a concentration of 10% by mass prepared using N-methyl-2-pyrrolidone as a solvent, using an E-type rotation The value measured by the viscometer at 25 °C.

<Other ingredients>

The liquid crystal alignment agent of the present invention contains the specific polymer as described above, and may contain other optional components as needed. Other optional components include, for example, the above. A polymer other than the specific polymer (hereinafter referred to as "other polymer"), a compound having one or more epoxy groups in the molecule (hereinafter referred to as "epoxy compound"), a functional decane compound, or the like.

[Other polymers]

The above other polymers may be used to improve the solution characteristics of the liquid crystal alignment agent. The liquid crystal alignment agent of the present invention is included in the objective of obtaining electrical characteristics of the liquid crystal alignment film.

The so-called other polymer in the present invention refers to a polymerization other than a specific polymer. A compound which does not have a divalent group represented by the above formula (1), a quinone imidized polymer of the polyglycolic acid, a polyphthalate, a polyester, a polyamide , polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or its derivative, poly(styrene-phenylmethylene iodide) derivative, poly(meth)acrylate, etc. One or more selected from these compounds can be used.

Total relative to polymer (refers to specific polymer and other polymers) In the liquid crystal alignment agent of the present invention, the content ratio of the other polymer in the liquid crystal alignment agent of the present invention is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the liquid crystal alignment agent of the present invention contains a polymer, the content ratio of the other polymer is preferably 0.1% by mass or more, and preferably 5% by mass or more, based on the total of the polymer. Effect such as improvement of solution characteristics and electrical characteristics.

[epoxy compound]

The liquid crystal alignment agent of the present invention exhibits a liquid by containing an epoxy compound The mechanical strength of the crystal alignment film is improved, and the adhesion between the formed liquid crystal alignment film and the substrate is improved.

The epoxy compound preferably has two or more epoxy groups in its molecule. Specific examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N' , N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane As the alkane, N,N-diglycidyl-cyclohexylamine, or the like, one or more selected from the group consisting of these compounds can be used.

Liquid crystal alignment agent of the present invention with respect to 100 parts by mass of the total of the polymer The content ratio of the epoxy compound in the medium is preferably 40 parts by mass or less, and more preferably 0.1 parts by mass to 30 parts by mass.

[functional decane compound]

The liquid crystal alignment agent of the present invention comprises a functional decane compound The coating property (printability) of the liquid crystal alignment agent is improved, and the adhesion between the formed liquid crystal alignment film and the substrate is improved.

The functional decane compound as described above may, for example, be 3-aminopropyltri Methoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl) 3-aminopropyltrimethoxy Baseline, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane , N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxymethylidenepropylpropyl Ethyltriamine, N-trimethoxyformamidopropyltriethylamine, 10-trimethoxycarbamimidyl-1,4,7-triazadecane, 10-triethoxy Formyl-1,4,7-triazadecane, 9-trimethoxycarbamido-3,6-diazadecyl acetate, 9-trimethoxycarbamimidin-3,6 -diazepine acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, 9-trimethoxyformamido-3,6-diazepine Methyl ester, methyl 9-triethoxycarbamido-3,6-diazadecanoate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-amine Propyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, glycidoxymethyltrimethoxy Base decane, glycidoxymethyl triethoxy Alkane, 2-glycidoxyethyltrimethoxydecane, 2-glycidoxyethyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl As the triethoxysilane or the like, one or more selected from the group consisting of these compounds can be used.

Liquid crystal alignment agent of the present invention with respect to 100 parts by mass of the total of the polymer The content ratio of the functional decane compound in the medium is preferably 2 parts by mass or less, and more preferably 0.02 parts by mass to 0.2 parts by mass.

<Preparation of Liquid Crystal Aligning Agent>

The liquid crystal alignment agent of the present invention is preferably prepared as described above as a necessity The specific polymer of the component and any other components used as needed are dissolved in the appropriate A solution composition contained in an organic solvent.

The organic solvent used in the liquid crystal alignment agent of the present invention is exemplified by N- Methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4- Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether, Ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone And isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, etc., and one or more selected from these compounds can be used.

