TWI547511B - Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display device, imidized polymer and diamine compound - Google Patents

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, quinone imidized polymer, and diamine compound

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, a polymer, and a compound, and more particularly to a liquid crystal alignment agent which can be suitably used for producing a vertical alignment type liquid crystal display element.

In the past, liquid crystal display elements have developed various driving methods in which the electrode structure or the physical properties of the liquid crystal molecules used are different. For example, a twisted nematic (TN) type or a super twisted nematic (STN) is known. ), vertical alignment (VA) type, multi-domain vertical alignment (MVA) type, in-plane switching (IPS) type, fringe field switching (FFS) Various types of liquid crystal display elements such as an optically compensated bend (OCB) type. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. The material of the liquid crystal alignment film is a polyamic acid, a polyimide, a polyamic acid ester, a polyester, a polyorganosiloxane, or the like. a polymer in which various properties such as heat resistance, mechanical strength, and affinity with a liquid crystal are good In terms of aspect, polyaminic acid or polyimine is usually used.

The characteristics required for the liquid crystal alignment film include one of the characteristics required to exhibit a desired pretilt angle corresponding to the driving method. For example, when applied to a vertical alignment type liquid crystal display element such as a VA type or an MVA type, it is required to be able to A high pretilt angle (for example, a pretilt angle of 87 degrees or more) is exhibited. Further, a method for controlling the alignment of liquid crystal molecules by using a liquid crystal alignment film has been proposed in which a long-chain alkyl group or a steroid skeleton is introduced into a side chain of a polymer component contained in a liquid crystal alignment agent, or a phenylene group or a cyclohexyl group is introduced. A structure in which a plurality of cyclic groups are connected to each other (for example, refer to Patent Document 1 to Patent Document 3).

However, in recent years, the liquid crystal display element has been used not only as a small display terminal such as a personal computer but also as a large-sized display device such as a large-screen liquid crystal television or an information display. In addition, as the use of the substrate has increased, the liquid crystal dropping method (One Drop Fill (ODF) method) has been attracting attention as a manufacturing technique of a liquid crystal display element. The ODF method is a method of filling liquid crystal molecules on the entire surface of a panel by dropping liquid crystal molecules on one of a pair of substrates on which a liquid crystal alignment film is formed, and bonding another substrate in a vacuum. According to this method, compared with the previously used vacuum injection method, there is an advantage that the process time of the liquid crystal filling step can be greatly shortened.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2008/117759

[Patent Document 2] International Publication No. 2008/117760

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-305549

The ODF method has the above advantages, but on the other hand, in the case of manufacturing a vertical alignment type liquid crystal display element, display unevenness called "ODF unevenness" easily occurs, resulting in unevenness. The display quality of the liquid crystal display element is degraded. One reason for such display unevenness is considered to be insufficient alignment performance of liquid crystal molecules using a liquid crystal alignment film. Therefore, in order to improve the display quality of the liquid crystal display element even when the ODF method is employed, a liquid crystal alignment film which can exhibit liquid crystal alignment superior to that of the conventional liquid crystal alignment film is required.

Further, in the production step of the liquid crystal alignment film, there are cases in which pinholes or uneven coating films are formed on the coating film formed on the substrate by using the liquid crystal alignment agent. When a defect occurs in the coating film, the coating film may be peeled off from the substrate to reuse the substrate. However, in such reworking, it is required to be able to easily peel the coating film from the substrate (good peeling property).

In addition, the operating principles of various liquid crystal display elements are roughly classified into a transmissive type and a reflective type. Among them, in the transmissive liquid crystal display device, since the display is performed by the backlight source from the back surface of the device, the liquid crystal alignment film is exposed to light from the backlight source for a long period of time. On the other hand, in the reflective liquid crystal display device, since the light source for backlight is not used but is displayed by reflected light from external light such as sunlight, power consumption is less than that of the transmissive liquid crystal display element. Advantages, but on the other hand exposed to strong UV rays. Therefore, liquid crystal display elements are required to have excellent light resistance under any of the operating principles.

The present invention has been made in view of the above-described problems, and a main object thereof is to provide a liquid crystal alignment agent which can exhibit excellent liquid crystal alignment properties and can form a coating film having good peelability and light resistance to a substrate. Further, another object of the present invention is to provide a liquid crystal alignment film which has excellent liquid crystal alignment properties, light resistance, and good releasability to a substrate, and a liquid crystal display element including the liquid crystal alignment film.

The inventors of the present invention conducted active research to achieve the above-described problems of the prior art, and found that the above problem can be solved by including at least a part of a polymer contained in a liquid crystal alignment agent as a polymer having a specific structure in a side chain. Thus, the present invention has been completed. in particular, The present invention provides the following liquid crystal alignment agents, liquid crystal alignment films, liquid crystal display elements, and compounds and polymers for producing the same.

An aspect of the present invention provides a liquid crystal alignment agent comprising at least one polymer selected from the group consisting of polylysine, polyphthalate, polyimine, and polyorganosiloxane, and comprising The polymer (P1) having a group represented by the following formula (0) is used as the above polymer.

(In the formula (0), Ac ¹ and Ac ² are each independently a cyclohexane ring or a benzene ring, and these rings may have a substituent; R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; and X is an oxygen atom. , +-CO-O-, +-O-CO-, +-O-CH ₂ -, +-CH ₂ -O-, +-CO-S-, +-S-CO-, +-CONH- or +-NHCO- (wherein "+" represents a bond to a phenylene group); n ¹ is 1 or 2, and n ² is 0 or 1; wherein, in the case where n ¹ is 2, a plurality of Ac ¹ are respectively Independently having the above definition; m is an integer from 1 to 3; "*" indicates a binding bond.)

According to the liquid crystal alignment agent of the present invention, by including the polymer (P1) as a polymer component in at least a part thereof, a liquid crystal alignment film which exhibits excellent liquid crystal alignment properties can be formed. Further, according to the liquid crystal alignment agent of the present invention, it is possible to form a liquid crystal alignment film which can be easily peeled off from the substrate and which is excellent in light resistance.

In the liquid crystal alignment agent of the present invention, the polymer (P1) is preferably at least one selected from the group consisting of polylysine, polyphthalate, and polyamidiamine, and the polyamine, polyamine The acid ester and the polyimine are selected from the group consisting of tetracarboxylic dianhydride and tetracarboxylic acid diester compound. At least one compound is obtained by reacting with a diamine containing a compound represented by the following formula (1). By reacting a diamine having a group represented by the above formula (0) with a tetracarboxylic dianhydride, a polymer having a group represented by the above formula (0) in a side chain can be relatively easily synthesized.

(In the formula (1), Ac ¹ , Ac ² , R ¹ , X, n ¹ , n ² , n ¹ and m have the same meanings as the above formula (0).)

In the liquid crystal alignment agent of the present invention, the polymer (P1) preferably has a sum of the above n ¹ and the above n ² of 2 or 3, and more preferably a sum of the above n ¹ and the above n ² is 2. Further, the above X is preferably an oxygen atom, +-COO- or +-O-CO- (wherein "+" represents a bond to a phenylene group). In this case, the voltage holding ratio of the liquid crystal display element can be further improved.

Another aspect of the present invention provides a liquid crystal alignment film formed using the liquid crystal alignment agent described above. Further, another aspect of the present invention provides a liquid crystal display element including the above liquid crystal alignment film.

According to still another aspect of the present invention, there is provided a polymer which is at least one compound selected from the group consisting of tetracarboxylic dianhydride and tetracarboxylic acid diester compound, and the compound represented by the above formula (1) The diamine of the compound is obtained by a reaction. Further, the present invention provides a compound represented by the above formula (1).

Hereinafter, the liquid crystal alignment agent of the present invention will be described in detail.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention contains, as a polymer component, at least one polymer selected from the group consisting of polyglycolic acid, polyphthalate, polyimine, and polyorganosiloxane. Further, in particular, the polymer (P1) having a group represented by the following formula (0) is contained as the polymer.

(In the formula (0), Ac ¹ , Ac ² , R ¹ , X, n ¹ , n ² , n ¹ , m and "*" have the same meanings as above.)

In the above formula (0), the alkyl group having 1 to 20 carbon atoms in R ¹ may be linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group and the like. Propyl, n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-decyl , n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-eight Alkyl, n-nonadecyl, n-icosyl, and the like.

R ¹ is preferably a linear alkyl group having 3 to 12 carbon atoms, and more preferably a linear alkyl group having 3 to 7 carbon atoms.

In terms of being able to increase the voltage holding ratio of the liquid crystal display element, X is preferably an oxygen atom, +-CO-O- or +-O-CO-, and particularly preferably an oxygen atom.

