TW200804465A - Vertical alignment mode liquid crystal alignment agent and vertical alignment mode liquid crystal display device - Google Patents

Abstract

The present invention provides a vertical alignment mode liquid crystal alignment agent having outstanding vertical alignment and image sticking resistance. The vertical alignment mode liquid crystal alignment agent includes polyamic acid or imidizaition compound which possesses the structure resulting from a tetracarboxylic acid dianhydride with aromatic ketone structure such as benzophenone tetracarboxylic acid and a phenylene diamine with steroid structure, fluorine atom or straight chain alkyl group of C1-22 as substitute.

Description

200804465 IX. Description of the Invention: [Technical Field] The present invention relates to a novel vertical alignment type liquid crystal alignment agent and a vertical alignment type liquid crystal display element. More specifically, it relates to a novel vertical alignment type liquid crystal alignment agent having a structure derived from a specific tetracarboxylic acid dianhydride having an aromatic ketone structure, excellent in image resistance, and a vertical alignment type liquid crystal display element having a beautiful image. [Prior Art] From the perspective of space saving, low power consumption, etc., liquid crystal display elements represented by liquid crystal displays have been applied to watches, portable game machines, and word processors since the liquid crystal calculator began mass production. , notebook computers, car navigators, cameras, PDAs, digital cameras, mobile phones, various monitors, LCD TVs and many other fields, and are still active development. As a display method of the prior art, a TN (Twisted Nematic) type and an STN (Super Twisted Nematic) type have been widely used. In recent years, in order to improve the display quality of a liquid crystal display, a liquid crystal using negative dielectric anisotropy has been developed. When a voltage is applied, the liquid crystal molecules are vertically aligned parallel to the substrate surface by a VA (Vertical Alignment) type. Compared with the TN type and the STN type, the VA type does not increase the brightness of the backlight, and thus can obtain a high contrast ratio, and generally does not require a rubbing process, and therefore is used for applications requiring a display having high display quality. (especially mobile phones and LCD TVs, etc.). In addition, a vertical alignment type liquid crystal display device (20084465) called MVA (Multi Domain Vertical Alignment) type and PVA (Patterned Vertical Alignment) type, which has improved high viewing angle characteristics, has been proposed, and the use of the VA type has been further expanded. However, since the VA type liquid crystal display element is used for applications requiring high-quality display performance, it is required to have a higher level of resistance (reliability) of the display panel afterimage caused by charge accumulation during long-term continuous driving. Now, there is an urgent need to establish techniques for strategies to further reduce image loss. In the vertical alignment type liquid crystal display element, the alignment of the liquid crystal is generally as described in Patent Documents 1 to 3, by polymerization of at least one polymer containing a polyamic acid selected from a group having a bulky side chain substituent and a ruthenium iodide polymer. The vertical alignment type liquid crystal alignment film formed by the liquid crystal alignment agent of the object is controlled. Since the liquid crystal alignment film is a member that directly contacts the liquid crystal molecules, it is known that it has a very large influence on the afterimage (charge accumulation) and voltage holding ratio of the liquid crystal display element, and thus it is urgent to develop a vertical alignment type liquid crystal by improvement. A means for aligning the film to improve the image sticking resistance of the liquid crystal display element. For example, Patent Document 4 and Patent Document 5 disclose an example of optimizing the composition of the vertical alignment type liquid crystal alignment film from the viewpoint of easily diffusing the retained electric charge and shortening the afterimage erasing time. With the demand for the improvement of the image-resistance of the vertical alignment type liquid crystal display element as described above, it is urgent to develop the same liquid crystal alignment agent capable of producing a vertical alignment type liquid crystal alignment film which is more difficult to generate charge. [Patent Document 1] Japanese Patent Laid-Open No. 289-367 (Patent Document 3) Japanese Patent Publication No. 289367 No. [Patent Document 5] Japanese Patent Application Laid-Open No. 2004-94 No. 79-A No. 200404465 [Invention] The present invention has been made based on the above-described circumstances. Accordingly, an object of the present invention is to provide a vertical alignment type liquid crystal alignment agent which exhibits excellent vertical alignment and which can produce a vertical alignment type liquid crystal alignment film excellent in image retention. According to the present invention, the above object of the present invention, which is achieved by a vertical alignment type liquid crystal alignment agent, is characterized by containing an aromatic ketone represented by the following formula (1 - 1) and formula (1-2) At least one first tetracarboxylic acid dianhydride

• (1 -1> • (wherein, a and b are independently an integer of 〇~3, and R" to R12 independently represent a hydrogen atom; a halogen atom; optionally having an oxygen atom, a sulfur atom, a nitrogen atom or a ruthenium a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, wherein a group of two adjacent groups selected from Ri~b and R7 to r12, respectively Interconnected to form a carboxylic anhydride group) 200804465

^19 R20 (1-2) (wherein X represents a single bond, a sulfur atom, an oxygen atom, a methyl group having 1 to 3 carbon atoms, a carbonyl group (-CO-), a sulfonyl group (-S〇2) -), any one of the imido groups (-NH-), c and d are independently an integer of 0 to 3, and r13 to R24 independently represent a hydrogen atom; a halogen atom; optionally having an oxygen atom, a sulfur atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms in a linking group of a nitrogen atom or a halogen atom; or a polar group, wherein a group selected from R i 3 to R18 and Ri9 to R24, respectively The two adjacent groups are bonded to each other to form a carboxylic acid anhydride group, and the second tetracarboxylic acid dianhydride different from the first tetracarboxylic acid dianhydride represented by the following formula (2) is 0 °RV ° human 0 0 Φ is a tetravalent organic group) a first diamine represented by the following formula (3) (2) (3) 200804465 corpse 26 ten R27")~R28 (wherein e is 0 or 1, and R26 is selected from -二_, -c〇-, -CO〇-, -0CCU, -NHC〇-, -C〇NH-, -S-, a divalent organic group of a methyl group, R27 is

R26 is a different divalent organic group, and R28 is a group selected from a group having a steroid skeleton, a group having a fluorine atom, or a group having a linear group having 1 to 22 carbon atoms) and The second diamine H2N-R29-NH2 different from the first diamine represented by the above formula (4) (4) (wherein Rm is a divalent organic group) The polylysine obtained by the reaction and/or Or a ruthenium imidized polymer obtained by dehydrating the polyamic acid ring.