The organic solvent used in the liquid crystal alignment agent of the present invention is specifically polymerized The solubility of the substance is high, and it is preferably an aprotic polar solvent, and it is more preferable to use one or more selected from the group consisting of N-methyl-2-pyrrolidone and γ-butyrolactone. It may also be selected from the group consisting of ethylene glycol-n-butyl ether (butyl cellosolve), diethylene glycol diethyl ether and 4-hydroxy-4-methyl-2- in the range which does not inhibit the solubility of the specific polymer. One or more solvents in the group consisting of pentanone.

Solid component concentration in the liquid crystal alignment agent of the present invention (liquid crystal alignment agent The ratio of the total mass of the components other than the solvent to the total mass of the liquid crystal alignment agent is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably in the range of 1% by mass to 10% by mass. Coating property can be made by setting the solid content concentration in this range A liquid crystal alignment agent excellent in balance with a film thickness.

Particularly preferred solid component concentration and solution viscosity range due to the substrate The method used when applying the liquid crystal alignment agent differs. For example, in the case of using the rotator method, it is preferable to set the solid content concentration to a range of 1.5% by mass to 4.5% by mass, thereby setting the solution viscosity to 4 mPa. s~13mPa. The scope of s. In the case of using the printing method, it is preferable to set the solid content concentration to a range of 3% by mass to 9% by mass, thereby setting the solution viscosity to 12 mPa. s~50mPa. The scope of s. In the case of using the inkjet method, it is preferable to set the solid content concentration to a range of 1% by mass to 5% by mass, thereby setting the solution viscosity to 3 mPa. s~15mPa. The scope of s.

The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 10 ° C to 50 ° C. More preferably, it is 20 ° C - 30 °C.

<Liquid crystal alignment film and liquid crystal display element>

The liquid crystal alignment film of the present invention is formed of the above liquid crystal alignment agent.

The liquid crystal alignment film of the invention can be applied to TN mode, STN mode, IPS A horizontal alignment type liquid crystal display element such as a mode or an FFS mode; or a vertical alignment type liquid crystal display element such as a VA mode.

However, the liquid crystal alignment agent of the present invention provides a liquid excellent in abrasion resistance Since the crystal is aligned to the film, it is preferably a horizontal alignment type liquid crystal display element which is often subjected to rubbing treatment in the step of forming the film, and more preferably a liquid crystal display element which is applied to the IPS mode or the FFS mode.

The liquid crystal display element of the present invention can be, for example, the following (1) to (3) Steps to make. In step (1), each of the required modes of operation uses a different base. board. Step (2) and step (3) are the same in each mode of operation.

[Step (1): Formation of coating film]

First, a coating film is formed on a substrate by applying the liquid crystal alignment agent of the present invention on a substrate and then heating the coated surface.

(1-1) In the case of manufacturing a liquid crystal display element of a TN mode, an STN mode or a VA mode, a substrate 2 provided with a patterned transparent conductive film is formed as a pair, and on each of the transparent conductive film forming faces, Preferably, the liquid crystal alignment agent of the present invention is applied by an offset printing method, a spin coating method, a roll coating method, or an inkjet printing method, and then each coated surface is heated to form a coating film.

For the substrate, for example, glass such as float glass or soda glass may be used; and resins such as poly(ethylene phthalate), polybutylene phthalate, polyether oxime, polycarbonate, and poly(alicyclic olefin) may be used. Transparent substrate, etc.

A transparent conductive film provided on one side of the substrate may be: a NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA), and indium tin oxide containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). (indium tin oxide, ITO) film or the like, in order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo etching after forming a transparent conductive film without pattern; A method of using a mask having a desired pattern or the like when using a transparent conductive film.

In order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, the surface of the substrate on which the coating film is to be formed may be pre-coated with a functional decane compound or a functional titanium compound before the liquid crystal alignment agent is applied. Waiting backward Pre-treatment of heating.

Forming by coating the coated surface after the liquid crystal alignment agent is applied membrane. This heating is preferably carried out by two-stage heating including preheating (prebaking) and calcination (postbaking). The prebaking conditions are, for example, from 40 ° C to 120 ° C for 0.1 minutes to 5 minutes, and the post-baking conditions are preferably from 120 ° C to 300 ° C, more preferably from 150 ° C to 250 ° C, and preferably for 5 minutes. 200 minutes, more preferably 10 minutes to 100 minutes.

The film thickness of the formed coating film is preferably 0.001 μm to 1 μm, more preferably It is 0.005 μm to 0.5 μm.