Ac ¹ and Ac ² may both be a cyclohexane ring or a benzene ring, or may be a combination of a cyclohexane ring and a benzene ring. Among them, from the viewpoints of liquid crystal alignment, solubility in a solvent, and the like, it is preferred that both Ac ¹ and Ac ² are cyclohexane rings. Further, in the case where Ac ¹ and Ac ² are a cyclohexane ring, the cis-trans isomers of 1,4-cyclohexylene are preferably trans isomers, respectively.

Ac ¹ and Ac ² may each have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, or an alkyl group having 1 to 5 carbon atoms, a fluoroalkyl group or an alkoxy group, a hydroxyl group, a cyano group or a nitro group.

As n ¹ and n ² , if n ¹ is 1 or 2 and n ² is 0 or 1, the combination is not particularly limited. Among them, it is preferable that the sum of (n ¹ + n ² ) of n ¹ and n ² is 2 or 3, and it is more preferable that (n ¹ + n ² ) is 2. That is, the combination of n ¹ and n ² is preferably n ¹ =1 and n ² = 2, n ¹ =1 and n ² =1, or n ¹ = 2 and n ² =0, more preferably n ¹ =1 and n ² =1, or n ¹ = 2 and n ² =0.

The group represented by the above formula (0) has an alkylene group having a carbon number of 2, 4 or 6 between the ring Ac ¹ and the ring Ac ² . In the side chain of the polymer, by having the alkylene group between the ring Ac ¹ and the ring Ac ² (between the ring Ac ¹ and the benzene ring in the case of n ² =0), the liquid crystal can be further improved. The alignment of the liquid crystal molecules of the alignment film is preferred. The alkylene group is preferably an alkylene group having 2 or 4 carbon atoms, and particularly preferably an alkylene group having 2 carbon atoms.

Specific examples of the group represented by the above formula (0) include, for example, a group represented by the following formula (0-1) to formula (0-10), and among these groups, the following formula is preferred ( 0-1)~ groups represented by formula (0-6).

[Chemical 4]

(wherein R ¹ and "*" have the same meaning as the above formula (0).)

<Polymer (P1): Polylysine>

One of the polymers (P1) of the present invention is exemplified by polyamines having a group represented by the above formula (0). The polyamic acid can be obtained, for example, by the following method: [I] a method of reacting a tetracarboxylic dianhydride having a group represented by the above formula (0) with a diamine; [II] a tetracarboxylic acid A method of reacting a dianhydride with a diamine having a group represented by the above formula (0). Among these methods, the method [II] is preferably used in terms of ease of manufacture. In the following, a case where the polyamic acid having the group represented by the above formula (0) is synthesized by the method [II] will be described as an example.

[tetracarboxylic dianhydride]

Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid of the present invention include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, which may, for example, be 1,2,3,4-butanetetracarboxylic dianhydride (1,2,3,4-butane tetracarboxylic acid). Dichydride), etc.; the alicyclic tetracarboxylic dianhydride may, for example, be 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo 3--3-furyl)-naphtho[1,2-c]furan-1,3-dione (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-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-di Keto-6-spiro-3'-(tetrahydrofuran-2',5'-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 (5 -(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride), 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3 , 5:6-dianhydride (3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride), 2,4,6,8-tetracarboxybicyclo[3.3.0]octane- 2:4,6:8-dianhydride (2,4,6,8-tetracarboxy bicyclo[3.3.0]octane-2:4,6:8-dianhydride), 4,9-dioxatricyclo[5.3 .1.0 ^2,6] undecane -3,5,8,10--tetraone ^{(4,9-dioxatricyclo [5.3.1.0 2,6]} undecane-3,5,8,10-tetraone), cyclohexane For example, a tetracarboxylic dianhydride or the like; and the aromatic tetracarboxylic dianhydride may, for example, be pyromellitic dianhydride or the like; in addition, Japanese Patent Laid-Open Publication No. 2010-97188 may be used. The tetracarboxylic dianhydride or the like described. In addition, the above-mentioned tetracarboxylic dianhydride may be used alone or in combination of two or more.

The tetracarboxylic dianhydride for synthesizing polyglycolic acid is preferably one containing an alicyclic tetracarboxylic dianhydride in terms of solubility in a solvent or transparency. Among them, it is more preferable to include Free 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-di Oxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4, At least one of the group consisting of 6:8-dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as "specific tetracarboxylic dianhydride") is particularly preferably contained Free choice of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride and 1,2 And at least one of the group consisting of 3,4-cyclobutanetetracarboxylic dianhydride.

The tetracarboxylic dianhydride for synthesizing polyamic acid is preferably one containing 20 mol% or more of the above specific tetracarboxylic dianhydride with respect to the total amount of tetracarboxylic dianhydride used for synthesis, and more preferably contains 50 mol% or more, particularly preferably 80 mol% or more.

[diamine]

. Specific diamine (D)

The diamine used for the synthesis of the poly-proline of the present invention contains a diamine having a group represented by the above formula (0) (hereinafter also referred to as a specific diamine (D)). The specific diamine (D) may be any of an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diaminoorganophthaloxane, and the like. The specific diamine (D) is preferably an aromatic diamine, and specific examples thereof include a compound represented by the following formula (1).

(In the formula (1), Ac ¹ , Ac ² , R ¹ , X, n ¹ , n ² and m have the same meanings as the above formula (0).)

In the formula (1), a preferred specific example of each of Ac ¹ , Ac ² , R ¹ , X, n ¹ , n ² and m can be directly applied to the description of the above formula (0).

The two primary amino groups of the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to X. Which of these binding positions is more preferred differs depending on the kind of X bonded to the diaminophenyl group, for example, in the case where X is an oxygen atom, preferably in the 2,4-position relative to X or The 3,5-position, in the case where X is "+-O-CO-" or "+-CO-O-", it is preferably located at the 3,5-position with respect to X.

Specific examples of the specific diamine (D) include a compound represented by the following formula (1-1) to formula (1-10), and the like.

(wherein R ¹ has the same meaning as the above formula (0).)

The specific diamine (D) is preferably a compound represented by the above formula (1-1) to formula (1-6) among these compounds, and more preferably the above formula (1-1) to formula (1-4). Compounds indicated separately.

. Synthesis of specific diamines

The above specific diamine (D) can be synthesized by appropriately combining a conventional method of organic chemistry. As an example, for example, dinitrobenzene having a group represented by the above formula (0) can be synthesized, and then the nitro group of the obtained dinitro group can be hydrogenated to form an amino group, using an appropriate reduction system.

Here, for example, in the case where "X" is an oxygen atom, the above dinitrogen can be made into a corresponding alkylcyclohexylphenol, and dinitrate in the presence of a base such as sodium hydrogencarbonate, potassium carbonate or lithium carbonate. A dinitro-containing halide such as chlorobenzene or dinitrofluorobenzene is reacted to synthesize. Alternatively, it may be synthesized by reacting a corresponding halide having an alkylcyclohexyl structure with a dinitro group-containing hydroxy derivative such as dinitrophenol in the presence of a base.

In the case where "X" is "+-O-CH ₂ -", the corresponding alkylcyclohexylphenol, dinitrobenzyl chloride or the like can be made to contain a dinitro group in the presence of a base. The halide is reacted to synthesize.

In the case where "X" is "+-CH ₂ -O-", the corresponding halide having an alkylcyclohexyl structure and a dinitro group-containing hydroxyl group such as dinitrophenol can be obtained by the presence of a base. The derivative is reacted to synthesize.

In the case where "X" is "+-O-CO-", the corresponding alkylcyclohexylphenols, and dinitrobenzoguanidine chloride can be obtained by the presence of a suitable base such as triethylamine. A dinitro-containing carboxylic acid halide such as dinitrobenzoyl chloride or dinitrobenzoyl bromide is reacted to synthesize.

In the case where "X" is "+-CO-O-", it can be made in the presence of a suitable base. The carboxylic acid halide having an alkylcyclohexyl structure is reacted with a dinitro group-containing hydroxy derivative such as dinitrophenol to be synthesized.

In the case where "X" is "+-S-CO-", the corresponding thiol compound having an alkylcyclohexyl structure and dinitro group can be obtained by the presence of a suitable base such as triethylamine. A dinitro-containing carboxylic acid halide such as benzamidine chloride is reacted to synthesize.

In the case where "X" is "+-CO-S-", the corresponding carboxylic acid halide having an alkylcyclohexyl structure and dinitrothiophenol can be obtained by the presence of a suitable base. A dinitrothiophenol-containing thiol derivative such as dinitrothiophenol is reacted and synthesized.