Further, according to the present invention, the above object of the present invention is achieved by a vertical alignment type liquid crystal display element comprising a vertical alignment type liquid crystal alignment film formed of the above-described vertical alignment type liquid crystal alignment agent. According to the vertical alignment type liquid crystal alignment agent of the present invention, a vertical alignment type liquid crystal alignment film excellent in vertical alignment and image resilience can be obtained, and a vertical alignment type liquid crystal display element capable of producing a beautiful image can be obtained from the liquid crystal alignment film. . [Embodiment] [Polyuric acid and hydrazinated polymer] .200804465 Hereinafter, the present invention will be specifically described. The polyamic acid to be used in the present invention can be obtained by subjecting the tetracarboxylic dianhydride represented by the above formula (1-1) and/or (1-2) to the above formula (2) to the above formula (3) and the above formula ( 4) The resulting diamine addition polymerization reaction is carried out. Further, the ruthenium iodide polymer used in the present invention can be obtained by dehydration ring closure of the above polyglycine. [Tetracarboxylic acid dianhydride] The vertical alignment type liquid crystal alignment agent of the present invention is obtained by using at least one selected from the group consisting of tetracarboxylic dianhydrides represented by the above formulas (1-1) and (1-2) as tetracarboxylic acid The acid anhydride undergoes (co)polymerization and can exhibit excellent anti-image sticking properties. In the present invention, the ratio of the tetracarboxylic acid dianhydride represented by each of the above formulas (1 to 1) and (1 to 2) is preferably 5 to 90 mol% based on the total tetracarboxylic acid dianhydride, more preferably 7 to 75 mol%, especially good for 1 〇 ~ 60 mol%. If the ratio of the tetracarboxylic dianhydride represented by each of the above formulas (1 - 1) and (1 - 2) is too small, it is difficult to obtain sufficient resistance to image sticking, and if too large, the coloring property of the alignment agent may become problematic. Case. a hydrogen atom represented by Ri~R24 in the above formula (1 -1), (1 - 2); a halogen atom; a substitution group optionally having an oxygen atom, a sulfur atom, a nitrogen atom or a ruthenium atom or An unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms; and a monovalent polar group will be described. The halogen atom may, for example, be a fluorine atom, a chlorine atom or a bromine atom. Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms include an alkyl group such as a methyl group, an ethyl group, and a propyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; and an alkenyl group such as a vinyl group or an allyl group; An alkylene group such as an ethylene group or a propylene group; an aromatic group such as a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group or a fluorenyl group; and the like. The hydrogen atom bonded to the carbonogen-10-200804465 in these groups may be optionally substituted by a halogen atom such as fluorine, chlorine or bromine, a cyano group or the like. Further, the above-mentioned substituted or unsubstituted monovalent hydrocarbon group may be directly bonded or bonded to the benzene ring structure represented by the formula (1-1) and/or the formula (1-2) by a linking group. The above linking group may, for example, be a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom (for example, a carbonyl group (-CO-), a carbonyloxy group (-COO-), or an oxycarbonyl group (-OCO-). ), sulfonyl (-S〇2-), sulfonyloxy (-S02-0-), oxysulfonyl (-0-S02-), ether bond (_〇·), thioether bond ( -S-), ® imine (-NH-), guanamine bond (-NHCO-), oxime bond (_si(R)2〇-) (wherein R is a methyl group, an ethyl group, etc.) a group in which two or more of them are bonded in combination. When the above substituted or unsubstituted monovalent hydrocarbon group is a cycloalkyl group or an aromatic group, the above linking group may have a carbon number of a divalent hydrocarbon group of 1 to 10 (for example, -(CH〇m- (wherein m is an integer of 1 to 10).) The monovalent polar group may, for example, be a hydroxyl group or a cyano group. , nitro, amidino, imido (= ΝΗ), triorganomethoxy, triorganoalkyl, arum, sulfhydryl, alkoxyalkyl, sulfonate (-SChH), sub Sulfo group (-SO2H), a carboxyl group, etc. More specifically, as the triorganomethoxy group, for example, Trimethyl decyloxy, triethyl decyloxy, etc. Examples of the triorganoalkylene group include a trimethyldecyl group and a triethyl decyl group; and examples of the amine group include a secondary amino group and three Examples of the alkoxyalkyl group and the like include, for example, a trimethoxydecylalkyl group, a triethoxydecylalkyl group, and the like. Among the above formulas (1 to 1), a and b are independently 〇3. Integer, -11- 200804465 A group of two adjacent groups selected from Ri~R6 and R7~R12, respectively, are bonded to each other to form a carboxylic anhydride group. Here, a and b are preferably in the range of 0Sa + bS3, in particular More preferably, a = b = 0. In the above (1-2), X represents a single bond, a sulfur atom, an oxygen atom, an alkylene group having 1 to 3 carbon atoms, a carbonyl group (-CO-), Any one of a sulfonyl group (-S〇2-) and an imido group (-NH-), and c and d are independently an integer of 0 to 3', a group selected from Rm~ and R19~, respectively. The two groups are each bonded to each other to form a carboxylic anhydride group. Here, c and d are preferably in the range of 0 ^ c + d S 3 , particularly preferably c = d = 0. As the above formula (1 - 1) And (1 to 2) each Specific examples of the tetracarboxylic acid diacid represented by the above may be exemplified by the following compounds: 3,3,4,4,-benzophenonetetracarboxylic acid represented by the following formula (A-1) Acidic 1,

2,3,3,,4,-benzophenonetetracarboxylic acid diacid represented by the following formula (A-2):

2,2,,3,3,-benzophenonetetracarboxylic acid diacid represented by the following formula (A-3): -12-.200804465 Ο p Q, Ό

Ο • · . ( Α — 3> 2,3,6,7-(9-fluorenone) tetracarboxylic acid dianhydride represented by the following formula (A-4)

(A - 4) 2,3,6,7-(9-thioxanthone)tetracarboxylic acid diacid anhydride represented by the following formula (A-5),

As described above, the first tetracarboxylic dianhydride may be used singly or in combination of two or more kinds. Examples of the second tetracarboxylic acid dianhydride different from the first tetracarboxylic acid dianhydride represented by the above formulas (1 to 1) and (1 to 2) include butane tetracarboxylic acid dianhydride and 1, 2 , 3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2 , 3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl- 1,2,3,4-cyclo-butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid di-13· 200804465 Anhydride, 1,2,4,5-cyclohexane Tetracarboxylic acid dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxy norbornazole Alkane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3&,4,5,9-seven-hexahydro-5-(tetrahydro-2,5- Dioxo-3-furanyl)-naphthalene [l,2-c]-furan·1,3-dione, 1,3,33,4,5,913-hexahydro-5-methyl-5-(four Hydrogen 2,5-monooxy-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5 -ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)_ [l,2-c]-furan-i,3-dione, 1,3,3&,4,5,91)-hexahydro-7-methyl-5-(tetrapulyhydro-2,5- Dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-7-ethyl- 5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-i,3-dione, l,3,3a,4,5,9b- Hexahydro-8-methyl-5.(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[i,2-c]-furan-1,3-dione, 1,3, 3&,4,5,91)-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-; I,3-dione, 13,33,4,5,91)-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan·1,3-dione, 5-(2,5-dioxotetrahydrofuranmethylidene)-; methyl „3 _cyclohexene, 2-dicarboxylic acid Diacid anhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-di Keto-6-spiro-3,-(tetrahydrofuran-2,5,-dione), 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, II Ring [3.3.0] octane·2,4,6,8-tetracarboxylic dianhydride, compound represented by the following formulas (7) and (8) Aliphatic and alicyclic tetracarboxylic acid wild; -14-200804465

(wherein R3 and R32 represent a divalent organic group having an aromatic ring, and R31 and R33 represent a hydrogen atom or a yard group, and a plurality of R 3 1 and R 3 3 present may be the same or different. Pyromellitic acid dianhydride, 3,3',4,4'-diphenyl maple tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic acid Anhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, ® 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-di(3,4-di Carboxyphenoxy)diphenyl sulfide dianhydride, 4,45-bis(3,4-dicarboxyphenoxy)diphenyl maple dianhydride, 4,4'-bis(3,4-dicarboxybenzene Oxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene di phthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride , di(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene bis(triphenylphthalic acid) dianhydride, Di(triphenylene) Terephthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-di(de-15-200804465 Water trimellitate), propylene glycol _ bis (dehydrated trimellitate), 1,4-butanediol · bis (dehydrated trimellitate), 1,6-hexanediol · two (dehydration partial Triphenyl ester), 1,8-octanediol-di(hydroper trimellitate), 2,2-bis(4-hydroxyphenyl)propane-di(hydroper trimellitate), An aromatic tetracarboxylic acid dianhydride such as a compound represented by each of the formulae (9) to (11).