(1-2) The case of manufacturing an IPS mode or an FFS mode liquid crystal display element Condition: A substrate provided with a transparent conductive film patterned into a comb shape and a substrate not provided with a conductive film were used as a pair of substrates.

a conductive film forming surface of a substrate provided with a transparent conductive film, and not provided The liquid crystal alignment agent of the present invention is applied to one surface of the substrate of the conductive film, and then each coated surface is heated to form a coating film. The material of the substrate used at this time, the material of the transparent conductive film, the patterning method of the transparent conductive film, the coating method, the heating conditions after coating, the pretreatment of the substrate, and the preferred film thickness of the formed coating film are as described above (1). -1) Same.

In any of the above (1-1) and (1-2), After coating the liquid crystal alignment agent on the board, the organic solvent is removed to form a coating film which becomes a liquid crystal alignment film. At this time, the polymer contained in the liquid crystal alignment agent of the present invention is polyamic acid, Alternatively, in the case of a partially ruthenium-imided polymer having both a quinone ring structure and a guanine structure, the dehydration ring-closure reaction may be carried out by further heating after the formation of the coating film, thereby further producing a further Aminated coating film.

[Step (2): Friction treatment]

In manufacturing TN mode, STN mode, IPS mode or FFS mode In the case of a crystal display element, the coating film formed as described above is subjected to a rubbing treatment in which rubbing in a certain direction is performed by, for example, a roll on which a cloth containing long fibers such as nylon, rayon, or cotton is wound. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.

The liquid crystal alignment film is subjected to the following treatment: by aligning the liquid crystal alignment film a part of irradiating ultraviolet rays to change a pretilt angle of a partial region of the liquid crystal alignment film; after forming a resist film on a part of the surface of the liquid crystal alignment film, rubbing is performed in a direction different from the previous rubbing treatment, and then removing the resist The treatment of the film of the film; thus, the liquid crystal alignment film has different liquid crystal alignment capabilities in each region, whereby the field of view characteristics of the resulting liquid crystal display element can be improved.

In the case of manufacturing a VA mode liquid crystal display element, it may not be Although the coating film formed by the method is subjected to rubbing treatment, it is used as a liquid crystal alignment film as it is, but the above-described rubbing treatment may be carried out.

[Step (3): Manufacturing of Liquid Crystal Display Element]

Next, a pair of bases in which the liquid crystal alignment film is formed in the above manner are formed. A liquid crystal cell having a structure in which a liquid crystal is sandwiched in a gap (cell gap) in which the plates are opposed to each other.

In order to constitute a liquid crystal cell, the following methods can be utilized: The two substrates on which the liquid crystal alignment film is formed are bonded to each other by a sealant disposed on the peripheral portion thereof, and the liquid crystal alignment film surface is opposed to each other, and the liquid crystal is injected into the cell gap defined by the liquid crystal alignment film surface and the sealant. A method of sealing an injection hole; a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed, for example, an ultraviolet curable sealing material is disposed, and further disposed in a predetermined number of portions on the liquid crystal alignment film surface After the liquid crystal, the liquid crystal alignment film is bonded to the other substrate so as to be bonded to each other, thereby laminating the liquid crystal in front of the liquid crystal alignment film, and then irradiating the entire surface of the substrate with ultraviolet rays to cure the sealant.

In any of the above cases, when the formation of the liquid crystal alignment film is carried out In the case of the rubbing treatment, it is preferable that the rubbing directions of the liquid crystal alignment films of the two substrates are orthogonal or anti-parallel.

Then, the polarizing plate is attached to the outer surface of the liquid crystal cell in a predetermined direction. Thereby, a liquid crystal display element can be manufactured.

As the sealant, for example, alumina containing a hardener and as a spacer can be used. Ball epoxy resin, etc.

Liquid crystal can use nematic liquid crystal or near Smectic liquid crystal. Among these liquid crystals, a nematic liquid crystal is preferable. Specific examples thereof include Schiff base liquid crystal, azocycloalkyl liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, and ester. Liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine (pyrimidine) is a liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal, or the like. It is also possible to use the following substances in these liquid crystals: for example, cholesteric liquid crystal such as choline chloride, cholesteryl phthalate or cholesteryl carbonate; as the trade names "C-15", "CB" Chiral agent sold by -15" (manufactured by Merck); p-decyloxybenzylidene-p-decyloxybenzylidene-p-decyloxybenzylidene-p-decyloxybenzylidene P-amino-2-methylbutylcinnamate) and the like ferroelectric liquid crystal (ferroelectric liquid crystal).