In the case where "X" is "+-NHCO-", the corresponding amino substituent having an alkylcyclohexyl structure, and dinitrobenzhydryl chloride may be contained in the presence of a suitable base. The nitrocarboxylic acid halide is reacted to synthesize.

In the case where "X" is "+-CONH-", the corresponding carboxylic acid halide having an alkylcyclohexyl structure, dinitroaniline or the like may be contained in the presence of a suitable base. The amino substituent is reacted to synthesize.

The reaction for obtaining the above dinitrogen is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 180 ° C, and more preferably 0 ° C to 120 ° C. Further, the reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours. As the organic solvent, a compound which is usually used in the case of the substitution reaction can be used, and specific examples thereof include an alcohol, tetrahydrofuran, toluene, dimethyl hydrazine, dimethylformamide, dimethylacetamide, and 1-methyl group. -2-pyrrolidone and the like.

The reduction reaction of the above dinitro group can be carried out in an organic solvent, for example, using zinc, lithium aluminum hydroxide, a palladium catalyst-hydrogen system or the like. As the organic solvent, a compound which is usually used in the case of a reduction reaction can be used, and specific examples thereof include tetrahydrofuran and an alcohol. The reaction temperature is preferably -20 ° C to 180 ° C, and more preferably 10 ° C to 120 ° C. Further, the reaction time is preferably from 0.1 to 72 hours, more preferably from 0.5 to 48 hours. However, the synthesis method of the specific diamine (D) It is not limited to the above method.

. Other diamines

The diamine used for synthesizing the polyglycolic acid of the present invention may be used alone or in combination with a specific diamine (D).

Examples of the other diamine which can be used herein include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diaminoorganosiloxane, and the like. Specific examples of the diamines include aliphatic mediamines such as metaxylylene diamine, 1,3-propane diamine, and tetramethylene diamine. (tetramethylene diamine), pentamethylene diamine, hexamethylene diamine, etc.; for example, alicyclic diamine: 1,4-diaminocyclohexane (1, 4) -diaminocyclohexane), 4,4'-methylene bis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane (1,3-bis) (aminomethyl)cyclohexane) and the like; examples of the aromatic diamine include p-phenylenediamine, 4,4'-diamino diphenyl methane, 4, 4 '4,4'-diamino diphenyl sulfide, 1,5-diamino naphthalene, 2,2'-dimethyl-4,4'-di Aminobiphenyl (2,2'-dimethyl-4,4'-diaminobiphenyl), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (2,2'-bis(trifluoromethyl) )-4,4'-diaminobiphenyl), 2,7-diaminofluorene, 4,4'-diaminodiphenylether (4,4'-diaminodiphenylether) , 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-amino) Phenyl) 9,9-bis(4-aminophenyl)fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (2,2-bis[4-( 4-aminophenoxy)phenyl]hexafluoropropane), 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diiso) Propylene) 4,4'-(p-phenylenediisopropylidene)bisaniline, 4,4'-(m-phenylenediisopropylidene)bisaniline (4,4'-(m-phenylenediisopropylidene)bisaniline ), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl (1,4) -bis(4-aminophenoxy)biphenyl), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine (2, 4-diaminopyrimidine), 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole (N-methyl-3,6-diaminocarbazole), N-ethyl-3,6-diaminocarbazole, N-benzene -3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine (N,N'-bis(4-aminophenyl)- Benzidine), N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine (N,N'-bis(4-aminophenyl)-N,N'-dimethyl benzidine), 1 , 4-bis-(4-aminophenyl)-piperazine, 1-(4-aminophenyl)-2,3-dihydro-1, 3,3-Trimethyl-1H-indene-5-amine, 1-(3-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine 4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indol-6-amine (1-(4-aminophenyl)-2,3-dihydro-1,3, 3-trimethyl-1H-indene-6-amine), 3,5-diaminobenzoic acid, cholestyloxy-3,5-diaminobenzene (cholestanyloxy-3,5 -diaminobenzene), cholestenyloxy-3,5-diaminobenzene, cholestaneyl-2,4-diaminobenzene ), cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, 3, 5-diaminobenzoic acid cholesteryl (cholestenyl 3,5-diaminobenzoate), 3,5-diaminobenzoate 3,5-diaminobenzoate, 3,6-bis(4-aminobenzylideneoxy)cholestane ( 3,6-bis(4-aminobenzoyloxy)cholestane), 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-three 4-(4'-trifluoromethoxybenzoyloxycyclohexyl-3,5-diaminobenzoate), 4-(4'-trifluoromethyl) 4-(4'-trifluoromethylbenzoyloxycyclohexyl-3,5-diaminobenzoate), 1,1-bis(4-((aminobenzene) 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane), 1,1-bis(4-((amino) Phenyl)methyl)phenyl)-4-heptylcyclohexane (1,1-bis(4-((aminophenyl)phenyl)phenyl)-4-heptylcyclohexane)), 1,1-bis(4-(( 1,1-bis(4-(aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4- ((Aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane (1,1-bis(4-((aminophenyl) )methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane), 2,4-diamino-N,N-diallylaniline, 4-aminobenzyl 4-aminobenzylamine, 3-aminobenzylamine, and the following formula (A-1)

(wherein, X ^I and X ^II are each a single bond, -O-, -COO- or -OCO-, respectively, R ^I is an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1 and b is 0 to 2 The integer, c is an integer from 1 to 20, and n is 0 or 1; where a and b are not 0)

Examples of the compound to be represented, and examples of the diaminoorganosiloxane include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane. In addition to the above, the diamine described in JP-A-2010-97188 can be used. As its As the diamine, these diamines may be used alone or in combination of two or more.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _n -" in the above formula (A-1) is preferably an alkanediyl group having a carbon number of 1 to 3, *-O-, *- COO- or *-OC ₂ H ₄ -O- (wherein the bond labeled "*" is bonded to the diaminophenyl group). Specific examples of the group "-C _c H _2c+1 " are exemplified as the alkyl group having 1 to 20 carbon atoms in R ¹ of the above formula (0). The two amino groups in the diaminophenyl group are preferably at the 2,4-position or the 3,5-position relative to the other groups.

Specific examples of the compound represented by the above formula (A-1) include a compound represented by the following formula (A-1-1) to formula (A-1-3), and the like.

The content ratio of the specific diamine (D) is preferably 1 mol% or more, and more preferably 1 mol% to 50 mol%, based on the total amount of the diamine used for the synthesis of the polyamic acid. By setting the content ratio to 1 mol% or more, the pretilt angle of the liquid crystal alignment film formed using the liquid crystal alignment agent can be further improved. The content ratio is particularly preferably from 5 mol% to 30 mol%.

[Molecular weight regulator]

When the polyamic acid is synthesized, a terminal modified polymer can be synthesized together with the tetracarboxylic dianhydride and the diamine as described above using a suitable molecular weight modifier. By preparing the terminal-modified polymer, the coating property (printability) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention.

The molecular weight modifier may, for example, be a monoanhydride or a monoamine compound. Monoamine compound, monoisocyanate compound, and the like. Specific examples of the molecular weight modifiers include, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, and n-decyl dibutylate. N-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride N-hexadecyl succinic anhydride); Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, and n-heptylamine (n). -heptylamine), n-octylamine or the like; examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

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

<Synthesis of polyaminic acid>

The ratio of the tetracarboxylic dianhydride to the diamine to be used in the synthesis reaction of the polyamic acid of the present invention is preferably such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 equivalent to 2 equivalents per 1 equivalent of the amino group of the diamine. The ratio is more preferably a ratio of 0.3 equivalent to 1.2 equivalents.

The synthesis reaction of polylysine is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. Further, the reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

Here, examples of the organic solvent include an aprotic polar solvent, a phenol solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon.

Specific examples of the organic solvent include, for example, the above aprotic polar solvent. N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl- N-ethyl-2-pyrrolidone, N,N-dimethyl acetamide, N,N-dimethyl formamide , dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, etc.; the above phenolic solvent is, for example, Phenol, m-cresol, xylenol, halogenated phenol, etc.; examples of the above alcohol include methanol, ethanol, isopropanol, cyclohexanol, and ethylene. Alcohol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc.; examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. Examples of the above esters include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and diethyl oxalate. Diethyl malonate, propionic acid An ester, isoamyl isobutyrate or the like; examples of the above ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol diethyl ether, ethylene glycol-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 diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, two Ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, diisoamyl ether, etc.; for the above halogenated hydrocarbon, for example, dichloromethane, 1,2-dichloroethane, 1 , 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, etc.; examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, xylene, and the like.