Among them, Dingyuan tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3·dimethyl-1 is preferred from the viewpoint of exhibiting good liquid crystal alignment. , 2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclo-16- 200804465

Amyl acetonic acid dianhydride, 5-(2,5-dioxotetrahydrofuran methylene, methyl hexamethyl hexyl-1,2-dicarboxylic acid dianhydride, 1,3,3&, 4,5,9 Hexahydro-5-(tetrahydro-2,5-monooxy-3-furanyl)-naphthalene [He]·furandione, ^'^^々^, “· hexahydro-^methyl^彳4 Hydrogen-夂Hong dioxo-furfuryl)-naphthalene [l,2-c]-furan-U·dione, hexahydro-5,1 dimethyl_5-(tetrahydro-2,5-dioxo 3--3-furyl)-naphthalene [l,2-c]-furan-1)·dione, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylate Acid dianhydride, 3_oxabicyclo[3.2.1]octane-2,4-dione·6_ spiro-3, ·(tetrahydrofuran-2,,5,_dione), 3,5,6-three Carboxy-2-carboxynorbornane-2:3,5:6-dianhydride, bicyclo[3·3·〇]octane-2,4,6,8-tetracarboxylic dianhydride, pyromellitic acid The dianhydride, 3,3,4,4,-diphenylphosphonium tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, and the compound represented by the above formula (7) The compound represented by the formula (1 2) to (14) and the compound represented by the following formula (15) in the compound represented by the above formula (8). Particularly preferred are 1, 2, 3, 4 - Cyclobutane Tetracarboxylic acid dianhydride, 1,3-dimethyl 4,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3 , 5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&,4,5,91)-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-i,3-dione, 1,3,3&,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-di Oxo-3-furanyl)·naphthalene [i,2-c]-furan-1,3-dione, 3·oxabicyclo[3.2.1]xinyuan-2,4-dione-6-snail -3,-(tetrahydrofuran',5'-dione), 3,5,6-decylcarboxyl-2-carboxyl-norbornane·2:3,5:6-dianhydride, bicyclo[3.3.0] octane Alkane-2,4,6,8-tetracarboxylic acid dianhydride, pyromellitic acid diacid 1 and a compound represented by the following formula (12). -17- 12)200804465

(13)

••(14) The above-mentioned second tetracarboxylic dianhydride may be used in combination of one type. [Diamine compound] The liquid crystal alignment agent of the present invention can exhibit an excellent ratio of the vertical alignment diamine by copolymerizing an appropriate amount of the diamine, and is preferably from 9 to 50 mol% based on the entire diamine. When the ratio of the diamine of 10 to 25 mol% is too small, it is difficult to obtain a sufficient amount, and if it occurs, the occurrence of the alignment film may occur. In the above formula (3), e is 〇 or 1, and R26 is represented by the above formula (3) in a single or two or more groups. The above formula (3) represents 8 to 60 mol%, more preferably. If the above formula (3) indicates vertical alignment, and f which is not well coated with pinholes or the like is selected from an ether bond (-0-), a carbonyl-18-200804465 group (-CO-), a carbonyloxy group (-COO-) ), the oxycarbonyl group (-OCO-), (-NHCO -, -CONH-), the thioether bond (-S-), and the methyl group have a valence of 2, particularly preferably an ether bond (-〇-), Carbonyloxy (-COO-). R27 is a divalent organic group of and, preferably having an aromatic group or a cyclohexyl group. Further, Ru is a group selected from a group having a steroid skeleton, or a linear alkyl group having 1 to 22 carbon atoms. As a specific example of the diamine represented by the above formula (3), the compounds listed may be Φ. • Amidoxime linkage. R26 different divalent linkages with fluorogenic groups are as follows

• (c-1 > • (C-2) 49- 200804465

(C-4)

Among them, (C-1) and (C-2) are shown from the viewpoint of showing excellent vertical alignment. Further, the first diamine may be used singly or in combination. The second diamine compound represented by the above formula (4) is the first dicampamine, and specific examples thereof include p-phenylenediamine, m- 4,4'-diaminodiphenylmethane, and 4,4. '-Diaminodiphenylethane, phenyl diphenyl sulfide, 4,4'-diaminodiphenyl maple, 2,2'-dimethylbiphenyl, 4,4'-diaminobenzoic acid Aniline, 4,4'-diaminodidiaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 5-amine-3-ylphenyl)-1,3,3· Trimethylindan, 6-aminoaminophenyltrimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diamine 2 3,4'-diaminobenzophenone , 4,4'-diaminobenzophenone, 2,2-di, particularly preferably more than 52 kinds of bis-phenylenediamine, 4,4,-diamine-4,4,-diamine Phenyl Ether, 1,5-S -1-(4'-Amino)-1,3,3-dibenzophenone, [4-(4-Amino-20-200804465 phenoxy)phenyl]hexafluoro Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2-di[4-( 4-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-di 3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone 2,7-diaminopurine, 9,9-bis(4-aminophenyl) ), 4,4'-methyl-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'diaminobiphenyl, 2,2, · Chloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,35-dimethoxy-4,4'-diaminobiphenyl, 1,4,4'-( p-Phenyl isopropylidene)diphenylamine, 4,4'-(m-stretched phenylisopropylidene)diphenylamine, 2,2'-bis[4-(4-amino-2- Trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diamino-2, 2'-Dimethylbiphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 1,3-bis(4-aminobenzene) Oxy)-2,2-dimethylpropane, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis(4-aminophenoxy)-2,2- An aromatic diamine such as dimethylpropane or 4,4'-bis(4-aminophenoxy)biphenyl; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4- Diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6- Diamino-2 -2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl) Pyridazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5·triazine, 2 ,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-S-triazine, 2,4-diamino-1,3 , 5-triazine, 4,6-diamino-2-vinyl-8-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6 -diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4.triazole, 6,9-diamino-2-ethoxy acridine lactate , 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopyridazine, 3,6-diaminoacridine, bis(4-amine-21-200804465-phenyl)benzene a diamine having two primary amino groups in the molecule and a nitrogen atom other than the primary amine group, such as a compound represented by each of the following formulas (16) and (17); X-R34

(wherein R34 represents a monovalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, acridine and 呱φazine, and X represents a divalent organic group)

(wherein R35 represents a divalent organic group having a cyclic structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, acridine and oxime); 1,3-bis(aminomethyl)cyclohexane, 1,3_propylenediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoheptyldiamine, 1,4-diamine Cyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-methylene quinone dimethylenediamine, tricyclo[6.2.1.02,7]- An aliphatic and alicyclic diamine such as carbene diamine, 4,4'-methyl bis(cyclohexylamine); a diamine organooxane represented by the following formula (18); -22- 200804465