The polarizing plate to be bonded to the outer surface of the liquid crystal cell is, for example, a polarizing plate in which a polarizing film called "H film" is sandwiched by a cellulose acetate protective film, and the H film is extended with polyvinyl alcohol. A polarizing film formed by absorbing iodine on one side or a polarizing plate containing the H film itself.

The liquid crystal display element obtained in the above manner can be effectively applied to various types The device can be used, for example, for: a clock, a portable game, a word processor, a note type personal computer, a car navigation system, a camcorder A display device such as a (camcorder), a personal digital assistant (PDA), a digital camera, a mobile phone, various monitors, and a liquid crystal television.

[Examples]

Hereinafter, the present invention will be further specifically described by way of examples, but The invention is not limited by these examples.

<Synthesis of Diamines>

The following synthesis examples are repeated as needed by the procedure described below to ensure the necessary amount for use in subsequent polymer synthesis.

Synthesis Example A-1

The compound (2-1-3) was synthesized according to the following Scheme 1.

In a 5 L separable flask equipped with a stirrer and a nitrogen gas introduction tube, 268.4 g of 4-aminobenzylamine was dissolved in 2,750 mL of tetrahydrofuran, and then 92.4 g of hexamethylene diisocyanate was slowly added, and recovered by filtration. The precipitate produced. The precipitate was recrystallized from N,N-dimethylacetamide to obtain 181.5 g of a white crystal of (2-1-3).

Synthesis Example A-2

The compound (2-1-5) was synthesized according to the following Scheme 2.

In the synthesis example A-1, a compound was obtained in the same manner as in the synthesis example A-1 except that instead of 4-aminobenzylamine, 299.2 g of 2-(4-aminophenyl)ethylamine was used. White crystals of 1-8.1) were 188.1 g.

Synthesis Example A-3

The compound (2-6-5) was synthesized according to the following Scheme 3.

[化18]

(1) Synthesis of Compound (2-6-5a)

Into a 500 mL three-necked flask equipped with a thermometer, a nitrogen gas introduction tube, and a dropping funnel, 36.8 g of 4-nitrophenylethanol and 200 mL of toluene were charged.

On the other hand, 16.8 g of 1,6-hexamethylene diisocyanate and 50 mL of toluene were placed in a dropping funnel.

While maintaining the temperature of the contents of the flask at 15 ° C to 25 ° C, the contents of the dropping funnel were gradually dropped. After completion of the dropwise addition, the reaction was carried out at 80 ° C for 1 hour with stirring. After the completion of the reaction, the reaction mixture was poured into 2 L of methanol, and the resulting precipitate was collected by filtration to be recovered, whereby 45.2 g of Compound (2-6-5a) was obtained.

(2) Synthesis of Compound (2-6-5)

Into a 1 L three-necked flask equipped with a reflux tube and a thermometer, the entire amount of the compound (2-6-5a) obtained above (45.2 g), 5% by weight of palladium carbon 2.3 g, and N,N-dimethyl 500 mL of carbamamine was used, and the inside was decompressed using an aspirator. Then, a balloon in which 3 L of hydrogen gas was sealed was attached to the reactor, and the system was filled with hydrogen gas, and then reacted at 60 ° C for 4 hours under stirring. After the completion of the reaction, the palladium carbon was removed by filtration through celite, and the filtrate was concentrated under reduced pressure, and the crystals thus precipitated were collected by filtration to recover 35.4 g of white crystals of compound (2-6-5).

<Synthesis of Polymers>

The solution viscosity of the polymer in each of the following synthesis examples was a value measured at 25 ° C using an E-type rotational viscometer.

Synthesis Example P-1

11 g (0.05 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 190 g (0.95 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as 4-diamine Aminophenyl = 4-aminobenzoic acid ester 71g (0.31 mole), 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl) )] 110 g (0.29 mol) of diphenylamine and 170 g (0.40 mol) of the compound (2-1-3) obtained in the above Synthesis Example A-1, dissolved in N-methyl-2-pyrrolidone (NMP) In 3,100 g, the reaction was carried out at 40 ° C for 6 hours, whereby a solution containing 15% by mass of poly-proline (PA-1) was obtained. The solution has a solution viscosity of 400 mPa. s.