Among these organic solvents, it is preferred to use one or more organic solvents selected from the group consisting of an aprotic polar solvent and phenol and a derivative thereof (the first group of organic solvents), or an organic group selected from the first group. A mixture of one or more organic solvents in the solvent and one or more organic solvents 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 group of organic solvents and the second group The total amount of the organic solvents is preferably 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 30% by weight or less.

The amount (a) of the organic solvent to be used is preferably in an amount of from 0.1% by weight to 50% by weight based on the total amount (a+b) of the reaction solution, and the total amount (b) of the tetracarboxylic dianhydride and the diamine.

A reaction solution obtained by dissolving polylysine was obtained in the above manner. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or the poly-proline acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal alignment agent, or the isolated polyamic acid may be purified. Provided to the preparation of a liquid crystal alignment agent. In the case of polyhydrazide dehydration ring closure to form polyimine, the above reaction solution can be directly supplied to the dehydration ring closure reaction, or the polylysine contained in the reaction solution can be isolated and then supplied to dehydration. The ring closure reaction, or the isolated polyamic acid can also be purified and then supplied to the dehydration ring closure reaction. The isolation and purification of polylysine can be carried out according to well-known methods.

<Polymer (P1): Polyphthalate>

The polymer (P1) contained in the liquid crystal alignment agent of the present invention is a polyglycolate having a group represented by the above formula (0). The polyperurethane can be obtained, for example, by the following method: [I] a method of synthesizing a polyamic acid obtained by the above-described synthesis reaction by using a hydroxyl group-containing compound or an ether compound; [II] A method of reacting a tetracarboxylic acid diester compound with a diamine compound containing the above specific diamine (D). Here, the tetracarboxylic acid diester compound in the method [II] may, for example, be a diester compound of a tetracarboxylic acid which is a precursor of the above tetracarboxylic dianhydride. Specifically, for example, a tetracarboxylic acid diester dichloride may be mentioned. A tetracarboxylic acid diester having two carboxyl groups. Further, the diamine used in the method [II] may be used together with the above specific diamine (D). Further, the polyglycolate as the polymer (P1) may have only a phthalate structure, or may be a partial ester compound in which a valeric acid structure and a phthalate structure coexist.

<Polymer (P1): Polyimine>

Other examples of the polymer (P1) contained in the liquid crystal alignment agent of the present invention include a polyimine having a group represented by the above formula (0). The polyimine can be obtained by subjecting polylysine having the group represented by the above formula (0) synthesized in the above manner to dehydration ring closure and imidization.

The polyimine may be a fully quinone imine compound obtained by dehydrating and ring-closing a glycine structure of a polyamic acid as a precursor thereof, or may be a mixture of only a part of a proline structure. A partial ruthenium imide of a proline structure and a quinone ring structure. The ruthenium imidization ratio of the polyimine of the present invention is preferably 30% or more, more preferably 50% to 99%, and particularly preferably 60% 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, a part of the quinone ring may be an isoindole ring.

The dehydration ring closure of polylysine is preferably carried out by heating the polyamic acid or by dissolving the polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, optionally heating. method. Among them, it is preferred to use the latter method.

In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of the above polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The dehydrating agent is preferably used in an amount of from 0.01 mol to 20 mol based on 1 mol of the proline structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, collidine, lutidine or triethyiamine can be used. The amount of the dehydration ring-closure catalyst used is preferably set to 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent to be used. The organic solvent used in the dehydration ring closure reaction is exemplified as an organic solvent exemplified as an 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 polyienimine was obtained in the above manner. The reaction solution can be directly The preparation of the liquid crystal alignment agent can also be carried out by removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and then supplying the liquid crystal alignment agent, or can be provided after the selenization of the liquid crystal alignment agent, or The isolated polyimine can also be purified and then supplied to the preparation of the liquid crystal alignment agent. These purification operations can be carried out in accordance with well-known methods.

The polyamic acid, polyphthalate and polyimine obtained in the above manner are preferably 10 mPa when it is made into a solution having a concentration of 10% by weight. s~800 mPa. The solution viscosity of s is more preferably 15 mPa. s~500 mPa. s solution viscosity. Further, the solution viscosity (mPa.s) of the above polymer is a polymerization prepared at a concentration of 10% by weight for a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer. The solution was measured at 25 ° C using an E-type rotational viscometer.

The polystyrene-reduced weight average molecular weight measured by gel permeation chromatography is preferably 1,000 to 500,000, more preferably 2,000 to 300,000.

<Polymer (P1): Polyorganooxane>

Other examples of the polymer (P1) contained in the liquid crystal alignment agent of the present invention include polyorganosiloxane having a group represented by the above formula (0). The polyorganosiloxane can be obtained, for example, by (I) hydrolyzing and condensing a hydrolyzable decane compound (s1) having an epoxy group or a mixture of the decane compound (s1) and another decane compound. a method of reacting a polymer with a carboxylic acid having a group represented by the above formula (0); (II) a hydrolyzable decane compound (s2) having a group represented by the above formula (0), or A method of hydrolyzing and condensing a mixture of a decane compound (s2) and another decane compound. Further, the methods (I) and (II) above may be carried out by appropriately combining conventional methods of organic chemistry.

The polyorganosiloxane is preferably a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of 500 to 1,000,000, more preferably 1,000 to 100,000, particularly preferably Choose from 1,000 to 50,000.

The liquid crystal alignment agent of the present invention contains one kind or a combination of two or more kinds of the above-mentioned polymers selected from the group consisting of polyproline, polyphthalate, polyimine and polyorganosiloxane. Polymer (P1). In the liquid crystal alignment agent of the present invention, the content ratio of each polymer to the total amount of the polymer (P1) can be appropriately selected depending on the use or environment to be used, and from the viewpoint of more preferably obtaining the effects of the present invention, it is preferably Having at least one selected from the group consisting of polylysine, polyphthalate, and polyimine as the polymer (P1), more preferably comprising a component selected from the group consisting of polylysine and polyimine At least one of the groups is as the polymer (P1), and it is particularly preferable that the polymer (P1) is at least one selected from the group consisting of polyglycine and polyimine.

In the case where at least one of the polyamic acid and the polyimine is used as the polymer (P1), the total content of the polymer (P1) contained in the liquid crystal alignment agent is preferably 1% by weight to 100% by weight, more preferably 5% by weight to 100% by weight. In addition, one type of the above-mentioned polymer may be used for the polymer (P1), or two or more types may be used in combination. In addition, when two or more types are used in combination, a combination of polymers having the same main skeleton may be used, or a combination of polymers having different main skeletons may be used.

Solvent

In the liquid crystal alignment agent of the present invention, the polymer is preferably dissolved in an organic solvent.

The solvent used for preparing the liquid crystal alignment agent of the present invention varies depending on the kind of the polymer contained in the liquid crystal alignment agent. Specifically, the liquid crystal alignment agent of the present invention alone contains at least one polymer selected from the group consisting of polyglycolic acid, polyphthalate, and polyamidiamine, or contains the polyamic acid or the like. In the case of a polymer and a polyorganosiloxane as a polymer, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactone, N,N-dimethylmethyl Indoleamine, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate Ester, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-positive Butyl ether (butyl cellosolve), 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, dipropylene glycol monomethyl ether (DPM), diisobutyl ketone, isoamyl propionate, Isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, and the like. These solvents may be used singly or in combination of two or more.

On the other hand, when the liquid crystal alignment agent of the present invention contains only polyorganosiloxane as a polymer, for example, an alcohol such as 1-ethoxy-2-propanol, propylene glycol monoethyl ether or butyl cellosolve may be mentioned; Ether such as diethylene glycol ethyl methyl ether; n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, acetic acid Ester such as amyl ester.

<Other ingredients>

The liquid crystal alignment agent of the present invention may contain other components as needed. Examples of the other component include a polymer other than the specific polymer, a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compound"), a functional decane compound, and the like.

[Other polymers]

The other polymers described above can be used to improve solution properties or electrical properties. Examples of the other polymer include a polymer, polyester, and poly group which do not have a group represented by the above formula (0), which is a polyphthalic acid, a polyphthalate, a polyamidene or a polyorganosiloxane. Amidoxime, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly(styrene-phenylmaleimide) derivative, a poly(meth)acrylate, or the like. In the case where other polymer is added to the liquid crystal alignment agent, the compounding ratio of the other polymer is preferably 50% by weight or less, more preferably 0.1% by weight to 40% by weight based on the total amount of the polymer in the composition. It is especially preferably from 0.1% by weight to 30% by weight.