(wherein R36 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R36 present may be the same or different, p is an integer of 1 to 3, and Q is an integer of 1 to 20). These second diamines may be used singly or in combination of two or more kinds. Among them, preferred p-phenylenediamine, 4,4, diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diamino group Bismuth, 4,4'-diaminodiphenyl ether, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane , 2,2-bis[4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4.aminobenzene) Oxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-2,2,-bis(trifluoromethyl)biphenyl, 4,4 '·Diamino-2,2'-dimethylbiphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4·diaminopyrimidine, 3,6-diamine A compound represented by the following formula (19) and a compound represented by the following formula (20) in the compound represented by the above formula (17), and a 1,3-di (a compound of the compound represented by the following formula (17); The following formula (21) in the compound represented by the above formula (18), wherein the amine methyl group) cyclohexane, 1,4-cyclohexanediamine, 4,4'-methyl bis(cyclohexylamine) 3,3'-(Tetramethyldioxane-1,3-diyl)di(propylamine). -23- 200804465

Particularly preferred are p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'. -diaminodiphenyl ether, 3,3'-(tetramethyldioxane-1,3-diyl)di(propylamine), 2,2-bis[4-(4-aminophenoxyl) Phenyl]propane, hydrazine, 3_bis(aminomethyl)cyclohexane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diamino 2, 2,-bis(trifluoromethyl)biphenyl, 2,7-diaminoguanidine. <Synthesis of Polyproline> The use ratio of the tetracarboxylic dianhydride to the diamine compound used in the polyproline synthesis reaction of the present invention is preferably relative to the amino group contained in 1 equivalent of the diamine compound. The acid anhydride group of the tetracarboxylic acid dianhydride is made to have a ratio of 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is carried out in an organic solvent preferably at a temperature of from -20 to 150 ° C, more preferably from 0 to 1 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyaminic acid, and for example, N-methyl-2-pyrrolidone and N,N-dimethylacetamidine 24-48 04465 amine can be exemplified. , apron polar solvent such as n,n-dimethylformamide, dimethyl sulfonium, r-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; m-methylphenol, xylenol A phenolic solvent such as phenol or a halogenated phenol, and these solvents may be used singly or in combination of two or more kinds. Further, the amount (a) of the organic solvent is preferably such an amount that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine compound is from 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. Further, in the above range in which the produced polyamine acid is not precipitated, a poor solvent alcohol of polylysine, a ketone Φ, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon may be used in combination in the above organic solvent. Classes, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, and ethylene glycol. Methyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, Ethyl ethoxypropionate, propylene carbonate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether Ethylene glycol monobutyl ether (butyl solvolysis agent), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichlorocarbyl, 1,2-dichloroethane, 1,4-dichlorobutane, Trichloroethane, chlorobenzene, o-dichlorobenzene, hexaxy, Gengyuan, Xinyuan, benzene, toluene, xylene, etc. These poor solvents may be used alone or in combination of two or more. As described above, a reaction solution in which polylysine was dissolved was obtained. Then, the reaction solution is poured into a large amount of a poor solvent and/or water to obtain a precipitate of -25-200804465, and then the precipitate is dried under reduced pressure to obtain a polyamic acid. Further, the polyproline is redissolved in an organic solvent, and then precipitated with a poor solvent and/or water, and the polyamine can be purified by performing one or several times. <醯i-Iminylated Polymer> The ruthenium iodide polymer used in the liquid crystal alignment agent of the present invention can be synthesized by dehydrating and ring-closing the above polyamic acid. (The so-called ruthenium iodide polymer herein includes a partial oxime imidization polymer and a 100% quinone imidized polymer which are partially ruthenized to the above polyglycine, and hereinafter, collectively referred to as "醯iminated polymer"). The oxime imidization ratio of the ruthenium iodide polymer used in the liquid crystal alignment agent of the present invention is preferably from 10 to 100%, more preferably from 20 to 80%, particularly preferably from 25 to 60%. Here, the "yttrium imidization ratio" means the ratio of the ratio of the number of repeating units forming the quinone ring to % based on the total number of repeating units in the polymer. At this time, a part of the quinone ring may also be an isoindole ring. As a method for synthesizing the ruthenium iodide polymer, (I) a method of synthesizing dehydration ring closure by heating the above polyamic acid, and (II) dissolving the above polyamic acid in an organic solvent, A dehydrating agent and a dehydration ring-closure catalyst are added to the solution, and if necessary, a method of synthesizing dehydration ring-closure is carried out, and by appropriately controlling the above reaction conditions, a polymer having a desired quinone imidization ratio can be obtained. The reaction temperature of the above method (I) for heating poly-proline is preferably from 50 to 300 ° C, more preferably from 100 to 250 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction cannot be completed completely. If the reaction temperature exceeds 30 (TC, -26-200804465, the molecular weight of the obtained ruthenium-imided polymer may decrease. On the other hand, In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyaminic acid solution of the above (II), as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent is relative to 1 mole polyproline repeating unit, preferably 〇. 1~2 0 mole. Further, as the dehydration ring-closing catalyst, for example, pyridine, trimethylpyridine, lutidine, triethylamine or the like can be used. The amine, however, the dehydrating agent and the dehydration ring-closing catalyst are not limited to these examples. The amount of the dehydration ring-closing catalyst is preferably 0.01 to 10 mol per mol of the dehydrating agent used. Further, as a dehydration ring closure reaction The organic solvent to be used may be the same organic solvent as exemplified as the solvent used in the synthesis of polylysine. Further, the reaction temperature of the dehydration ring-closure reaction is preferably 〇. 180 ° C, more preferably 60 to 1 50 ° C. Further, the ruthenium iodide polymer can be purified by subjecting the reaction solution thus obtained to the same procedure as the polyamic acid purification method. The poly-proline and the quinone imidized polymer constituting the liquid crystal alignment agent of the present invention may also be a terminal-modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, it is possible to On the premise of the effects of the invention, the coating properties and the like of the liquid crystal alignment agent are improved. The terminal modified polymer can be synthesized by adding a monobasic acid anhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system when synthesizing the polyamic acid. Here, examples of the monobasic acid field include a dicarboxylic acid monobasic acid anhydride, and examples thereof include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-xyl-based succinic anhydride, and positive fourteen. Alkyl succinic anhydride, n-hexadecyl amber -27-.200804465 acid anhydride, etc. Further, examples of the monoamine compound include aniline, cyclohexylamine, and p-ethylaniline. Butylamine, n-amylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, It is a fifteen-amine amine, a hexadecanolamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, etc. Further, as the monoisocyanate compound, for example, phenyl isocyanate or the like can be mentioned. Naphthyl cyanate, etc. <Logarithmic viscosity of polymer> The logarithmic viscosity _ (7? In) 醯 of the polylysine and the ruthenium-imided polymer obtained as above is preferably 0.05 to 10 dl/g, more Preferably, it is 0.05 to 5 dl/g. In the present invention, the logarithmic viscosity (7? In) 値 is a viscosity of a solution having a concentration of 0.5 g/100 ml at 30 ° C by using N-methyl-2-pyrrolidone as a solvent. The enthalpy obtained by the following formula (a) was measured. = ln (polymer solution flow time / solvent flow time) (a) η ΐ η = (weight concentration of polymer τ < liquid crystal alignment agent > The liquid crystal alignment agent of the present invention is preferably composed of poly- lysine The hydrazine imidized polymer is dissolved in an organic solvent. The liquid crystal alignment agent of the present invention can also be added to the alignment agent in order to improve the electrical properties of the residual DC and the coating film properties at the time of formation of the alignment film. The structure of the tetracarboxylic dianhydride represented by each of the above formulas (1 - 1) and (1 - 2) and the polyamine and/or hydrazine derived from the structure of the first diamine represented by the above formula (3) An imidized polymer, which does not contain a structure derived from tetracarboxylic acid good 200804465 dianhydride represented by the above formulas (1 to 1) and (1 - 2), and a first diamine derived from the above formula (3) The polyglycolic acid and/or quinone imidized polymer of the structure may be one kind or a plurality of kinds according to the purpose, preferably poly-proline acid, and particularly preferably selected from the group consisting of cyclobutyric acid tetracarboxylic acid dianhydride, 1 ,3-dimethyl-1,2,3,4-cyclobutane tetraresic acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5·(tetrahydro-2,5-dioxofuranyl)_na[l ,2-c]-furan-1,3·one, l,3,3a,4,5,9b-hexahydromethyl (four