Synthesis Example P-2

In the above Synthesis Example P-1, in place of the compound (2-1-3), The compound (2-1-5) obtained in Synthesis Example A-2 was obtained in the same manner as in Synthesis Example P-1 except that 180 g (0.40 mol) of the compound (II-5) was used in an amount of 3,200 g. A solution of 15% by mass of aminic acid (PA-2). The solution viscosity of this solution is 420mPa. s.

Synthesis Example P-3

200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, 2,2'-dimethyl-4,4'-di as diamine 130 g (0.6 mol) of aminobiphenyl and 180 g (0.40 mol) of the compound (2-1-5) obtained in the above Synthesis Example A-2, dissolved in 4,600 g of NMP, and carried out at 40 ° C for 3 hours The reaction was carried out, whereby a solution containing 15% by mass of polyglycolic acid (PA-3) was obtained. The solution has a solution viscosity of 160 mPa. s.

Synthesis Example P-4

200 g (0.90 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 22 g (0.100 mol) of 1,2,3,5-tricarboxycyclopentyl acetic acid dianhydride, p-benzene as diamine Diamine 22g (0.20 mole), 4,4-diaminodiphenyl ether 20g (0.10 mole), 3,5-diaminobenzoic acid 46g (0.30 mole) and the above synthesis example A-2 180 g (0.40 mol) of the obtained compound (2-1-5) was dissolved in a mixed solvent containing 1,400 g of NMP and 1,400 g of γ-butyrolactone (γ-BL), and carried out at 40 ° C for 4 hours. The reaction was carried out, whereby a solution containing 15% by mass of polyglycine (PA-4) was obtained. The solution viscosity of the solution is 410mPa. s.

Comparative Synthesis Example P-5

11 g (0.05 m) of pyromellitic dianhydride as tetracarboxylic dianhydride And 1,2,3,4-cyclobutanetetracarboxylic dianhydride 190 g (0.95 mol), 4-aminophenyl=4-aminobenzoate 160 g (0.71 mol) as a diamine, and 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine 110g (0.29 mol), dissolved in 1,300 g of NMP and 1,300 In a mixed solvent of γ-BL of g, the reaction was carried out at 40 ° C for 6 hours to obtain a solution containing 15% by mass of polyglycine (PA-5). The solution viscosity of this solution is 420mPa. s.

Comparative Synthesis Example P-6

40 g (0.20 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride And 1,2,3,4-cyclobutanetetracarboxylic dianhydride 160 g (0.80 mol), 4-aminophenyl=4-aminobenzoic acid ester as a diamine, 140 g (0.62 mol), 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine 110g (0.29 mol) and diethylene glycol (di-4- 26 g (0.09 mol) of aminophenyl) ether, dissolved in a mixed solvent containing 1,400 g of NMP and 1,400 g of γ-BL, and reacted at 40 ° C for 6 hours, thereby obtaining a polyglycine ( PA-6) 15% by mass solution. The solution has a solution viscosity of 850 mPa. s.

Comparative Synthesis Example P-7

200 g (0.90 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride And 1,2,3,5-tricarboxycyclopentyl acetic acid dianhydride 22 g (0.10 mol), p-phenylenediamine as a diamine 22 g (0.20 mol), 4,4-diaminodiphenyl ether 100 g (0.50 mol) and 3,5-diaminobenzoic acid 46 g (0.30 mol), dissolved in a mixed solvent containing 1,100 g of NMP and 1,100 g of γ-BL, and reacted at 40 ° C for 4 hours. Thus, a solution containing 15% by mass of poly-proline (PA-7) was obtained. The solution The solution viscosity is 410mPa. s.

Comparative Synthesis Example P-8

11 g (0.05 m) of pyromellitic dianhydride as tetracarboxylic dianhydride And 1,2,3,4-cyclobutanetetracarboxylic dianhydride 190 g (0.95 mol), diamine 4-aminophenyl=4-aminobenzoate 120 g (0.51 mol), 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine 110g (0.29 mol) and 4-(4-aminophenoxyl) 62-hydroxycarbonyl)-1-(4-aminophenyl)piperidine 62 g (0.20 mol), dissolved in a mixed solvent containing 1,400 g of NMP and 1,400 g of γ-BL, and reacted at 40 ° C for 6 hours. Thus, a solution containing 15% by mass of polyglycine (PA-8) was obtained. The solution viscosity of this solution is 420mPa. s.