[epoxy group-containing compound]

The epoxy group-containing compound can be used to improve the adhesion or electrical properties of the liquid crystal alignment film to the surface of the substrate. Here, examples of the epoxy group-containing compound include the following compounds as preferred compounds: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol epoxide. Propyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane tricyclic Oxypropyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, N,N,N',N'-tetraepoxypropyl-m-xylylenediamine, 1,3-double (N, N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, N,N-diepoxy Propyl-benzylamine, N,N-diepoxypropyl-aminomethylcyclohexane, N,N-diepoxypropyl-cyclohexylamine and the like.

Further, as an example of the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane having the disclosure of WO 2009/096598 may be used.

When the epoxy compound is added to the liquid crystal alignment agent, the compounding ratio of the epoxy compound is preferably 40 parts by weight or less, more preferably 100 parts by weight or less based on 100 parts by weight of the total of the polymer contained in the liquid crystal alignment agent. 0.1 parts by weight to 30 parts by weight.

[functional decane compound]

The above functional decane compound can be used for the purpose of improving the printability of the liquid crystal alignment agent. Examples of such a functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxy group. Decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxy decane, 3-ureidopropyltriethoxy decane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-triethoxydecylpropyltriethylenetriamine , 10-trimethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-trimethoxydecyl- Methyl 3,6-diazepine, N-benzyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, glycidoxymethyltrimethyl Oxyquinone Alkyl, 2-glycidoxyethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, and the like.

In the case where the functional decane compound is added to the liquid crystal alignment agent, the compounding ratio of the functional decane compound is preferably 2 parts by weight or less, more preferably 0.02 part by weight to 0.2% by weight based on 100 parts by total of the total of the polymer. Parts by weight.

Further, in addition to the above, other components may be a compound having at least one oxetanyl group in the molecule, an antioxidant, or the like.

The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably selected. It is in the range of 1% by weight to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described later, and is preferably heated to form a coating film as a liquid crystal alignment film or a coating film to be a liquid crystal alignment film. In this case, the solid content concentration is less than 1 weight. In the case of %, the film thickness of the coating film became too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large to obtain a favorable liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases to form a liquid crystal having poor coating properties. Orientation film.

A particularly preferable range of the solid content concentration differs depending on the method used when the liquid crystal alignment agent is applied onto the substrate. For example, in the case of using a spinner method, the solid content concentration is particularly preferably in the range of 1.5% by weight to 4.5% by weight. In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3% by weight to 9% by weight, thereby setting the solution viscosity to 12 mPa. s~50 mPa. The scope of s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1% by weight to 5% by weight, thereby setting the solution viscosity to 3 mPa. s~15 mPa. 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, and more preferably from 20 ° C to 30 ° C.

<Liquid crystal alignment film and liquid crystal display element>

The liquid crystal alignment film of the present invention is formed by using a liquid crystal alignment agent prepared in the above manner. Further, the liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The mode of operation of the liquid crystal display element is not particularly limited, and a vertical alignment type such as a VA type or an MVA type is particularly preferable.

Hereinafter, a method for producing a liquid crystal display device of the present invention will be described, and a method for producing the liquid crystal alignment film of the present invention will be described in the same description. In addition, a method of manufacturing a VA liquid crystal display element will be described below as an example.

[Step (1): Formation of coating film]

First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate.

First, a two-layer substrate provided with a patterned transparent conductive film is used as a pair, and the liquid crystal alignment agent of the present invention is applied to the surface of the transparent conductive film formed on each of the substrates, preferably by offset printing (offset) Printing method), a spin coating method, a roll coater method, or an inkjet printing method. For the substrate, for example, glass such as float glass or soda glass may be used; and polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate may be used. A transparent substrate of plastic such as poly(alicyclic olefin). The 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), an ITO film containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), 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 a pattern, and a mask having a desired pattern when forming a transparent conductive film can be utilized. The method of the cover, etc. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, the surface on which the coating film is to be formed on the surface of the substrate may be coated with a functional decane compound or a functional titanium compound. deal with.

After the liquid crystal alignment agent is applied, preheating (prebake) is preferably performed for the purpose of preventing the sag of the applied liquid crystal alignment agent. The prebaking temperature is preferably from 30 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C, and particularly preferably from 40 ° C to 100 ° C. The prebaking time is preferably from 0.25 minutes to 10 minutes, more preferably from 0.5 minutes to 5 minutes. Then, the solvent is completely removed, and a calcination (postbake) step is carried out for the purpose of thermally imidating the proline structure present in the polymer as needed. The post-baking temperature is preferably from 80 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C. The post-baking time is preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 100 minutes. Thus, the film thickness of the formed film is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

The organic solvent is removed by heating after coating the liquid crystal alignment agent, thereby forming a coating film to be an alignment film. In this case, the polymer contained in the liquid crystal alignment agent of the present invention is a polyphthalic acid, or a polyamidomate, or a ruthenium iodide polymer having a quinone ring structure and a proline structure. Further, a dehydration ring-closure reaction may be carried out by further heating after the formation of the coating film to prepare a coating film which is further imidized.

[Step (2): Construction of liquid crystal cell]

A liquid crystal cell is manufactured by preparing two substrates in which the liquid crystal alignment film is formed as described above, and disposing liquid crystal between the two substrates arranged in the opposite direction.

In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a previously known method (vacuum injection method). First, the two substrates are placed facing each other with a gap (cell gap) so that the liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, and are divided by the surface of the substrate and the sealant. After filling the liquid crystal in the cell gap, the injection hole is sealed, thereby manufacturing a liquid crystal cell. The second method is a method called the One Drop Fill (ODF) method. In two substrates on which a liquid crystal alignment film is formed For example, an ultraviolet curable sealing material is applied to a predetermined portion of one of the substrates, and the liquid crystal is dropped on a predetermined number of portions on the liquid crystal alignment film surface, and then the other substrate is bonded to the liquid crystal alignment film so as to face each other. The liquid crystal cell is manufactured by spreading the liquid crystal over the entire surface of the substrate, and then irradiating the entire surface of the substrate with ultraviolet light to harden the sealant. In the case of using any of the methods, it is preferred to remove the liquid crystal cell by heating the liquid crystal cell produced in the above manner to a temperature at which the liquid crystal to be used becomes an isotropic phase, and then slowly cooling to room temperature. Flow alignment. Then, the liquid crystal display element of the present invention can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell.

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

The liquid crystal may, for example, be a nematic liquid crystal or a smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, Schiff base liquid crystal or azo azo (azoxy) may be used. Liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane Liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal, or the like. Further, a cholesteric liquid crystal such as cholesteric alcohol, cholesteryl phthalate or cholesteryl carbonate may be added to these liquid crystals; for example, the trade name "C" Chiral agent sold by -15", "CB-15" (manufactured by Merck); p-methoxybenzylidene-p-amino-2-methylbutyl cinnamate (ferroelectric liquid crystal) such as (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate).

The polarizing plate to be bonded to the outer surface of the liquid crystal cell may be a polarizing film called an "H film" sandwiched between a cellulose acetate protective film (the H film is formed by stretching the polyvinyl alcohol sideways). A polarizing plate made of a polarizing film that absorbs iodine or a polarizing plate including the H film itself.

The liquid crystal display element of the present invention can be effectively applied to various devices, for example, can be used for: a timepiece, a portable game console, a word processor, a note type personal computer, a car. Car navigation system, camcorder, personal digital assistant (PDA), digital camera, mobile phone, smart phone, various monitors, LCD TV, information Various display devices such as an information display.

[Examples]

The invention is further illustrated by the following examples, but the invention is not limited by the examples.

The solution viscosity of each polymer solution in the synthesis example and the oxime imidization ratio of polyimine were measured by the following methods.

[Solid viscosity of polymer solution]

Solution viscosity of polymer solution [mPa. s] was prepared by using a T-type rotational viscometer to prepare a solution having a polymer concentration of 10% by weight using a predetermined solvent, and measuring at 25 °C.

[醯Iminization rate of polyimine]

The solution of polyimine is put into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl hydrazine, and tetramethyl decane is used as a reference substance at room temperature. ¹ H- NMR measurement ^{(1 H-Nuclear magnetic resonance,} 1 H-NMR). The oxime imidization ratio [%] was determined from the obtained ¹ H-NMR spectrum by the formula represented by the following formula (1a).

醯 imidization rate [%] = (1-A ¹ / A ² × α) × 100 (1a)

(In the formula (1a), A ¹ is the peak area of the proton derived from the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of other protons relative to the polymer The ratio of the number of protons of the NH group in (polyglycine).)