Hydrogen-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]-furan-1,3-dione, 3-oxabicyclo[3·2·1] 辛院-2 , 4 - —^丽-6-spiro-3'-(tetrachlorofuran·2,,5,-one ketone), 3,5,6-di-residue-2-residue norbornene-2:3 , 5: 6• dianhydride, bicyclo [3.3.0] xinyuan-2,4,6,8-tetradecanoic acid dianhydride, pyromellitic dianhydride, more than one acid dianhydride and selected from p-benzene Diamine, 4,4,-diaminobenzophenone, 4,4,-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminopurine, 4,4 ,-Diaminodiphenyl ether, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2- Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diamino-2,2,- Bis(trifluoromethyl)biphenyl, 4,4'-diamino-2,2,-dimethylbiphenyl, 3,3-(tetramethyldioxane-1,3-diyl) Polylysine obtained by reacting one or more diamines of bis(propylamine). a polyglycine containing a structure derived from a tetracarboxylic dianhydride represented by each of the above formulas (1 to 1) and/or (1 to 2) and a structure derived from the first diamine represented by the above formula (3) And/or a ruthenium imidized polymer (which is referred to as a polymer "X"), and a structure derived from the tetracarboxylic dianhydride derived from each of the above formulas (1 to 1) and (1 - 2) and derived from the above The ratio of the above polyamine and/or quinone imidized polymer (which is the polymer "Y") of the structure of the first diamine represented by the formula (3) is -29-200804465, preferably by weight. For the range of Χ/Ύ = 10/90~90/10, better range of X/Y = 15/8 5 ~ 60/40, especially good X/Y = 20/80 ~ 50/50 range. The temperature at which the liquid crystal alignment agent of the present invention is formulated is preferably from 〇 ° C to 200 ° C, more preferably from 10 ° C to 100 ° C, particularly preferably from 20 ° C to 60 ° C. The organic solvent constituting the liquid crystal alignment agent of the present invention may be the same solvent as exemplified as the solvent used in the synthesis reaction of polylysine. Among them, a solvent having a boiling point of 1 60 ° C or higher is preferably from the viewpoint of printability, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and dimethyl hydrazine. , 7-butyrolactone, tetramethylurea, trimethylamine hexamethylphosphite, m-methylphenol, xylenol, phenol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, Triethylene glycol, diacetone alcohol, butyl lactate, butyl acetate, ethyl ethoxypropionate, propylene carbonate, diethyl oxalate, diethyl malonate, ethylene glycol monobutyl ether (butyl cellosolve) ), diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, 1, 4 - Dichlorobutane, o-dichlorobenzene®, etc. Among them, preferred are N-methyl-2-pyrrolidone, r·butyrolactone, dipropanol, ethylene glycol monobutyl ether (butyl cellosolve), propylene carbonate, and diethylene glycol diethyl ether. A particularly preferable solvent composition is a composition obtained by combining the above solvents, and is a composition in which the polymer in the alignment agent is not precipitated and the surface tension of the alignment agent is in the range of 25 to 40 mN/m. The concentration of the solid component in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1 to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film of the liquid crystal alignment film of 30-200804465. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small, so that the coating film cannot be obtained. A good liquid crystal alignment film; when the solid content concentration exceeds 10% by weight, the thickness of the coating film is too thick, so that a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal alignment agent is increased, and the coating property is deteriorated. The viscosity of the liquid crystal alignment agent of the present invention (the viscosity obtained by measuring the liquid crystal alignment agent at 25 ° C by a rotary viscometer) needs to be appropriately adjusted according to the coating method of the alignment agent, preferably 3 to 100 mPai, more preferably 3 ~50mPa· Xin s, especially good for the range of 3~35mPa.s. Further, the particularly preferable solid content concentration range differs depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, when the spin coating method is employed, it is particularly preferably in the range of from 1 to 5 to 4.5% by weight. When the printing method is employed, it is particularly preferable that the solid content concentration is in the range of 3 to 9 % by weight, so that the solution viscosity falls within the range of 12 to 50 mPa*s. When the ink jet method is employed, it is particularly preferable that the solid content concentration is in the range of 1 to 5 % by weight, so that the viscosity of the solution falls within the range of 3 to 15 mPa * s. 1 The liquid crystal alignment agent of the present invention may further contain a functional decane-containing compound or an epoxy group-containing compound from the viewpoint of improving adhesion to the surface of the substrate. As such a functional decane-containing compound, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-amine can be mentioned. Propyltriethoxydecane, Ν(2-aminoethyl)-3-aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3-aminopropylmethyl Dimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxy-31-200804465 decane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, triethoxydecylpropyltriethylethylamine, N-trimethoxydecylpropyltriethylamine, 10 -trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3 6-diazaindolyl acetate, 9-triethoxydecylalkyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N -benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-benzene tomb-3-aminopropyltri Oxydecane, 3-glycidoxypropyltrimethoxyindole#, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N-bis(oxyethylene)-3-amine Propyltriethoxydecane, and the like. Further, as the epoxy group-containing compound, preferred are, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol dihydrate. Glycerol ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5 ,6-tetraglycidyl-2,4-hexanediol, 1^,1^川',1^-tetraglycidyl-111-di-toluenediamine, 1,3-di(N,N- Diglycidylaminomethyl)cyclohexane, >1 Chuanxiong, ^['-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like. The mixing ratio of the functional decane-containing compound and the epoxy group-containing compound is preferably 60 parts by weight or less based on 100 parts by weight of the total amount of the polyamic acid and/or the ruthenium-imiding polymer. More preferably, it is 50 parts by weight or less. <Liquid Crystal Display Element> The liquid crystal display element 'of the present invention can be manufactured by the following method, for example. -32-.200804465 (1) The liquid crystal alignment agent of the present invention is applied to a film provided with a pattern by a roll coater method, a spin coating method, a printing method, an inkjet method, or the like. On one side of the substrate, a coating film is formed by heating the coated surface. Here, as a method of applying a liquid crystal alignment agent to a substrate, a spin coating method is preferred for the small substrate, a printing method is preferred for the medium substrate, and an ink jet method is preferred for the large substrate. As the substrate, for example, glass such as float glass or soda lime glass; plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, or cyclic polyolefin can be used. ® Transparent substrate. As the transparent conductive film provided on one side of the substrate, tin oxide (NESA film manufactured by SnOO (registered trademark of PPG, USA), indium tin oxide (ITO film made of Ιιΐ2〇3 - SnO), etc. can be used. These transparent conductive materials can be used. The pattern formation of the film is by photolithography and a method of using a mask in advance. The reflective electrode may be a metal such as A1 or Ag, an alloy containing these metals, or the like. However, as long as it has a sufficient reflectance, it is not limited thereto. In the coating of the liquid crystal alignment agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film or the reflective electrode and the coating film, a functional decane-containing compound or a functional titanium-containing compound may be previously coated on the surface of the substrate. After the liquid crystal alignment agent is applied, preheating (prebaking) is usually performed for the purpose of preventing the coating agent liquid from sagging, etc. The prebaking temperature is preferably 30 to 300 ° C, more preferably 40 to 40. 200 ° C, particularly preferably 50 to 150 ° C. Then, completely remove the solvent, in order to heat amidoxime to polyimine, aging (post-baking) process The aging temperature is preferably from 80 to 300 ° C, more preferably from 120 to 0.25 ° C. Thus, the liquid crystal alignment agent of the present invention containing poly-proline is removed by coating to remove an organic solvent to form a coating film as an alignment film. The film is further heated and dehydrated by -33- •200804465 to form a further yttrium imidized coating film. The thickness of the formed coating film is preferably 0.001 to 1/zm, more preferably 0.005 to 0. 