Comparative Synthesis Example P-9

1,2,3,4-cyclobutanetetracarboxylic dianhydride 200 g as tetracarboxylic dianhydride (1.0 mol) and 210 g (1.0 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl as a diamine were dissolved in 3,700 g of NMP and carried out at 40 ° C for 3 hours. The reaction was carried out, whereby a solution containing 15% by mass of polyglycine (PA-9) was obtained. The solution has a solution viscosity of 160 mPa. s.

Comparative Synthesis Example P-10

11 g (0.05 m) of pyromellitic dianhydride as tetracarboxylic dianhydride And 1,2,3,4-cyclobutanetetracarboxylic dianhydride 190 g (0.95 mol), 4-aminophenyl = 4-aminobenzoic acid ester as a diamine 71 g (0.31 mol), 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine 110g (0.29 mol) and the following formula (R-1) The indicated compound was 120 g (0.40 mol) dissolved in 2,800 g of NMP. The reaction was carried out at 40 ° C for 6 hours, whereby a solution containing 15% by mass of poly-proline (PA-10) was obtained. The solution has a solution viscosity of 40 mPa. s.

Synthesis Example P-11

1.1 g (0.005 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 19 g (0.095 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4 as diamine -aminophenyl = 4-aminobenzoate 7.1 g (0.031 mol), 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4- Diphenylamine 11 g (0.029 mol) and 18 g (0.040 mol) of the compound (2-6-5) obtained in the above Synthesis Example A-3, dissolved in 318 g of NMP, and carried out at 40 ° C. The reaction was carried out in an hour, whereby a solution containing 15% by weight of polyglycine (PA-11) was obtained. The solution viscosity of this solution is 380mPa. s.

<Preparation and evaluation of liquid crystal alignment agent>

Example 1

(1) Preparation of liquid crystal alignment agent

In a solution containing 15% by mass of poly-proline (PA-1) obtained in the above Synthesis Example P-1, 5 parts by mass is added to 100 parts by mass of the polylysine in the polyamic acid solution. N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, further adding γ-BL, NMP and butyl cellosolve (BC) to form a solvent group A solution having γ-BL:NMP:BC=40:40:20 (mass ratio) and a solid content concentration of 4.0% by mass. This solution was filtered using a filter having a pore size of 0.45 μm, thereby preparing a liquid crystal alignment agent.

(2) Evaluation of abrasion resistance

The liquid crystal alignment agent prepared above was applied onto a transparent electrode surface of a glass substrate with a transparent electrode containing an ITO film using a spin coater, and heated (prebaked) on a hot plate at 80 ° C for 1 minute to remove the solvent. The film was heated (post-baked) by nitriding in a clean oven at 230 ° C for 15 minutes to form a coating film having an average film thickness of 100 nm. This coating film was subjected to five rubbing treatments under the conditions of a roller rotation speed of 1,000 rpm, a table moving speed of 2 cm/sec, and a hair pressing length of 0.4 mm by a friction machine having a roller wound with a cotton cloth. This rubbing treatment condition is an extremely accelerated acceleration test as compared with the rubbing treatment performed in the actual liquid crystal alignment film forming step.

The coating film after the rubbing treatment was observed with an optical microscope, and the number of foreign matter (the exfoliated material having a long diameter of 1 μm or more) in a region (0.25 mm ² ) of 500 μm × 500 μm was counted, and the rubbing resistance was evaluated based on the following criteria. Be "good".

Foreign matter is 4 / 0.25mm ² or less: good

Foreign matter is 5 / 0.25mm ² ~ 10 / 0.25mm ² : bad

Foreign objects are 11 / 0.25mm ² or more: extremely bad

(3) Evaluation of transparency

The liquid crystal alignment agent prepared above was applied onto a quartz substrate by a spin coater, heated (prebaked) on a hot plate at 80 ° C for 1 minute to remove the solvent, and then nitrided in a clean oven at 230 ° C. To heat (post-bake) for 15 minutes, A coating film having an average film thickness of 100 nm was formed. For the quartz substrate on which the coating film was formed, an ultraviolet-visible near-infrared spectrophotometer (manufactured by JASCO Corporation, product name "V-670") was used, and the same type of quartz substrate without a coating film was used as a reference to measure ultraviolet rays. The absorption spectrum in the visible light region was found to have a transmittance at a wavelength of 400 nm, and the result was 95%.