<Synthesis of Specific Diamines (D)>

[Synthesis Example 1: Synthesis of Compound (D-1)]

Compound (D-1) was synthesized according to the following Scheme 1.

The compound represented by the above formula (1-1-1A) is added to a 500 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube (wherein the cis-trans isomerization of 1,4-cyclohexylene is trans The isomer) 35.7 g, 20.3 g of 2,4-dinitrochlorobenzene, 15.2 g of potassium carbonate and 300 mL of N,N-dimethylacetamide were reacted at 100 ° C for 4 hours. After completion of the reaction, 1 L of ethyl acetate, 500 mL of tetrahydrofuran, and 1 L of 1 M hydrochloric acid water were added to remove the aqueous layer, which was washed three times with water. Then, magnesium sulfate was added to the organic layer and dried, and the mixture was concentrated, and the precipitated crystals were collected and dried to obtain 36.6 g of pale yellow crystals of the compound of the formula (1-1-1B).

Then, 36.6 g of the compound represented by the above formula (1-1-1B), 1.83 g of palladium carbon, 350 mL of tetrahydrofuran, 350 mL of ethanol, and 80% of hydrazine were added to a 1 L three-necked flask equipped with a thermometer and a nitrogen introduction tube. 39.4 g of an aqueous hydrate solution was reacted at room temperature for 20 hours. After completion of the reaction, 1 L of ethyl acetate was added, and after washing with water for 3 times, the organic layer was concentrated to precipitate crystals. The mixture was filtered and dried to obtain 25.9 g of pale brown crystals of Compound (D-1) represented by the above formula (1-1-1).

[Synthesis Example 2: Synthesis of Compound (D-2)]

Compound (D-2) was synthesized according to the following Scheme 2.

The compound represented by the above formula (1-1-1A) is added to a 500 mL three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen introduction tube (wherein cis-trans isomerism of 1,4-cyclohexylene) They were 35.7 g of trans isomer, 200 mL of tetrahydrofuran and 11.13 g of triethylamine, and cooled to below 5 °C in an ice bath. Next, a solution obtained by dissolving 23.0 g of 3,5-dinitrobenzimidyl chloride in 100 mL of tetrahydrofuran was slowly dropped over 30 minutes, and the mixture was returned to room temperature for 1 hour. After completion of the reaction, 500 mL of ethyl acetate and 500 mL of a 1 M aqueous hydrochloric acid solution were added for liquid separation, and the organic layer was separated and washed three times with water, and then the organic layer was dried over magnesium sulfate, concentrated, and the precipitated crystal was filtered. After drying, 49.6 g of pale yellow crystal of the compound represented by the above formula (1-2-1B) was obtained.

Then, 49.6 g of the above formula (1-2-1B), 2.48 g of 5% palladium carbon powder, 300 mL of tetrahydrofuran, and 300 mL of ethanol were added to a 2 L three-necked flask equipped with a thermometer and a nitrogen introduction tube, and then 80 was slowly added. 51 g of % hydrazine monohydrate aqueous solution, stirred at room temperature for 1 hour, heated to The reaction was further carried out at 70 ° C for 2 hours. After the completion of the reaction, the filtrate obtained by removing palladium carbon by filtration was concentrated to about 200 mL, and ethyl acetate 500 mL was added thereto, and the mixture was washed three times with water, and then the organic layer was concentrated, and the precipitated crystal was filtered and dried. Thus, 39.8 g of a white crystal of the compound (D-2) represented by the above formula (1-2-1) was obtained.

[Synthesis Example 3: Synthesis of Compound (D-3)]

Compound (D-3) was synthesized according to the following Scheme 3.

The compound represented by the above formula (1-3-1A) is added to a 500 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube (wherein the cis-trans isomerization of 1,4-cyclohexylene is trans The isomer) 35.7 g, 20.3 g of 2,4-dinitrochlorobenzene, 15.2 g of potassium carbonate and 300 mL of N,N-dimethylacetamide were reacted at 100 ° C for 4 hours. After completion of the reaction, 1 L of ethyl acetate, 500 mL of tetrahydrofuran, and 1 L of 1 M hydrochloric acid water were added to remove the aqueous layer, and the mixture was washed three times with water. Then, magnesium sulfate was added to the organic layer and dried, and then concentrated, and the precipitated crystal was collected and dried to obtain 35.8 g of pale yellow crystal of the compound represented by the above formula (1-3-1B).

Then, 35.8 g of the compound represented by the above formula (1-3-1B), 1.83 g of palladium carbon, 350 mL of tetrahydrofuran, and B were added to a 1-L three-necked flask equipped with a thermometer and a nitrogen introduction tube. 350 mL of an alcohol and 39.4 g of an 80% aqueous solution of hydrazine monohydrate were reacted at room temperature for 20 hours. After completion of the reaction, 1 L of ethyl acetate was added, and the mixture was washed with water for 3 times, and then the organic layer was concentrated, and the precipitated crystals were filtered and dried to obtain a compound represented by the above formula (1-3-1) (D- 3) Light brown crystals 25.0 g.

[Synthesis Example 4: Synthesis of Compound (D-4)]

Compound (D-4) was synthesized according to the following Scheme 4.

The compound represented by the above formula (1-3-1A) was added to a 500 mL three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen introduction tube (wherein cis-trans isomerization of 1,4-cyclohexylene) They were 35.7 g of trans isomer, 200 mL of tetrahydrofuran and 11.13 g of triethylamine, and cooled to below 5 °C in an ice bath. Next, a solution obtained by dissolving 23.0 g of 3,5-dinitrobenzimidyl chloride in 100 mL of tetrahydrofuran was slowly dropped over 30 minutes, and the mixture was returned to room temperature for 1 hour. After completion of the reaction, 500 mL of ethyl acetate and 500 mL of a 1 M aqueous hydrochloric acid solution were added for liquid separation, and the organic layer was separated and washed three times with water, and then the organic layer was dried over magnesium sulfate, concentrated, and the precipitated crystal was filtered. And dried, thereby obtaining 49.0 g of pale yellow crystals of the compound represented by the above formula (1-4-1B).

Then, 49.0 g of the compound represented by the above formula (1-4-1B), 2.48 g of 5% palladium carbon powder, and 300 mL of tetrahydrofuran were added to a 2 L three-necked flask equipped with a thermometer and a nitrogen introduction tube. After 300 mL of ethanol, 51 g of an 80% aqueous solution of hydrazine monohydrate was slowly added, and the mixture was stirred at room temperature for 1 hour, heated to 70 ° C, and further reacted for 2 hours. After the completion of the reaction, the filtrate obtained by removing palladium carbon by filtration was concentrated to about 200 mL, and ethyl acetate 500 mL was added thereto, and the mixture was washed three times with water, and then the organic layer was concentrated, and the precipitated crystal was filtered and dried. Thus, 38.8 g of a white crystal of the compound (D-4) represented by the above formula (1-4-1) was obtained.

<Synthesis of Polymer (P1)>

[Polymerization Example 1: Synthesis of Polyimine (PI-1)]

2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic dianhydride 22.4 g (0.1 mol), p-phenylenediamine (PDA) as a diamine 7.5 g (0.07 mol) Compound (D-1) 13.8 g (0.03 mol) was dissolved in N-methyl-2-pyrrolidone (NMP) 175 g, and reacted at 60 ° C for 6 hours to obtain 20% by weight of polydecylamine. Acid solution. A small amount of the obtained polyaminic acid solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity of the solution was 78 mPa. s.

Next, 406 g of NMP was added to the obtained polyamic acid solution, and 11.8 g of pyridine and 15.3 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was solvent-substituted with a new NMP (by this operation, the pyridine and acetic anhydride used for the dehydration ring-closure reaction were removed to the outside of the system; the same applies hereinafter), thereby obtaining 22% by weight. A solution of polyamidolimine (PI-1) having a ruthenium imidization rate of about 62%. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a solution having a polyimine concentration of 10% by weight, and the solution viscosity of the solution was 44 mPa. s.

[Polymerization Example 2: Synthesis of Polyimine (PI-2)]

22.5 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 7.6 g (0.07 mol) of PDA as diamine, and 14.8 g (0.03 mol) of compound (D-2) were dissolved in NMP 179 g. The reaction was carried out at 60 ° C for 6 hours to obtain a solution containing 20% by weight of poly-proline. Divide a small amount of income The polyaminic acid solution was added with NMP to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity of the solution was 88 mPa. s.

Next, 416 g of NMP was added to the obtained polyamic acid solution, and 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP, thereby obtaining a solution containing 22% by weight of polyimine (PI-2) having a ruthenium iodide ratio of about 65%. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a solution having a polyimine concentration of 10% by weight, and the solution viscosity of the solution was 49 mPa. s.