5 μm. The crucible (2) can be subjected to a rubbing treatment by rubbing a surface of the formed coating film with a cloth made of a fiber such as nylon, rayon, cotton or the like in a certain direction, and can also control the alignment angle of the liquid crystal molecules. In addition, in addition to the method of polishing, it is also possible to use a method of irradiating the surface of the coating film with polarized ultraviolet light to control the alignment energy. In addition, in order to remove the fine powder (foreign matter) generated during the polishing treatment, the surface of the coating film is cleaned. In the state, the liquid crystal alignment film to be formed is preferably washed with isopropyl alcohol and/or pure water, etc. Further, for the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention, for example, JP-A-6 - a process of partially irradiating ultraviolet rays to change a pretilt angle as shown in Japanese Laid-Open Patent Publication No. H06-281937, or after performing a sanding process as shown in Japanese Laid-Open Patent Publication No. Hei 5-107544 The protective film is partially formed on the liquid crystal alignment film, and after the polishing process is performed in a direction different from the previous polishing process, the protective film is removed, and the alignment of the liquid crystal alignment film can be changed, whereby the visual field characteristics of the liquid crystal display element can be improved. (3) Two substrates in which the liquid crystal alignment film is formed as described above are formed, and two substrates are placed opposite each other through a gap (cell gap), and the peripheral portions of the two substrates are bonded together with a sealant to the surface of the substrate and the sealant. The divided cell gap is filled with liquid crystal, and the injection hole is closed to form a liquid crystal cell. Then, a polarizing plate was provided on the outer surface of the liquid crystal cell, i.e., the outer surface of each of the substrates constituting the liquid crystal cell, to obtain a liquid crystal display element. -34- 200804465 Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like which is a cured product can be used. Examples of the liquid crystal include nematic liquid crystals and disc-type liquid crystals, and may be, for example, a Schiff base liquid crystal, a base liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or an ester terphenyl. For example, chlorinated cholesteryl alcohol, cholesteryl H cholesteryl carbonate may be added to liquid crystals such as liquid crystal, biphenylcyclohexane liquid crystal, pyrimidine liquid hexacyclo liquid crystal, bicyclooctane liquid crystal, or cuba liquid crystal. It is used as a cholesteric liquid crystal and a chiral agent sold under the trade name "C-15" (manufactured by Merck & Co., Inc.). Further, a p-methoxybenzylidene-P-amino-2-methylbutylcinnazone dielectric liquid crystal is used. Further, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate or a polarizing plate made of a polarizing plate or η which is obtained by sandwiching polyvinyl alcohol and absorbing iodine at the same time as η film sandwiched in a cellulose acetate protective film is used. EXAMPLES Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to these examples. The examples and the comparative orientation, the anti-image-resistance, and the printability were carried out by the following method f [vertical alignment] by the cross-Nicol prism when turning on/off the voltage; indicating whether or not the element has an abnormal region (domain). It is "not good" for an abnormal area with no abnormal area. Agent and separation. Among them, oxidized azo liquid crystal, crystal, and dioxygen. In addition, the phthalic acid ester and the "CB-15" may be exemplified by the polarizing film itself which is strong only by the ester, but in the vertical direction. The liquid crystal of the meal is "good", -35- 200804465 [Resistance resistance] After applying a DC voltage of 17V to the liquid crystal display element for 20 hours in a loot environment, the application of the voltage is released. 'Attenuation at room temperature for 15 minutes. Thereafter, the voltage remaining in the liquid crystal cell (residual DC voltage) was obtained by the scintillation elimination method. When the residual DC voltage 値 is smaller, it can be determined that the liquid crystal display element having the anti-image-resistance property is determined, and if the residual DC voltage 値 is 600 mV or less, the liquid crystal display element is judged to have a good anti-image resistance, and the residual DC voltage 値 is higher than 600 mV. It is judged that the anti-image resistance is "not good". # [Printability Experiment] The liquid crystal alignment agent of the present invention (the liquid crystal alignment agent having a total solid concentration of 6.5%) was applied to the belt by a liquid crystal alignment film printer (manufactured by Nippon Photoprinting Co., Ltd.). A transparent electrode surface of a glass substrate having a strip-shaped transparent electrode formed of an IKO film having a thickness of 20 nm and a width of 20 μm at intervals of 1 μm, which was subjected to a hot plate at 80 ° C for 1 minute. The pre-drying was then aged in a clean oven (under a nitrogen atmosphere) at 200 ° C for 1 hour to form a liquid crystal alignment film. The peripheral portion and the central portion of the alignment film of the liquid crystal ® were observed with a microscope at a magnification of 20, and it was judged as "good" when there was no coating unevenness, and "not good" when uneven coating was applied. The evaluation results of the printability of each of the alignment agents are shown in Table 2. Synthesis Example 1 3,3,4,4,-benzophenonetetracarboxylic acid dianhydride as a tetracarboxylic acid dianhydride 3 3.028 9 g (〇, l〇25 mol) and 2,3,5-tricarboxyl 22.9777g (〇.l〇25mol) of cyclopentyl acetic acid dianhydride, 17.1477g (0.0519 mole) of diamine represented by the above formula (C-1) as a diamine compound, and 16.8457g of p-phenylenediamine ( 0.1558 -36- 200804465 Mohr) was dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 4 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. Then, it was washed with methanol, and dried at 40 ° C for 24 hours under reduced pressure to give 87 g of polylysine having a logarithmic viscosity of 0.62 dl / g. The polyamine acid is referred to as "P-1". Synthesis Example 2 47.1326 g (0.1463 mol) of 2,3,4,4,4-benzophenonetetracarboxylic acid dianhydride as tetracarboxylic acid dianhydride, and 2,3,5-tricarboxycyclopentylacetic acid Anhydride • 10.929 8g (0.0488 mol), which is a diamine compound represented by the above formula (C-1), which is 25.8791 g (0. 〇495 mol) and p-phenylenediamine 16.0585 g (0.1485 mol). In 400 g of N-methyl-2-pyrrolidone, it was reacted at 6 (TC for 4 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. Then, it was washed with methanol and passed under reduced pressure. Drying at 40 ° C for 24 hours ' yielded 91 g of poly-proline with a logarithmic viscosity of 0.65 di / g. The poly-proline was used as "P - 2". Synthesis Example 3 ® 3, 3 as tetracarboxylic acid dianhydride ,, 4,4,-benzophenone tetracarboxylic acid dianhydride l〇, 65 86g (〇.〇331 mol) and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 42.0184g (〇.1874莫Ear), diamine 29_2024g (0.055 9 mole) represented by the above formula (C-1) as a diamine compound, p-phenylenediamine 1 8.1 206 g (0.1676 ounce) dissolved in 400 g of N-methyl-2- Pyrrole ketone, at 60 ° C It should be 4 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product, and then washed with methanol and dried at 4 ° C for 24 hours under reduced pressure to obtain 85 g of a logarithmic viscosity of 0.58 dl / Poly-proline acid of g. Polypyrene-37·, 200804465 Aminic acid as "P-3". Synthesis Examples 4 to 7, Comparative Synthesis Examples 1 to 3 except that tetracarboxylic acid dianhydride and diamine compound were replaced by the table. In the same manner as in Synthesis Examples 1 to 3, the poly-proline and polyimine shown in Table 1 were obtained (these were referred to as "P-4" to "P-1"). In Table 1, the acid dianhydrides A to D and the diamines E to G respectively represent the following acid dianhydride: 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride #acid dianhydride B : 2,2,,3,3,-benzophenonetetracarboxylic acid dianhydride dianhydride C: 2,3,5·tricarboxycyclopentyl acetic acid dianhydride dianhydride D: pyromellitic dianhydride II Amine E: a diamine compound represented by the above formula (C-1): a diamine compound represented by the above formula (C-2): diamine G: p-phenylenediamine Comparative Synthesis Example 4 As a tetracarboxylic acid Anhydride 2,3,5- Carboxycyclopentyl acetic acid diacid anhydride anhydride, 8.9096g (〇.〇17〇莫耳), p-phenylenediamine 7.3715g (0.0682Mo) represented by the above formula (C-1) as a diamine compound The ear was dissolved in i4 〇g N-methyl-2-pyrrolidone and reacted at 6 ° C for 4 hours. Next, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. Then, it was washed with methanol, and dried at 40 ° C for 24 hours under reduced pressure to obtain 32 g of polylysine having a logarithmic viscosity of 〇.65 dl / g. 30.0 g of the poly-proline was dissolved in 4 g of methyl-2-pyrrolidone, and 5.67 g of pyridine and 73 g of acetic anhydride were added (pyridine, acetic anhydride phase -38-200804465 for poly-proline The repeating units were all 1 equivalent), and the mixture was dehydrated and closed for 4 hours at no °c. This was precipitated, washed, and reduced in pressure in the same manner as above to obtain 24.4 g of a ruthenium iodide polymer having a logarithmic viscosity of 0.62 dl/g and a ruthenium iodide ratio of 51% (this is referred to as "P_1 1"). . Table 1 Polymeric acid dianhydride indicates the molar ratio of the molar ratio of the molar ratio of all the diamines in the molar ratio of the molar ratio of the total amount of the acid anhydride to the total amount of the acid anhydride. 醯 醯 imidization ratio (%) Synthesis Example 1 P-1 A(50) C(50) E(25) G(75) 0.62 0 Synthesis Example 2 丨P-2 A(75) C(25) E(25) G(75) 0.65 0 Synthesis Example 3 P —3 A(15) C(85) E(25) G(75) 0.58 0 Synthesis Example 4 P-4 B(50) C(50) E(25) G(75) 0.70 0 Synthesis Example 5 P-5 A(10) C(90) F(10) G(90) 0.90 0 Synthesis Example 6 P-6 A(50) C(50) F(25) G(75) 0.81 0 Synthesis Example 7 P-7 A( 90) C(i0) F(50) G(50) 0.65 0 : 匕Comparative Example 1 P-8 A(50) C(50) E(70) G(30) 0.45 0 ftComparative Example 2 P- 9 A(5) C(95) E(7) G(93) 0.80 0 Comparative Synthesis Example: P-10 D(25) C(75) E(25) G(75) 0.70 0 Suppose Synthesis Example z 1 P -11 — C(100) E(20) G(80) 0.62 51 Example 1