(4) Evaluation of liquid crystal alignment

Coating the liquid crystal alignment agent prepared above by spin coating The transparent electrode surface of the glass substrate with the transparent electrode of the ITO film was heated (prebaked) on a hot plate at 80 ° C for 1 minute to remove the solvent, and then heated by nitriding in a clean oven at 230 ° C (after Baking) For 15 minutes, a coating film having an average film thickness of 100 nm was formed. The coating film was subjected to a rubbing treatment under the conditions of a roll rotation speed of 1,000 rpm, a table moving speed of 2 cm/sec, and a hair press-in length of 0.4 mm by a friction machine having a roll on which a cotton cloth was wound, thereby imparting a liquid crystal to the coating film. The alignment ability is used to form a liquid crystal alignment film. Then, after ultrasonic cleaning for 1 minute in ultrapure water, it was dried in a clean oven at 100 ° C for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. The above operation was repeated to obtain a pair of (two pieces) substrates having a liquid crystal alignment film.

a liquid crystal alignment film of one of the pair of substrates The outer edge of the surface was coated with an epoxy resin adhesive to which alumina balls having a diameter of 5.5 μm were applied, and then the pair of substrates were superposed and pressure-bonded so that the liquid crystal alignment film faces were opposed to each other to harden the adhesive. Then, a nematic liquid crystal (MLC-2042, manufactured by Merck & Co., Inc.) was filled between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell.

With respect to the liquid crystal cell produced as described above, the presence or absence and degree of the abnormal region were observed by a microscope under crossed nicols, and the liquid crystal alignment property was evaluated in accordance with the following criteria. A region of 500 μm × 500 μm on the liquid crystal alignment film surface was reflected on a monitor attached to the microscope, and microscopic observation was performed while scanning it little by little.

No abnormal area observed: good

A situation in which an abnormal area is observed in a part of the component: defective

The situation where an abnormal area is observed on the entire surface of the component: extremely bad

Example 2 to Example 5 and Comparative Example 1 to Comparative Example 6

In the above-mentioned Example 1, a liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the type of polylysine contained in the polyamic acid solution to be used was changed to that described in Table 1. Evaluation.

The evaluation results are shown in Table 1.

Claims (8)

A liquid crystal alignment agent comprising a group selected from the group consisting of polyglycines having a divalent group represented by the following formula (1) and a quinone imidized polymer of the polyglycolic acid. At least 1 polymer: In the formula (1), n1 is an integer of 1 to 3; a plurality of X are independently an oxygen atom or a sulfur atom; and a plurality of Y are independently -NH- or an oxygen atom; and two R are present ^{1 is} independently a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms, and R ² is independently a divalent organic group in the presence of a plurality of, and "*" represents a bond, respectively. The liquid crystal alignment agent according to claim 1, wherein R ² in the formula (1) is a hydrocarbon group having 1 to 30 carbon atoms or a halogenated hydrocarbon group. The liquid crystal alignment agent according to claim 1 or 2, wherein: n1 in the formula (1) is 1; X is an oxygen atom; and Y is -NH-. The liquid crystal alignment agent according to claim 1 or 2, wherein the polymer is selected from the group consisting of reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (2). And at least one of the group consisting of the obtained polyamic acid and the ruthenium iodide polymer of the polyproline: N1 (2) in the formula, X, Y, R ¹ and R ² respectively and n1 (1) in the same formula, X, Y, R ¹ and R ² meanings. A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of claims 1 to 4. A liquid crystal display element comprising the liquid crystal alignment film according to item 5 of the patent application. A polymer selected from the group consisting of polylysine obtained by reacting a tetracarboxylic dianhydride with a diamine containing a compound represented by the following formula (2), and a ruthenium of the polyglycolic acid. At least one of the groups consisting of imidized polymers: [Chem. 20] In the formula (2), n1 is an integer of 1 to 3; a plurality of X are independently an oxygen atom or a sulfur atom; and a plurality of Y are independently -NH- or an oxygen atom; and two R are present ^{1 is} independently a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms, and R ² is independently a divalent organic group in the case where a plurality of R ² are present. A compound represented by the following formula (2): In the formula (2), n1 is an integer of 1 to 3; a plurality of X are independently an oxygen atom or a sulfur atom; and a plurality of Y are independently -NH- or an oxygen atom; and two R are present ^{1 is} independently a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms, and R ² is independently a divalent organic group in the case where a plurality of R ² are present.