[Polymerization Example 3: Synthesis of Polyimine (PI-3)]

22.4 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 7.5 g (0.07 mol) of PDA as diamine, and 13.8 g (0.03 mol) of compound (D-3) were dissolved in NMP 175 g. The reaction was carried out at 60 ° C for 6 hours to obtain a solution containing 20% by weight of poly-proline. A small amount of the obtained poly-proline solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity of the solution was 89 mPa. s.

Next, 406 g of NMP was added to the obtained polyamic acid solution, and 11.8 g of pyridine and 15.3 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP, whereby a solution containing 22% by weight of polyimine (PI-3) having a ruthenium iodide ratio of about 67% was obtained. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a solution having a polyimine concentration of 10% by weight, and the solution viscosity of the solution was 49 mPa. s.

[Polymerization Example 4: Synthesis of Polyimine (PI-4)]

22.5 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 7.6 g (0.07 mol) of PDA as diamine, and 14.8 g (0.03 mol) of compound (D-4) were dissolved in NMP 179 g. The reaction was carried out at 60 ° C for 6 hours to obtain a solution containing 20% by weight of poly-proline. Divide a small amount of income Polylysine solution, NMP was added to make a solution with a polyglycine concentration of 10% by weight, and the solution viscosity of the solution was 70 mPa. s.

Next, 416 g of NMP was added to the obtained polyamic acid solution, and 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP, whereby a solution containing 22% by weight of polyimine (PI-4) having a ruthenium iodide ratio of about 63% was obtained. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a solution having a polyamidene concentration of 10% by weight, and the solution viscosity of the solution was determined to be 45 mPa. s.

[Polymerization Example 5: Synthesis of Polyimine (PI-5)]

A solution containing 20% by weight of polylysine was obtained by the same composition and the same conditions as in the above Polymerization Example 1. A small amount of the obtained poly-proline solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity of the solution was 75 mPa. s.

Next, 406 g of NMP was added to the obtained polyamic acid solution, and 13.4 g of pyridine and 17.3 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP, whereby a solution containing 22% by weight of polyimine (PI-5) having a ruthenium iodide ratio of about 76% was obtained. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a solution having a polyimine concentration of 10% by weight, and the solution viscosity of the solution was 55 mPa. s.

[Polymerization Example 6: Synthesis of Polyimine (PI-6)]

2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride (BODA) 25.0 g (0.1 mol) as tetracarboxylic dianhydride, as two Amine PDA 7.6 g (0.07 mol), compound (D-2) 14.7 g (0.03 mol) was dissolved in NMP 189 g, and reacted at 60 ° C for 8 hours to obtain 20% by weight of polylysine. The solution. A small amount of the obtained poly-proline solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity of the solution was 36. mPa. s.

Next, 439 g of NMP was added to the obtained polyamic acid solution, and 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP, thereby obtaining a solution containing 22% by weight of polyimine (PI-6) having a ruthenium iodide ratio of about 64%. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a solution having a polyimine concentration of 10% by weight, and the solution viscosity of the solution was 30 mPa. s.

[Polymerization Example 7: Synthesis of Polyimine (PI-7)]

BODA 18.9 g (0.075 mol) and 1,2,3,4-cyclobutane tetracarboxylic dianhydride (CB) 4.9 g (0.025 mol) as tetracarboxylic dianhydride, PDA 7.6 as diamine g (0.07 mol) and compound (D-2) 14.8 g (0.03 mol) were dissolved in NMP 185 g, and reacted at 60 ° C for 8 hours to obtain a solution containing 20% by weight of polyglycine. A small amount of the obtained polyamic acid solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity of the solution was determined to be 40 mPa. s.

Next, 429 g of NMP was added to the obtained polyaminic acid solution, and 11.9 g of pyridine and 15.4 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP, thereby obtaining a solution containing 22% by weight of polyimine (PI-7) having a ruthenium iodide ratio of about 66%. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a solution having a polyamidene concentration of 10% by weight, and the solution viscosity of the solution was 29 mPa. s.

[Polymerization Example 8: Synthesis of Polyimine (PI-8)]

22.3 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 5.4 g (0.05 mol) of PDA as diamine, and 24.4 g (0.05 mol) of compound (D-2) were dissolved in NMP 209 g. The reaction was carried out at 60 ° C for 6 hours to obtain a solution containing 20% by weight of poly-proline. Divide a small amount of income The polyaminic acid solution was added with NMP to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity of the solution was 55 mPa. s.

Next, 484 g of NMP was added to the obtained polyamic acid solution, and 7.9 g of pyridine and 10.2 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP, whereby a solution containing 22% by weight of polyimine (PI-8) having a ruthenium iodide ratio of about 50% was obtained. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a solution having a polyimine concentration of 10% by weight, and the solution viscosity of the solution was 36 mPa. s.

[Comparative Polymerization Example 1: Synthesis of Polyimine (PI-9)]

22.4 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 7.6 g (0.07 mol) of PDA as diamine, 11.3 g (0.03 mol) of 4-octadecyloxy-1,3-diaminobenzene The ear was dissolved in 165 g of NMP, and reacted at 60 ° C for 6 hours to obtain a solution containing 20% by weight of poly-proline. A small amount of the obtained poly-proline solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity of the solution was 99 mPa. s.

Next, 384 g of NMP was added to the obtained polyamic acid solution, and 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP, thereby obtaining a solution containing 22% by weight of polyimine (PI-9) having a ruthenium iodide ratio of about 69%. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a solution having a polyamidene concentration of 10% by weight, and the solution viscosity of the solution was 67 mPa. s.

[Comparative Polymerization Example 2: Synthesis of Polyimine (PI-10)]

22.4 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 7.6 g (0.07 mol) of PDA as diamine, 1,3-diamino-4-{4-[trans-4-(reverse) 1-4-g-pentylcyclohexyl)cyclohexyl]phenoxy}benzene 13.0 g (0.03 mol) was dissolved in NMP 172 g, and reacted at 60 ° C for 6 hours to obtain A solution containing 20% by weight of polylysine. A small amount of the obtained polyaminic acid solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity of the solution was 59 mPa. s.

Next, 400 g of NMP was added to the obtained polyamic acid solution, and 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP, whereby a solution containing 22% by weight of polyimine (PI-10) having a ruthenium iodide ratio of about 62% was obtained. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a solution having a polyamidene concentration of 10% by weight, and the solution viscosity of the solution was determined to be 40 mPa. s.

[Comparative Polymerization Example 3: Synthesis of Polyimine (PI-11)]

A solution containing 20% by weight of polylysine was obtained by the same composition and the same conditions as in Comparative Polymerization Example 10 described above. A small amount of the obtained polyaminic acid solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity of the solution was 62 mPa. s.

Next, 400 g of NMP was added to the obtained polyamic acid solution, 13.5 g of pyridine and 17.4 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement with a new NMP, whereby a solution containing 22% by weight of polyimine (PI-11) having a ruthenium iodide ratio of about 74% was obtained. A small amount of the obtained polyimine solution was added, and NMP was added to prepare a solution having a polyimine concentration of 10% by weight, and the solution viscosity of the solution was 42 mPa. s.

<Preparation and evaluation of liquid crystal alignment agent>

[Example 1]

(1) Preparation of liquid crystal alignment agent

In a solution containing polyimine (PI-1) as a polymer, N, N, N', N'- is added to 100 parts by weight of the polyimine (PI-1) contained in the above solution. Tetraepoxypropyl-4,4'-diaminodiphenyl 5 parts by weight of methane (E-1) as an epoxy compound, and further adding NMP and ethylene glycol mono-n-butyl ether (BC) as a solvent to prepare a solvent composition of NMP: BC = 60: 40 (weight ratio), And a solution having a solid concentration of 3.5% by weight. The liquid crystal alignment agent (S-1) was prepared by filtering the solution using a filter having a pore size of 1 μm.

(2) Manufacturing of liquid crystal display element for evaluation of vertical alignment

The liquid crystal alignment agent (S-1) was coated on the transparent conductive film containing the ITO film on one side of the glass substrate having a thickness of 1 mm by a spinner, and prebaked on the hot plate at 80 ° C for 1 minute. The film was heated at 200 ° C for 60 minutes to form a coating film having a film thickness of 0.08 μm.