To the poly-proline (P-1) obtained in Synthesis Example 1, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether were added to make N-methyl-2-pyrrolidone/ethylene glycol single The mixed weight ratio of butyl ether = 40/60, and 20% by weight of N, N, N', N'-tetraglycidyl-4, 4'-di is added relative to polyglycine (P-1). Aminodiphenylmethane was prepared to have a liquid crystal alignment of -39-200804465 with a total solid concentration of 3.5% by weight (however, when performing a printability test, a liquid crystal alignment agent having a total solid concentration of 6.5% by weight) was prepared. . After thoroughly stirring the mixture, it was filtered through a filter having a pore size of 0.2/m, and applied to a transparent conductive film made of an ITO film provided on one surface of a glass substrate by a spin coater, and subjected to a heating plate at 8 〇 (: 1). Minute pre-drying, followed by aging in a clean oven (under a nitrogen atmosphere) at 200 ° C for 1 hour to form a transparent electrode substrate having a liquid crystal alignment film having a film thickness of 60 nm. Then, in a pair of transparent electrodes / transparent On the outer edge of the substrate coated with the liquid crystal alignment film of the electrode substrate having the liquid crystal alignment film, an epoxy resin binder of alumina balls having a diameter of 5.5/zm is applied, and then the liquid crystal alignment film is applied. The surface is relatively recombined and pressed to cure the adhesive. Next, after the negative liquid crystal (manufactured by Merck & Co., MLC-203 8) is filled between the substrates through the liquid crystal injection port, the acrylic photocurable adhesive is used. The liquid crystal display element was sealed to produce a liquid crystal display element. The results of evaluation of the vertical alignment property and the image sticking resistance of the obtained liquid crystal display element are shown in Table 2. Example 2 In addition to the polylysine obtained in Synthesis Example 2 ( P — 2) Replacement of polyamine The alignment agent and the liquid crystal display element of the present invention were obtained in the same manner as in Example 1 except for the acid (P-1). The evaluation results of the vertical alignment property and the image sticking resistance of the obtained liquid crystal display device are shown in Table 2. 3 The alignment agent and the liquid crystal display device of the present invention were obtained in the same manner as in Example 1 except that polylysine (p-3) obtained in Synthesis Example 3 was used instead of polyglycine (P-1). The evaluation results of the vertical alignment property and the image sticking resistance of the obtained liquid crystal display element are shown in Table 2. -40 - 200804465 Example 4 In place of the polyamine derivative (p-4) prepared in Synthesis Example 4 The alignment agent and the liquid crystal display of the present invention were obtained in the same manner as in Example 1 except for the acid (P-1). The evaluation results of the vertical alignment property and the image retention resistance of the obtained liquid crystal display device are shown in Table 2. Example 5 A mixture of N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether was used instead of polylysine (P-5) prepared in Synthesis Example 5 instead of polyglycine (P-1). The alignment agent and the liquid crystal display element of the present invention were obtained in the same manner as in Example 1 except that the weight ratio was 30/70. The evaluation results of the vertical alignment property and the image retention resistance of the crystal display element are shown in Table 2. Example 6 In place of the poly-proline (P-6) instead of polylysine (P-1) prepared in Synthesis Example 6. The alignment agent and the liquid crystal display device of the present invention were obtained in the same manner as in Example 1 except that the weight ratio of N-methyl-2-pyrrolidone/ethylene glycol monobutyl ether was 30/70. The results of the evaluation of the vertical alignment and the anti-image resistance of the element are shown in Table 2. Example 7 In place of polylysine (P-1) instead of polylysine (P-1) prepared in Synthesis Example 7, An alignment agent and a liquid crystal display element of the present invention were obtained in the same manner as in Example 1 except that N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane was not added. The results of evaluation of the vertical alignment property and the image sticking resistance of the obtained liquid crystal display element are shown in Table 2. Comparative Example 1 -41- 200804465 In addition to the polyplysine (P-1) which was prepared in Comparative Synthesis Example 3, instead of polylysine (P-1), N-methyl-2-pyrrolidone/ethylene glycol An alignment agent and a liquid crystal display element were produced in the same manner as in Example 1 except that the weight ratio of monobutyl ether was 30/70. The results of evaluation of the vertical alignment property and the image sticking resistance of the obtained liquid crystal display element are shown in Table 2. Comparative Example 2 In place of the polyamido acid (P-1), N-methyl-2-pyrrolidone/ethylene glycol monobutyl, except that the ruthenium iodide polymer (p-11) obtained in Comparative Synthesis Example 4 was used instead. An alignment agent and a liquid crystal display element were produced in the same manner as in Example 1 except that the weight ratio of the ether® was changed to 50/50. The results of evaluation of the vertical alignment property and the image sticking resistance of the obtained liquid crystal display element are shown in Table 2. Table 2 Polymer Vertical Alignment Anti-Image Residual Printable Residual DC (mV) Judgment Example 1 P-1 Good 550 Good Good Example 2 P-2 Good 500 Good Good Example 3 P-3 Good 580 Good Good Practice Example 4 P-4 Good 560 Good Good Example 5 P-5 Good 590 Good Good Example 6 P-6 Good 400 Good Good Example 7 P-7 Good 350 Good Good Comparative Example 1 P -10 Good 800 Not good Comparative Example 2 P-1I Good 800 Not good -42-200804465 From the above Table 2, the liquid crystal alignment film obtained from the liquid crystal alignment agents obtained in Examples 1 to 7 showed excellent vertical alignment, and The anti-image resistance was better than that obtained in Comparative Examples 1 to 2. It is to be noted that the anti-image resistance of the vertical alignment type liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can be at least one of containing an aromatic ketone represented by the above formula (1 - 1) and formula (1-2). The structure of the tetracarboxylic dianhydride structure is selected and the copolymerization composition of the monomer is adjusted. As described above, according to the present invention, it is possible to provide a vertical alignment type liquid crystal alignment agent which exhibits excellent vertical alignment property and excellent in image retention resistance, and a vertical alignment type liquid crystal display element having the alignment film and having a beautiful image. [Simple diagram description] 4επι None. [Main component symbol description] Turtle / \ \Λ