The coating film was subjected to a rubbing treatment using a rubbing machine having a roller wound with a rayon cloth at a roll rotation speed of 400 rpm, a table moving speed of 3 cm/sec, and a hair press-in length of 0.4 mm. Then, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a clean oven at 200 ° C for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film subjected to rubbing treatment. This operation was repeated to obtain a pair (two pieces) of substrates having a liquid crystal alignment film.

Next, an epoxy resin adhesive having an alumina ball having a diameter of 3.5 μm is applied to each outer edge of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film surface is antiparallel. Connect to harden the adhesive. Next, a nematic liquid crystal (manufactured by Merck & Co., MLC-6608) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photocurable adhesive to form a liquid crystal cell, and further, the liquid crystal cell A polarizing plate was bonded to both outer sides to prepare a liquid crystal display element for evaluation of vertical alignment.

(3) Evaluation of vertical alignment

The pretilt angle was measured by the crystal rotation angle method for the liquid crystal display element for the above vertical alignment evaluation. The evaluation was carried out as follows: the case where the pretilt angle was 87° or more was referred to as “good” in the vertical alignment, and the case where the pretilt angle was less than 87° was referred to as “defective” in the vertical alignment. The evaluation results are shown in Table 1 below.

Further, when a liquid crystal display element for evaluation of the vertical alignment property is produced, the coating film formed on the substrate is subjected to a rubbing treatment, but it is known that the rubbing treatment has an effect of weakening the vertical alignment control force of the liquid crystal alignment film. Therefore, in the case where the pretilt angle of 87° or more is displayed even when the rubbing treatment is performed, the liquid crystal alignment film can be said to have extremely excellent vertical alignment properties of the liquid crystal molecules. Further, it is known from the prior art that when the liquid crystal alignment agent which provides the result is used for manufacturing a vertical alignment type liquid crystal display element by the ODF method, display unevenness (ODF unevenness) is hardly generated.

(4) Manufacturing of liquid crystal display element for voltage retention evaluation

A liquid crystal display element for voltage holding ratio evaluation was produced by the same method as in the case of manufacturing a liquid crystal display element for evaluation of vertical alignment, except that the coating film was not subjected to the rubbing treatment and the subsequent cleaning and drying treatment. .

(5) Evaluation of voltage retention rate

The liquid crystal display element for evaluation of the voltage holding ratio produced as described above was applied with a voltage of 1 V at an application time of 60 μsec and a span of 1670 μsec at 60 ° C, and then measured from the release voltage application. The voltage holding ratio after the millisecond is VHR [%]. The measurement was carried out using VHR-1 manufactured by Toyo Corporation. The measurement results are shown in Table 1 below.

(6) Evaluation of reworkability of liquid crystal alignment film

The liquid crystal alignment agent (S-1) was applied onto the transparent conductive film containing ITO provided on one surface of the glass substrate having a thickness of 1 mm by a spinner, and prebaked at 100 ° C for 90 seconds on a hot plate. A coating film having a film thickness of about 80 nm was formed. This operation was repeated to form two substrates with a coating film. Next, the obtained two substrates were stored in a dark room at 25 ° C in a nitrogen atmosphere. After 12 hours and 48 hours from the start of storage, one substrate was removed, and immersed in a beaker to which NMP adjusted to 40 ° C was added for 2 minutes, and then washed several times with ultrapure water to remove by blast. Water droplets on the surface. The substrate was observed by an optical microscope to find out whether or not the coating film had a residue, thereby evaluating the ease of peeling (reworkability) of the liquid crystal alignment film from the substrate. Evaluation is The substrate which was taken out 48 hours after the start of storage was evaluated as having no residue of the coating film after immersion in NMP, and was considered to be "excellent" in reworkability; it was observed on the substrate after 48 hours. In the case of the residue of the coating film, the case where the residue of the coating film was not observed on the substrate after 12 hours was described as "good" in reworkability; the case where the residue of the coating film was observed in the substrate after 12 hours was recorded as Reworkability is "bad". The evaluation results are shown in Table 1 below.

(7) Evaluation of light resistance

The initial voltage holding ratio was measured on the liquid crystal display element manufactured as described above under the same conditions as the evaluation of the voltage holding ratio. Then, it was placed at a distance of 5 cm under a 100-watt white fluorescent lamp, and after 500 hours of light irradiation, the voltage holding ratio was measured again under the same conditions as above. The case where the rate of decrease in the voltage holding ratio compared with the initial value is 1% or less is referred to as "A", and when it is more than 1% and not more than 2%, it is referred to as "B", and when it exceeds 2%, Lightfastness "C".

[Example 2 to Example 10, Comparative Example 1 to Comparative Example 4]

A liquid crystal alignment agent (S-2) to a liquid crystal alignment agent (S-14) were prepared in the same manner as in Example 1 except that the type of the polymer and the content of the epoxy compound were changed as shown in Table 1 below. And each evaluation of vertical alignment, voltage holding ratio, reworkability, and light resistance was performed. The results of these evaluations are shown in Table 1 below.

As shown in Table 1, in the liquid crystal alignment film formed of the liquid crystal alignment agent of the examples, the pretilt angles were all as high as 87° or more, and the liquid crystal molecules were excellent in the perpendicular alignment. Further, in the liquid crystal alignment agent of the embodiment, even if the coating film formed on the substrate is subjected to the rubbing treatment, the pretilt angle is high. Therefore, when the vertical alignment type liquid crystal display element is manufactured by the ODF method, it can be appropriately Suppresses the occurrence of display unevenness. Further, in the liquid crystal alignment agent of the examples, not only the light resistance is good, but also when the epoxy compound is contained in the liquid crystal alignment agent, the reworkability is also good.

Further, in the liquid crystal alignment agent of the examples, the voltage holding ratio was also good, in which polyimine (PI-1), polyimine (PI-3) or polyimine (PI-5) was contained as a polymerization. In Example 1, Example 3, Example 5, and Example 10 of the material components, a high voltage holding ratio of 98.0% or more was exhibited.

On the other hand, in Comparative Example 1 to Comparative Example 3, although the reworkability was good, the vertical alignment property and the light resistance were poor. Further, in Comparative Example 4, although the vertical alignment property and the light resistance were good, the reworkability was poor.

Claims (8)

A liquid crystal alignment agent containing at least one polymer selected from the group consisting of polylysine, polyphthalate, polyimine, and polyorganosiloxane, and the liquid crystal alignment agent is characterized by : a polymer (P1) having a group represented by the following formula (0) as the above polymer: (In the formula (0), Ac ¹ and Ac ² are each independently a cyclohexane ring or a benzene ring, and these rings may have a substituent; R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; and X is an oxygen atom. n ¹ is 1 or 2, and n ² is 0 or 1; wherein, in the case where n ¹ is 2, a plurality of Ac ¹ independently have the above definition; m is an integer of 1 to 3; "*" indicates combination key). The liquid crystal alignment agent according to claim 1, wherein the polymer (P1) is at least one selected from the group consisting of polylysine, polyphthalate, and polyimine. The polyaminic acid, the polyphthalate, and the polyimine are at least one compound selected from the group consisting of tetracarboxylic dianhydride and tetracarboxylic acid diester compound, and include the following formula (1) The diamine of the indicated compound is reacted to obtain: (In the formula (1), Ac ¹ and Ac ² are each independently a cyclohexane ring or a benzene ring, and these rings may have a substituent; R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; and X is an oxygen atom. n ¹ is 1 or 2, and n ² is 0 or 1; wherein, when n ¹ is 2, a plurality of Ac ¹ independently have the above definition; m is an integer of 1 to 3). The liquid crystal alignment agent according to claim 1 or 2, wherein the sum of the above n ¹ and the above n ² is 2 or 3. The liquid crystal alignment agent according to claim 1 or 2, wherein the sum of the above n ¹ and the above n ² is 2. A liquid crystal alignment film formed using 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 obtained by reacting at least one compound selected from the group consisting of tetracarboxylic dianhydride and tetracarboxylic acid diester compound with a diamine containing a compound represented by the following formula (1): (In the formula (1), Ac ¹ and Ac ² are each independently a cyclohexane ring or a benzene ring, and these rings may have a substituent; R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; and X is an oxygen atom. n ¹ is 1 or 2, and n ² is 0 or 1; wherein, when n ¹ is 2, a plurality of Ac ¹ independently have the above definition; m is an integer of 1 to 3). A compound represented by the following formula (1): (In the formula (1), Ac ¹ and Ac ² are each independently a cyclohexane ring or a benzene ring, and these rings may have a substituent; R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; and X is an oxygen atom. n ¹ is 1 or 2, and n ² is 0 or 1; wherein, when n ¹ is 2, a plurality of Ac ¹ independently have the above definition; m is an integer of 1 to 3).