-43-

Claims (1)

200804465 X. Patent application scope: 1. A vertical alignment type liquid crystal alignment agent characterized by containing at least one type 1 which is an aromatic ketone selected from each of the following formulas (1 to 1) and (1 to 2) a tetracarboxylic acid dianhydride, a second tetracarboxylic acid dianhydride different from the first tetracarboxylic acid dianhydride represented by the following formula (2), a first diamine represented by the following formula (3), and the following formula ( 4) a polyaminic acid obtained by a second diamine reaction different from the first diamine and/or a ruthenium-imided polymer obtained by dehydrating and ring-closing the polyamic acid, Wherein a and b are independently an integer of 0 to 3, and Ri to Ru independently represent a hydrogen atom; a halogen atom; or a substitution group optionally having an oxygen atom, a sulfur atom, a nitrogen atom or a ruthenium atom; a substituted hydrocarbon group having 1 to 30 carbon atoms; or a monovalent polar group, wherein a group of two adjacent groups selected from Ri to R6 and R7 to Rn, respectively, are bonded to each other to form a carboxylic anhydride group. Mission, -44- 200804465 (1 - 2> wherein X represents a single bond, a sulfur atom, an oxygen atom, an alkylene group having 1 to 3 carbon atoms, a carbonyl group (-CO-), a sulfonyl group (-S〇2-), Any of the imine groups (-NH-) 'c and d are independently an integer of 0 to 3, and R13 to R 2 4 independently represent a hydrogen atom; a halogen atom; optionally having an oxygen atom, sulfur a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a monovalent polar group; wherein one of R13 to R18 and R19 to R24, respectively, is selected from a linking group of an atom, a nitrogen atom or a halogen atom; Two adjacent groups of the group are each connected to each other to form a carboxylic anhydride group; (2) wherein R25 is a tetravalent organic group; -45- 200804465 Wherein e is 0 or 1, and R26 is selected from the group consisting of an ether bond (-〇-), a carbonyl group (-CO-), a carbonyloxy group (-COO-), an oxycarbonyl group (-OCO-), a guanamine bond ( -NHCO-, -CONH-), a thioether bond (-S-), a divalent organic group of a methyl group, R27 is a divalent organic group different from R26, and R28 is a group selected from a steroid skeleton. a group having a group having a fluorine atom or a group having a linear alkyl group having 1 to 22 carbon atoms; H2N-R29-NH2 wherein R29 is a divalent organic group. 2. The vertical alignment type liquid crystal alignment agent of claim 1, wherein the ratio of the first tetracarboxylic dianhydride to the total of the first tetracarboxylic dianhydride and the second tetracarboxylic dianhydride is 5 to 90 moles %. 3. The vertical alignment type liquid crystal alignment agent of claim 1 or 2, wherein the first tetracarboxylic acid dianhydride is selected from the group consisting of 3, 3, 4, 4, benzophenone tetracarboxylic acid dianhydride , 2,3,3,,4,-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, at least one tetracarboxylic acid dianhydride, second The carboxylic acid dianhydride is selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,3,4·cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2 , 3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro- 8--46- 200804465 methyl·5·(tetrahydro-2,5 -dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5 : at least one tetracarboxylic dianhydride of 6-dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride. The vertical alignment type liquid crystal alignment agent of any one of the above-mentioned formula (3), wherein the first diamine represented by the above formula (3) is the following formula (5) or the following formula (6) At least one of each of the diamines having a steroid skeleton, A vertical alignment type liquid crystal display element comprising a vertical alignment type liquid crystal alignment film formed of a vertical alignment type liquid crystal alignment agent according to any one of claims 1 to 4. -47- 200804465 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 /\\\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: