TW201109367A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, polyamic acid and polyimide - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent which could give a liquid crystal alignment film with good pretilt characteristic given by photoalignment method, and yet does not worsen display performance even in the case of being driven for a long time. The liquid crystal alignment agent comprises at least one kind of polymer selected from a group consisted of a polyamic acid obtained from reacting a tetracarboxylic acid dianhydride with a diamine, and a polyimide formed by dehydration cyclization of the polyamic acid. The diamine comprises a first diamine represented by a compound represented by formula (A-1-1) below and a second diamine with photoreactive structure.

Description

201109367 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, polylysine, and polyimine. More specifically, a liquid crystal alignment agent for a liquid crystal alignment film having suitable properties can be provided even by a photo-alignment method in which light irradiation is small. [Prior Art] At present, as an operation mode of a liquid crystal display element, a TN (Twisted Nematic) type, an STN (Super Torque Nematic) type, and the like using liquid crystal molecules having positive dielectric inductivity are known and used. A liquid crystal display element such as a VA (vertical alignment) type having a liquid crystal molecule having a negative dielectric conductivity is mainly used as a liquid crystal alignment film formed of an organic film in order to control the alignment of various liquid crystal molecules (Patent Documents 1 to 4). In order to fix the liquid crystal alignment film in the above-mentioned V A type or the like, the liquid crystal alignment film in the TN type 'STN type or the like is required to have a pretilt angle characteristic in order to fix the tilt direction in the liquid crystal driving. The method of providing the pretilt angle characteristic is generally a brush film method, and the latter is generally a brush film method, a method of providing a projection on a surface of a substrate, and the like. Among them, the 'brushing method may cause poor display or circuit damage due to dust or static electricity generated in the step; on the other hand, the method of providing protrusions on the surface of the substrate may damage the brightness of the obtained liquid crystal display element, etc. Both have problems. Therefore, as a method of imparting a change in the pretilt angle to them, a method of photo-alignment method of 201109367 is proposed, which is a method of irradiating a photosensitive film with an external line from a direction inclined with respect to a film normal (Patent Document 5 and Non-patent) Literature 1). In recent years, liquid crystal display elements have been rapidly developed, particularly in television applications, and can be viewed for a particularly long time as compared with conventional liquid crystal display elements. However, it is known that the conventionally known liquid crystal display element deteriorates in display quality if it is continuously operated for a long period of time. One of the reasons may be considered to be that the long-term operation of the liquid crystal alignment film may be deteriorated when exposed to light for a long time. Therefore, in the field of liquid crystal alignment films, materials which do not deteriorate in display performance even when continuously operated for a long period of time are being studied. For example, Patent Document 6 proposes the use of an alignment film material having a crosslinked structure. However, even with the technique of the same document, the degree of suppression of display quality deterioration is insufficient when continuously operated for a long period of time. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-56-91277 [Patent Document 2] Japanese Patent Laid-Open Publication No. H-12-528 (Patent Document 3) Japanese Patent Laid-Open Publication No. JP-A-2002-83810 (Patent Document No.) JP-A-2010-97188 [Non-Patent Document] 201109367 [Non-Patent Document 1] J. of the SID 11/3, 2003, p579 [Non-Patent Document 2] TJ Scheffer et. al., J. Appl. Phys. Vo 1. 48, pi 7 8 3 (1 9 7 7) [Non-Patent Document 3] F. Nakano et. al., JPN. J. Appl. Phys. vol. 19, p20 1 3 (1 9 8 0) SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a liquid crystal alignment agent which can provide good pretilt characteristics by photo-alignment method, and which does not even operate continuously for a long time. A liquid crystal alignment film which causes deterioration in display performance. [Means for Solving the Problems] According to the present invention, the above objects and advantages of the present invention are achieved by a liquid crystal alignment agent containing a polyamic acid selected from the group consisting of a reaction of a tetracarboxylic dianhydride and a diamine, and At least one polymer of the group consisting of polyamidene formed by dehydration of the polyamine, wherein the diamine comprises a first diamine and a second diamine having a photoreactive structure, the first The diamine is represented by the following formula (A-0).

(In the formula (A-0), X1 represents a single bond, a methylene group, an alkylene group having a carbon number of 2 or 3 '*-〇-, *-CO〇-, *-OCO-, IX'-R1- , K-Rj-X'- or ♦-X'-R^-X'J where X represents +-0_, +-COO- or + -OCO-, respectively (the "+" in 201109367 indicates The connection key is oriented to the left of the formula (A_〇), and R1 is an alkylene group having a carbon number of 2 or 3, respectively, with a "*,, a linkage and a diaminophenyl linkage",

Ring1 and Ring2 are each independently a cyclohexyl group or a phenyl group, X" is a single bond, +-0-, +-COO- or +-〇CO- (where "+" means that the bond with it is oriented In the left direction of the formula (A-0), a is 0 or 1, and b is an integer of 0 to 3. When b is 2 or more, a plurality of X's and Ring2 existing may be the same or different, and a is 0. When the 'leftmost X' of the formula (A_0) is a single bond, c is an integer of 0~2 0, and α and β are integers of 〇~2c+l, respectively, where α + β = 2ο+1, and a When + b = 0, c is not 0). [Effect of the Invention] The liquid crystal alignment agent of the present invention can be formed into a liquid crystal alignment agent which can be applied to a photo-alignment method, and can be formed even when it is continuously operated for a long period of time. When the liquid crystal alignment element of the present invention is used for a liquid crystal display element, the obtained liquid crystal display element is excellent in various characteristics such as display characteristics and reliability. Therefore, the liquid crystal display element is excellent in various characteristics. Alignment elements can be effectively applied to a variety of devices, such as desktop calculators, watches, clocks, counting boards, word processors , a personal computer, a liquid crystal television, etc. [Embodiment] The liquid crystal alignment agent of the present invention, as shown above, includes a polyamic acid selected from the reaction of a tetracarboxylic dianhydride and a diamine, and dehydrating the polyamic acid. a closed-loop formed polyimine of at least one polymer (hereinafter referred to as "specific polymer" under 201109367), wherein the diamine comprises the first two represented by the above formula (A-〇) An amine and a second diamine having a photoreactive structure. <tetracarboxylic dianhydride> For the synthesis of the tetracarboxylic dianhydride of the polyproline in the present invention, for example, an aliphatic tetracarboxylic acid can be used. The acid dianhydride, the alicyclic tetracarboxylic dianhydride, the aromatic tetracarboxylic dianhydride, etc., as a specific example, as an aliphatic tetracarboxylic dianhydride, a butane tetracarboxylic dianhydride etc. are mentioned, for example. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and 1,3. 3&,4,5,91)-hexahydro-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphtho[l,2-c]furan-1,3-dione , l, 3, 3a, 4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphtho[l,2-c]furan-1,3-di Ketone, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2,5,-dione)' 5-(2,5-di-side oxygen Tetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 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, 4,9-dioxatricyclo[5.3.1.02 '6] undecane-3,5,8,10-tetraketone, etc.; J aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, etc.; and Patent Document 7 (JP-2010) The tetracarboxylic dianhydride described in JP-A-97188. Among the tetracarboxylic dianhydrides for synthesizing the aforementioned polyaminic acid, among them, those having an alicyclic tetracarboxylic dianhydride are preferred, and particularly preferably containing a 2,3,5-tricarboxyl ring. Amyl phthalic anhydride dianhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride and 2,4,6,8-tetracarboxybicyclo[3.3.0 ] octane-2:4,6:8- 201109367 At least one species of the group consisting of dianhydride. _ The tetra-residual acid dianhydride used for the synthesis of the aforementioned poly-araminic acid preferably contains 80% by mole or more of the total tetracarboxylic dianhydride, more preferably 90% by mole or more. Free 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxy-2-carboxymethylnordecane-2:3,5:6-dianhydride and 2,4,6 At least one of the group consisting of 8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride. The tetracarboxylic dianhydride for synthesizing the aforementioned polyamic acid is preferably selected only from 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxy-2-carboxyl Group consisting of decane-2:3,5:6-dianhydride and 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride At least one form of formation. The diamine used for the synthesis of the poly-proline in the present invention is a diamine comprising a first diamine represented by the above formula (A-0) and a second diamine having a photoreactive structure. The diamine may further contain a group selected from the group consisting of a third diamine represented by the following formula (A-3) and a fourth diamine as a diamine other than the first to third diamines. At least one.

(In the formula (A-3), R111 is each independently a hydrogen atom or a 'hospital group' having a carbon number of 1 to 12, and Rv and Rv are each independently a hydrogen atom or a methyl group.) 201109367 [First diamine] The above first diamine is a compound represented by the above formula (A-0). X1 in the above formula (A-0) is preferably *_〇_, *-COO· or *-〇CO- (wherein the bond of "band" is bonded to the diaminophenyl group).

The ring-extension or phenyl group of Ring1 and Ring2 are preferably, respectively, 4_cyclohexylene and 1,4-phenyl. R i n g 1 is preferably 1,4 - stretched phenyl, and R i n g 2 is preferably 1,4-cyclohexylene. .X" is preferably a single bond. (X is 2c + 1 and β is 〇, that is, the group CeHaFp - preferably a group CeH2e + l - preferably. a + b is an integer of 2 to 4' or When a + b is 0 or 1, c is preferably 6 or more. Among them, a + b is preferably an integer of 2 to 4. Preferred of the compound represented by the above formula (A-0) The structure is, for example, a compound represented by the following formula (A-1).

(In the formula (A-1), X1 is *·0-, *-COO- or *-OCO- (wherein, a bond having a "*,, and a diaminophenyl group"), a is 0 or 1 , b is an integer of 0 to 2, and c is an integer of 1 to 20.) X1 in the above formula (A-1) is preferably *-〇- or *-COO- (wherein the bond and diamine of the band) Specific examples of the group phenyl group) of CeH2e+1- may, for example, be methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, or Sulfhydryl, n-decyl, n-twelve-10-201109367 alkyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl An alkyl group, n-nonadecyl 'n-icosyl group, etc. The two amine groups in the diaminophenyl group are preferably 2,4-position or 3,5-position relative to other groups. Specific examples of the compound represented by the formula (A-1) include h2n such as a compound represented by the following formula (A-1-1) to (A-1-4).

C5H11 (A-1-1)

H2N

(A-1-2)

(A-1-3) H2N—~0_(CH2)17CH3 (A-1-4) nh2 In the above formula (A-1), a and b are preferably not simultaneously 0, and a + b is more preferably 2 Or 3. [Second Diamine] The above second diamine is a diamine having a photoreactive structure. The photoreactive structure preferably has a structure capable of performing at least one reaction selected from the group consisting of isomerization and dimerization by light irradiation, and may be exemplified by the following formula (A- ) The structure shown.

(A-2) (In the formula (A-2), d is 0 or 1, and A1 and A2 are each an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or The cyano group, e and f are integers of 0 to 4, respectively, and " " represents a linkage bond). A1 and A2 in the above formula (A-2) are each preferably an alkoxy group having a carbon number. Preferably, e and f are each 〇^ The second diamine preferably further includes a moiety having a function of aligning liquid crystal molecules, and a photoreactive structure having the site, for example, may be exemplified by the following formula At least one of the structures represented by (A-2-1) and (A_2-2), respectively.

(In the formulas (A-2-1) and (A-2-2), Ai, A2, d, e, and f are the same as defined in the above formula (A-2), respectively, -12- 201109367 R1 and Rn respectively It is an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 4 to 30 carbon atoms having an alicyclic structure, and X11 and X111 are -〇-, -CO-, respectively. , -CO-O-, -O-CO-, -NR-, -NR-CO-, -CO-NR-, -NR-C0-0-, -O-CO-NR-, -NR-CO- NR- or -0-CO-〇- (wherein R is a hydrogen atom or an alkyl group having a carbon number of 1 to 4), and RM1 is a methylene group, an aryl group, a divalent alicyclic group, and -Si ( CH3)2-, -CH=CH- or -CeC-, wherein one or more of the hydrogen atoms of Rln may be substituted by a cyano group, a halogen atom or an alkyl group having 1 to 4 carbon atoms, h is An integer of 1 to 6, i is an integer of 0 to 2, and when there are a plurality of the above X11 and R111, 'they may be the same or different, j is 〇 or 1, and "+" respectively represents a connection key)" The alkyl group having a carbon number of R20 and R" in the formulae (A-2-1) and (A-2-2) is 20, and examples thereof include a methyl group, a n-butyl group, a n-pentyl group, and a n-hexyl group. N-heptyl, n-octadecyl and the like. R1 and R11 have an alkyl group having 1 to 20 carbon atoms, and each of them is preferably a linear group having a carbon number of 1 to 12, more preferably a carbon number, from the viewpoint of exhibiting good liquid crystal alignment. 3 to 12 linear chain bases, particularly preferably linear alkyl groups having a carbon number of 4 to 12. The fluoroalkyl group having 1 to 8 carbon atoms as R1 and R11 is preferably a linear fluorine compound having 3 to 6 carbon atoms from the viewpoint of exhibiting good liquid crystal alignment properties, and examples thereof include For example, 3,3,3-trifluoro-n-propyl, 4,4,4-tri-13- 201109367 fluoro-n-butyl, 4,4,5,5,5-pentafluoro-n-pentyl, 4,4,5 , 5,6,6,6-heptafluorohexyl and the like. Specific examples of the hydrocarbon group having 4 to 30 carbon atoms of the alicyclic structure of R1 and Rn include a cyclohexylmethyl group, a gallstone base, a cholesteryl group, and a sheep's alkyl group. X11 and X111 are each preferably °. The second diamine may have one or two or more photo-alignment structures in one molecule, and preferably has one or two such structures. In the specific example of the second diamine having such a structure, each of the diamines having a structure represented by the above formula (A-2-1) can be exemplified by the following formula (A-2-1- 1) ~(A-2-1-13) respectively indicate compounds, etc.; -14- 201109367

(A-2-1-2) (A-2-1-3)

O

-15- 201109367

-16 - 201109367

(Α-2-1-13) ο As a diamine having a structure represented by the above formula (Α-2-2), for example, a compound represented by the following formula (Α-2-2-1) can be given.

[Third diamine] -17- 201109367 The above third diamine is a compound represented by the above formula (A-3). In the above formula (A-3), Riv and Rv are each preferably a hydrogen atom. The two amine groups attached to the benzene ring of the above formula (A-3) are preferably at the 2,4-position with respect to the nitrogen atom. As the third diamine, the most preferred is N,N-diallyl-2,4-diaminoaniline. [Four Diamine] The above fourth diamine is two of the above first to third diamines

Amine 'diamine-based organooxane and the like. Specific examples thereof can be exemplified as the aliphatic diamine, for example, 1,1-m-xylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,5- Pentaamine, 1,6-hexanediamine, etc.; as the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), i,3_bis(aminomethyl)cyclohexane or the like; examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-di Aminodiphenyl sulfide, it diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4,-diamino 2,2,_bis ( Trifluoromethyl)biphenyl, 2,7-diaminostilbene, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl] Propyl, 9,9-bis(4-aminophenyl) burial, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2_bis (4_ Aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediphenylene)bis(aniline), 4,4,-(meta-phenylenediisopropyl)bis(aniline) ' 1,4-bis(4-aminophenoxy)benzene, 4,4,·bis(4-amine Phenyloxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, -18- 201109367 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3 ,6-diaminocarbazole, N-methyl-3,6-diaminosostazole, N_ethyl-3,6-diaminocarbazole 'N_phenyl-3,6-diamine Ketrazole, N,N'-bis(4-aminophenyl)-benzidine, N,N,-bis(4-aminophenyl)-N,N'-dimethylbenzidine 'cholesterol Alkoxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene '3,5-diaminobenzoic acid cholesteryl ester, 3,5·diamine Cholesteryl benzoate, lanthanum alkyl 3,5-diaminobenzoate, etc.; as the diamine organooxane, for example, bis(3-aminopropyl)-tetramethyl In addition to the dioxane or the like, the diamine described in Patent Document 7 (Japanese Laid-Open Patent Publication No. Hei. No. Hei. [Composition of Diamine] The diamine used for the synthesis of the poly-proline in the present invention is a diamine containing the first diamine and the second diamine as described above, and may further comprise any one selected from the above The group consisting of the third diamine and the fourth diamine to /J/-* is used as a diamine for synthesizing the polyamic acid in the present invention, and preferably contains 1 with respect to the whole ~ 5 0 moles, more preferably contains 2 to 2 moles. /. The above first diamine; preferably contains 5 〇 to 9 9 mol%, more preferably 70 to 95 mol% of the above second diamine relative to all limbs; relative to all diamines, a third diamine having a range of 20 mol% or less and further containing a range of 1 to 1 mol%; -19- 201109367 may contain a range of 20 mol% or less with respect to all diamines, further The above fourth diamine may be contained in a range of 10 mol% or less. The diamine for synthesizing the poly-proline in the present invention is preferably composed only of the above-mentioned first diamine and the above-mentioned second diamine, or only the above-mentioned first diamine, second type II The amine and the third diamine are composed. [Molecular weight modifier] In the synthesis of the above polyamic acid, a terminal modified polymer can be synthesized by using an appropriate molecular weight modifier together with the tetracarboxylic dianhydride and the diamine as described above. By forming the terminal-modified polymer', the coating property (printability) of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The molecular weight modifier may, for example, be an acid monoanhydride, a monoamine compound or a monoisocyanate compound. Specific examples thereof are: as the acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl group Succinic anhydride, n-hexadecyl succinic anhydride, etc.; as the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc.; The isocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 1 part by weight or less with respect to the total of 1 〇 〇 by weight of the tetracarboxylic dianhydride and the diamine used, and more preferably 1 part by weight or less. <Synthesis of polyglycolic acid> -20- 201109367 The ratio of use of tetracarboxylic dianhydride and diamine used in the synthesis reaction of polyproline is 1 equivalent to the amine group of diamine, tetracarboxylic acid The acid anhydride group of the dianhydride is preferably a ratio of 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at -20T: to 150 ° C, more preferably at 〇 ° C to 10 ° C, preferably 0.1 to 120 ° Hours, preferably for 0.5 to 48 hours. Among them, the organic solvent may, for example, be N-methyl-2-pyrrolidone, N,N-dimethylacetamide, hydrazine, hydrazine-dimethylformamide, dimethyl hydrazine, γ-butyl An aprotic polar solvent such as lactone, tetramethylurea or hexamethylphosphonium triamine; a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The amount (a) of the organic solvent is preferably an amount of the total amount (b) of the tetracarboxylic dianhydride and the diamine relative to the total amount (a + b) of the reaction solution of 0.1 to 50% by weight. As described above, a reaction solution obtained by dissolving polylysine can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after separating the polyamic acid contained in the reaction solution, or purifying the separated polyamic acid to prepare a liquid crystal alignment. Agent. When polypyridic acid is dehydrated and closed to form a polyimine, the above reaction solution can be directly used for the dehydration ring closure reaction; the polylysine contained in the reaction solution can be separated and used for the dehydration ring closure reaction; or the separation can be carried out. After the polyamic acid is refined, it is used for the dehydration ring closure reaction. The separation and purification of polylysine can be carried out by a known method. <Synthesis of Polyimine> The above polyiminoimine can be obtained by imidization of a polyfluorene acid synthesized as described above by dehydration of -21-201109367. The polyimine in the present invention may be a complete hydrazine imide of a glycine structure having a proline structure as a precursor of polyproline, or may be a part of a proline structure. A partial quinone imide that has an acid structure and a quinone ring structure. The ruthenium imidization ratio of the polyimine in the present invention is preferably 30% or more, more preferably 40 to 90%. The ruthenium imidization ratio is a ratio indicating the number of the quinone ring structure in the percentage of the amount of the guanidine structure of the polyimine and the total amount of the quinone ring structure. The dehydration ring closure of polylysine is preferably carried out by heating poly-proline, or dissolving poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating according to the need . Among them, it is preferred to carry out the latter method. In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic acid solution, the dehydrating agent may, for example, be an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The amount of the dehydrating agent to be used is preferably from 0.01 to 20 mols per mol of the proline structure of 1 mol of polylysine. The dehydration ring-closure catalyst ′ is, for example, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine. As the dehydration ring-closing catalyst, the amount of the dehydrating agent to be used is preferably 〇 1 1 1 1 耳 耳. The organic solvent used in the dehydration ring closure reaction may, for example, be an organic solvent exemplified as a solvent used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 〇~丨8 〇 ° C, more preferably 10 to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours. -22- 201109367 This gives a reaction solution containing polyimine. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after removing a dehydrating agent and a dehydration ring-closing catalyst from the reaction solution; and can also be used for preparing a liquid crystal alignment agent after separating the polyimine. Or after the isolated polyimine is refined, it is used to prepare a liquid crystal alignment agent. These purification operations can be carried out according to a known method. <Other components> The liquid crystal alignment film of the present invention contains the above specific polymer as an essential component, but may contain other components as necessary. Examples of the other component include a polymer other than the specific polymer (hereinafter referred to as "other polymer"), a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), A functional decane compound or the like. [Other Polymers] The above other polymers can be used to improve solution properties and electrical properties. The other polymer is a polymer other than the specific polymer as described above, and examples thereof include polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing no such second diamine (hereinafter, It is called "other poly-proline"), polyimine (hereinafter referred to as "other polyimine") formed by dehydration and ring closure of the poly-proline, polyphthalate, polyester, polyfluorene An amine, a polyoxyalkylene, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly(styrene-phenylmaleimide) derivative, a poly(meth)acrylate, or the like. Among them, other polyamines or other polyimines, more preferably other polyamines, are preferred. As the tetra-23-201109367 carboxylic acid dianhydride for synthesizing the above other polyaminic acid or other polyimine, the same four as described above and tetracarboxylic dianhydride for synthesizing a specific polymer can be cited. The carboxylic acid dianhydride is preferably at least one selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and pyromellitic dianhydride. A diamine for synthesizing the above other polyaminic acid or other polyimine, preferably at least one selected from the group consisting of the above first diamine, third diamine and fourth diamine. More preferably, at least one selected from the group consisting of a fourth diamine is used. The diamine for synthesizing other polyaminic acid or other polyimine is preferably composed of only at least one selected from the above-mentioned fourth diamines, and preferably contains 5 with respect to all diamines used. 0 mol% or more, more preferably 80 mol% or more, selected from the group consisting of p-phenylenediamine, 4,4-diaminodiphenylmethane and 4,4-diaminodiphenyl ether At least one of the other polymers used in a proportion relative to the total amount of the polymer (refers to the total amount of the above specific polymer and other polymers, the same below), preferably 90% by weight or less, more preferably 5 0 ~80% by weight. [Epoxy compound] Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether 'propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl glycol. 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^,:^,]^,,:^,-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N- Diglycidylaminomethyl)cyclohexane, -24 - 201109367 N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-di Glycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, and the like. The mixing ratio of these epoxy group-containing compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total of the polymer. [Functional decane compound] The above functional decane compound may, for example, be 3-aminopropyltrimethoxydecane or 3-aminopropyltriethoxydecane '2-aminopropyltrimethoxydecane , 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-amino Propylmethyldimethoxydecane, 3-guanidinopropyltrimethoxydecane, 3-guanidinopropyltriethoxylate, N-ethoxymercapto-3-aminopropyldimethyl Alkyl samarium, N-ethoxycarbonyl-3-aminopropyltriethoxy decane, N-triethoxycarbenylpropyltriethylamine, N-trimethoxymethylidene Propyltriethylamine, 10-trimethoxycarbamido-1,4,7-trioxane, 10-triethoxycarbamido-1,4,7-trioxane, 9-trimethoxyindolyl-3,6-dimercaptoacetate, 9-triethoxyindolyl-3,6-dimercaptoacetate, N-benzyl-3-amino Propyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyl Base Silane ethoxy, N- bis (ethyl extend oxide) _3- aminopropyl trimethoxy Silane, N - bis (Oxidation extending aminoethyl) -3-aminopropyl triethoxy silane-like. The mixing ratio of these functional decane compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight - 25 to 201109367 parts, based on 100 parts by weight of the total of the polymer. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is constituted by dissolving and containing the above specific polymer and other additives optionally mixed as needed in a preferred organic solvent. The organic solvent which can be used in the liquid crystal alignment agent of the present invention may, for example, be a solvent exemplified as a solvent used in the synthesis reaction of polyglycine. Further, it is also possible to appropriately select an organic solvent which has been confirmed as a poor solvent of polyglycine and polyimine. Preferred examples of the organic solvent include, for example, N-methyl-2-pyrrolidone' γ-butyrolactone, γ-butene amide hydrazine, hydrazine-dimethylformamide, hydrazine, Ν-Dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl Ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether 'ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene two Alcohol 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, diisobutyl ketone, isoamyl propionate 'isoamyl butyrate' diisoamyl Ether and the like. They may be used singly or in combination of two or more. The solid content concentration of the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the organic solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc. 26- 201109367 1 ~ 1 0% by weight range. That is, the liquid crystal alignment agent of the present invention can form a coating film of a liquid crystal alignment film by applying it to the surface of the substrate to remove the organic solvent, but when the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small. It may be difficult 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 is too large, it may be difficult to obtain an equally good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases. Coating characteristics may be deteriorated. The range of the solid component concentration which is particularly preferable differs depending on the method employed when the liquid crystal alignment agent is coated on the substrate. For example, when the spin coating method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. When the printing method is carried out, the solid content concentration is in the range of 3 to 9 % by weight, whereby the solution viscosity is particularly preferably in the range of 1 2 to 50 mPa 's. When the solid content concentration is in the range of 1 to 5 wt%, the viscosity of the solution is particularly preferably in the range of 3 to 15 mPa_s. <Method of Forming Liquid Crystal Alignment Film> The liquid crystal alignment agent of the present invention is suitably used for forming a liquid crystal alignment film by a photo-alignment method. The method of forming a liquid crystal alignment film may, for example, apply a liquid crystal alignment agent onto a substrate to form a coating film, and irradiate polarized light or unpolarized ultraviolet light on the coating film from a direction inclined with respect to the coating film surface, or from a relative A method in which a polarized light is applied to the coating film in a direction perpendicular to the coating film surface to impart a liquid crystal alignment energy to the coating film. First, the liquid crystal of the present invention is applied to the transparent conductive film side of the substrate on which the pattern-like transparent conductive film is provided by a suitable coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method, ς -27-201109367. An aligning agent. After coating, the coated surface is formed by preheating (prebaking) the coated surface and then firing (post-baking). The prebaking conditions are, for example, carried out at 40 to 120 ° C for 0.1 to 5 minutes, and the post-baking conditions are preferably at 120 to 300 ° C, more preferably 150 to 250 ° C, preferably 5 to 2 00. Minutes, preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably from 〇1 to 1 μmη, more preferably from 0.005 to 0.5 μmη. As the substrate, for example, a glass such as float glass or soda glass: a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether or polycarbonate, or the like can be used. Transparent substrate, etc. For the transparent conductive film, a NESA film made of Sn02, an ITO film made of In203-Sn02m, or the like can be used. For patterning of these transparent conductive films, a photolithography method or a method of using a mask when forming a transparent conductive film can be used. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate or the transparent conductive film and the coating film, a functional decane compound, a titanate compound or the like may be applied to the substrate and the transparent conductive film in advance. Next, by irradiating polarized light or ultraviolet rays of unpolarized light, liquid crystal alignment energy is imparted to the coating film, and the coating film serves as a liquid crystal alignment film. Here, as the radiation, ultraviolet rays and visible light containing light having a wavelength of 150 to 800 nm can be used, and ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. When the radiation to be used is polarized light (linearly polarized light or partially polarized light), it may be irradiated from a direction perpendicular to the surface of the coating film, or may be irradiated from an oblique direction in order to impart a pretilt angle -28-201109367. On the other hand, when irradiating radiation of unpolarized light, the irradiation must be performed in a direction inclined from the surface of the coating film. As the light source for irradiating the radiation, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The ultraviolet light in the above preferred wavelength region can be obtained by means of a light source and a means such as a filter, a diffraction grating or the like. The irradiation amount of the radiation is preferably 1 J/m2 or more, less than 1 〇, 〇〇〇j/m2, more preferably 10 to 3,000 J/m2. Further, when the liquid crystal alignment energy is imparted to the coating film formed of the liquid crystal alignment agent known in the art by the photo-alignment method, a radiation irradiation amount of 10,000 J/m2 or more is required. However, when the liquid crystal alignment agent of the present invention is used, the amount of radiation irradiation in the photo-alignment method is 3,000 J/m 2 or less, and further i, 〇〇〇J/m 2 is obtained, and the further step is 3 〇〇 J / M2 below 'can also give good liquid crystal alignment energy, which helps to reduce the manufacturing cost of liquid crystal display elements; <Manufacturing Method of Liquid Crystal Display Element> The liquid crystal display element of the stomach of the present invention has a liquid crystal alignment agent of the present invention having a shape of $%$g S5 (3⁄4 film). The liquid crystal display element of the present invention can be produced, for example, as follows. In the substrate of the liquid crystal alignment film, liquid crystal cells are produced by disposing liquid crystal between the two substrates. For the production of liquid crystal cells, for example, the following two methods are available. The first method is a currently known method. Each of the liquid crystal alignment films is disposed opposite to each other with a gap (cell gap) therebetween, and -29-201109367 is used to bond the peripheral portions of the two substrates by using a sealant, on the surface of the substrate and the sealant. The liquid crystal cell can be fabricated by injecting the liquid crystal into the divided cell gap and sealing the injection hole. The second method is a method called 〇DF (One Drop Fill) method, one of the two substrates forming the liquid crystal alignment film. a predetermined position on the substrate, applying, for example, an ultraviolet curable sealant, and then dropping the liquid crystal on the liquid crystal alignment film surface, bonding the other substrate and facing the liquid crystal alignment film, and then, The liquid crystal cell can be produced by irradiating ultraviolet light on the entire surface of the substrate to harden the sealant. In either case, it is desirable to heat the liquid crystal cell to the temperature of the liquid crystal isotropic, and then slowly cool to room temperature. The flow alignment at the time of liquid crystal injection is removed. Then, the liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. Here, when the liquid crystal alignment film is horizontally aligned, the liquid crystal alignment is formed by adjustment. In the two substrates of the film, the angle formed by the polarization direction of the irradiated linearly polarized light and the angle between each substrate and the polarizing plate can obtain a liquid crystal display element having a TN type or STN type liquid crystal cell. When the film has a vertical alignment property, the cells are formed in parallel with the direction of the axis which is easily aligned in the two substrates on which the liquid crystal alignment film is formed, and the polarizing plate is bonded thereto, and the polarization direction and the axis which is easily aligned are formed. A liquid crystal display element having a vertically aligned liquid crystal cell can be formed at an angle of °. The foregoing sealant can be used, for example, as a Alumina ball 30-201109367 of the separator and epoxy resin of the curing agent, etc. The liquid crystal is preferably, for example, a nematic liquid crystal, a smectic liquid crystal, or the like. When it is a TN type liquid crystal cell or an STN type liquid crystal cell It is preferable to use a nematic liquid crystal having a positive dielectric conductivity, and for example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, or a biphenyl cyclohexane system can be used. a liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, etc. Further, for example, cholesteryl chloride or cholesteryl phthalate may be further added to the liquid crystal. Cholesteric liquid crystal such as cholesteryl carbonate: a chiral reagent sold under the trade names "C-1 5", "CB-15" (manufactured by MerCk); p-oxybenzylidene-p-amino-2-yl A ferroelectric liquid crystal such as butyl cinnamate or the like. On the other hand, in the case of a vertical alignment type liquid crystal cell, a nematic liquid crystal having a negative dielectric conductivity is preferable, and for example, a dicyanobenzene liquid crystal, a germanium well liquid crystal, or a Schiff base liquid crystal can be used. An oxy-azo-based liquid crystal, a biphenyl-based liquid crystal, a phenylcyclohexane-based liquid crystal, or the like. The polarizing plate used for the outer side of the liquid crystal cell is a polarizing plate formed by stretching a polyvinyl alcohol and arranging a polarizing film called an "H film" which absorbs iodine with a cellulose acetate protective film. A polarizing plate formed by the diaphragm itself. The liquid crystal display element of the present invention thus produced is excellent in display performance, and the display performance is not deteriorated even when used for a long period of time. [Embodiment] -31 - 201109367 The present invention will be more specifically described by the following examples, but the present invention is not limited by these examples. The solution viscosity of the polymer and the ruthenium iodide ratio of the polyimine in the following synthesis examples were evaluated by the following methods, respectively. [Solid viscosity of the polymer] The solution viscosity (mPa.s) of the polymer was measured at 25 ° C for each polymer solution using an e-type rotational viscometer. <Rigmine imidization ratio of polyimine> A polyimine-containing solution obtained in each synthesis example was added in a small amount, poured into pure water, and the obtained precipitate was filtered to separate polyimine. The polyimine was sufficiently dried under reduced pressure at room temperature, and then dissolved in dimethyl hydrazine, and tetramethyl decane was used as a reference material, and 1 H-NMR measured at room temperature was used. The mathematical formula (1) is obtained.醯 imidization rate (XisO-AWA^cOxlOO (1) (In the mathematical formula (1), A1 is the peak area from the protons of the NH group appearing near l〇Ppm, and A2 is the peak area from other protons, α It is the ratio of the number of other protons to the proton of the sulfhydryl group in the precursor of one polyimine (polyproline). <Synthesis Example and Comparative Synthesis Example of Specific Polymer> Synthesis Example of Amine Acid] Synthesis Examples ΡΑ-1 to ΡΑ-24 and RPA-1 to RPA-6 The kinds and amounts of diamine and tetracarboxylic dianhydride shown in Table 1 were added to 135 g of hydrazine in this order. Dissolving in -methyl-2-pyrrolidone and forming a solution of the total weight of the diamine and the tetracarboxylic dianhydride from 1 〇 to 32 to 201109367% by weight based on the total weight of the reaction solution, at 60 ° The reaction was carried out for 6 hours under c' to obtain 15 0 g of a solution each containing 10% by weight of β-polyglycine (ΡΑ-1)~(ΡΑ-24) and (RPA-1)~(RPA-6). The obtained viscosity of each solution was combined and shown in Table 1. [Synthesis of Polyimine] Synthesis Examples PI-1-PI-18 and RPI-1 to RPI_6 The kinds and amounts of diamines shown in Table 2 were Tetracarboxylic dianhydride Adding to 135 g of N-methyl-2-pyrrolidone and dissolving 'and forming a total weight of diamine and tetracarboxylic dianhydride of 10% by weight relative to the total weight of the reaction solution, at 60 ° The reaction was carried out for 6 hours at C to obtain 150 g of a solution each containing 10% by weight of polylysine. The viscosity of each solution obtained here was combined and shown in Table 1. Next, these were each containing a poly-proline. In the solution, the amount of pyridine and acetic anhydride shown in Table 2 were added separately, and the dehydration ring-closure reaction was carried out for 4 hours at 110 ° C. After the dehydration ring-closing reaction, 'by using the new N-methyl solvent in the system Solvent replacement with keto-2-pyrrolidone (by this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction were removed to the outside of the system) to obtain 15% by weight of polyimine (PI-1)~(PI, respectively) -18) and (rpi-1) ~ (rpu) solution. The yield of each solution, respectively, a small amount of each solution was added to the N-methyl-2-indole diluted with D-butanone to 1% by weight, determined The solution viscosity and the ruthenium imidization ratio of each polyimine are shown in Table 2. -33- 201109367 Table 1 Diamine tetracarboxylic acid dianhydride polyamide acid synthesis type dosage type dosage name solution viscosity (g) (mole) (g) (mole) (mPas) PA-1 d-1 9.60 0.021 t-3 5.0 0.022 PA-1 22 d-17 0.42 0.001 PA-2 d-2 9.82 0.020 t-3 4.8 0.021 PA-2 24 d-17 0.41 0.001 PA-3 d-3 9.91 0.020 t-3 4.7 0.021 PA-3 d-17 0.40 0.001 19 PA-4 d-4 10.08 0.019 t-3 4.5 0.020 PA-4 22 d-17 0.38 0.001 PA-5 d-5 9.50 0.021 t-3 5.1 0.023 PA-5 23 d-17 0.43 0.001 PA-6 D-6 10.32 0.018 t-3 4.3 0.019 PA-6 17 d-17 0.37 0.001 PA-7 d-6 10.28 0.018 t-3 4.3 0.019 PA-7 24 dl 6 0.42 0.001 PA-8 d-7 10.02 0.019 t- 3 4.6 0.020 PA-8 20 d-17 0.39 0.001 PA-9 d-7 9.98 0.019 t-3 4.6 0.020 PA-9 21 dl 6 0.44 0.001 PA-10 d-8 12.03 0.012 t-3 2.7 0.012 PA-10 22 D-17 0.23 0.001 PA-11 d-8 12.01 0.012 t-3 2.7 0.012 PA-11 20 d-16 0.26 0.001 PA-12 d-9 10.11 0.019 t-3 4.5 0.020 PA-12 20 d-17 0.38 0.001 PA -13 d-9 10.07 0.019 t-3 4.5 0.020 PA-13 17 dl 6 0.44 0.001 PA-14 d-10 10.40 0.018 t-3 4.2 0.019 PA-14 24 d-17 0.36 0.001 PA-15 d-10 10.36 0.018 t-3 4.2 0.019 PA-15 dl 6 0.41 0.001 20 -34- 201109367 Table 1 (Continued) Synthesis Example Diamine Tetracarboxylic Acid Dehydride Polyamine Acid Type Dosage Type Name Solution Viscosity (mPa*s) (g) (mole) (g) (mole) PA-16 d-11 12.16 0.011 t-3 2.6 0.012 PA-16 20 d-17 0.22 0.001 PA-17 d-12 11.94 0.012 T-3 2.8 0.013 PA-17 16 d-17 0.24 0.001 PA-18 d-13 12.03 0.012 t-3 2.7 0.012 PA-18 23 d-17 0.23 0.001 PA-19 d-14 10.61 0.017 t-3 4.0 0.018 PA -19 21 d-15 0.41 0.001 PA-20 d-14 10.63 0.017 t-3 4.0 0.018 PA-20 22 d-16 0.39 0.001 PA-21 d-14 10.66 0.017 t-3 4.0 0.018 PA-21 16 d-17 0.34 0.001 PA-22 d-14 10.33 0.016 t-3 4.1 0.018 PA-22 19 d-16 0.40 0.001 d-19 0.19 0.001 PA-23 d-14 10.36 0.016 t-3 4.1 0.018 PA-23 21 d-17 0.35 0.001 d-19 0.19 0.001 PA-24 d-14 10.66 0.017 t-3 4.0 0.018 PA-24 22 d-18 0.34 0.001 RPA-1 d-6 10.23 0.018 t-3 4.3 0.019 RPA-1 18 d-20 0.50 0.001 RPA-2 d-7 9.92 0.019 t-3 4.5 0.020 RPA-2 21 d-20 0.53 0.001 RPA-3 d-8 11.97 0.012 t-3 2.7 0 .012 RPA-3 17 d-20 0.32 0.001 RPA-4 d-9 10.01 0.019 t-3 4.5 0.020 RPA-4 21 d-20 0.52 0.001 RPA-5 d-10 10.31 0.018 t-3 4.2 0.019 RPA-5 16 D-20 0.49 0.001 RPA-6 d-14 10.57 0.017 t-3 4.0 0,018 RPA-6 23 d-20 0.46 0.001 -35- 201109367 醯i-imidized polymer solution viscosity (mPa*s) ο CN (N 〇〇 VO (N 醯 imidization rate (%) Ό \ v〇IT) 〇〇 <N g wi solution yield (g) ^•Η etc. rH and other names PI-1 ΡΙ-2 PI-3 PI-4 PI- 5 PI-6 PI-7 PI-8 1 PI-9 Dehydrating agent · Dehydration ring closure catalyst dosage (g) 1.96 . 1 1.52 3.92 3.03 2.08 1.62 4.17 3.23 1.24 0.96 2.48 1.92 2.05 On 4.09 3.17 m as 1 1.49 Type of acetic anhydride batch Steep 1 acetic anhydride pyridine acetic anhydride pyridine 1 acetic anhydride 1 D ratio steep 1 acetic anhydride 1 pyridine acetic anhydride lysate acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine poly-proline acid solution viscosity (mPas) <N 00 oo IT) Tetracarboxylic acid dianhydride rm rm (mole) 0.019 0.019 0.020 0.020 0.012 0.012 0.020 0.020 — 0.019 nt 3 rn Γ〇 — v〇 — vq — 卜 CN r- (N inch (N — type ΓΟ cn CO rn r n rn CO ΓΛ Diamine dosage (mole) 0.018 0.001 0.018 0.001 0.019 0.001 0.019 0.001 0.012 0.001 0.012 0.001 0.019 0.001 0.019 0.001 0.018 0.001 3 10.3 ο 10.3 ο 10.0 inch Ο 10.0 inch ο 12.0 md 12.0 rn o rH oo 10.1 ^ro 10.4 inch ο Type Ό 4 d-16 ο d-16 卜 d-16 卜"O d-16 00 d-16 00 T5 d-16 〇\ d-16 On "6 d-16 d-10 d- 16 Synthesis Example ΡΙ-1 _ί ΡΙ-2 PI-3 PI-4 PI-5 PI-6 PI-7 PI-8 PI-9 201109367 醯i-imidized polymer solution viscosity (mPas) 00 卜 (N < N Bu 〇醯 imidization rate (%) § !〇§ *T) !〇<N solution yield (g) o TH name PI-10 PI-11 PI-12 PI-13 PI-14 PI-15 PI-16 I PI-17 1 PI-18 Dehydrating agent · Dehydration closed-loop catalyst _ 2 00 rn 00 α\ CS (Ν ΟΟ CO OO (N (N OO t-H (N oo <N VO v〇cn cn ( N 00 in v〇cn CM oo <N m «K1S Umil w acetic anhydride acetic anhydride m acetic anhydride n acetic anhydride acetic anhydride m acetic anhydride m acetic anhydride n acetic anhydride m solution viscosity of m-acetic acid poly-proline (mPa -s) Ο oo oo v〇tetracarboxylic dianhydride _ πρ (mole 9 18 18 18 18 18 18 18 18 _ 旺 (莫耳) 0.018 0.001 : 0.017 0.001 0.017 0.001 0.017 0.001 0.017 0.001 0.016 0.001 0.016 : 0.001 0.017 0.001 0.017 0.001 3 ο » * - Η inch d νο Ο inch dv 〇〇 inch d 〇 〇 rO d ddmd inch ο Cn 〇 inch d 卜dm 〇d d de de Ο ο Χ Χ ί v〇1-H T3 inch V〇T5 inch π3 inch"6 inch T3 VO inch*0 inch XJ 00 xi -^r tj 00 T3 1 Synthesis Example PI 1 PI-11 PI-12 PI-13 PI-14 PI-15 PI-16 PI-17 PI-18 201109367 醯 imidized polymer solution viscosity (mPas) m (N (N (N o < N 醯 imidization rate (%) in 〇\ oo solution yield (g) 〇\ 〇\ name RPI-1 RPI-2 RPI-3 RPI-4 1 RPI-5 RPI-6 m Dosage (g) 1.95 2.07 1.61 1.24 0.96 2.04 1.58 ON 1.48 1.81 1 ! 1.40 笺S w acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine poly-proline acid solution Degree (mPas) i _1 ίΝ 〇 \ tN 卜 m < N tetracarboxylic dianhydride dosage (mole) 0.019 0.020 0.012 0.020 1 0.019 0.018 3 ΓΛ inch i〇 inch r- <N CN Tf o — category_1 ΓΟ rn ro diamine dosage (mole) 0.018 0.001 0.019 0.001 0.012 0.001 0.019 0.001 0.018 0.001 0.017 0.001 3 10.2 d On 〇\d 12.0 mo 10.0 o 10.3 o 10.6 o Type VO d-20 Divination d-20 00 T3 d -20 On *〇d-20 1 1 d-10 1 d-20 d-14 d-20 Synthesis Example RPI-1 RPI-2 RPI-3 RPI-4 RPI-5 RPI-6

Oo CO 201109367 In addition, the abbreviations of diamine and tetracarboxylic dianhydride in Tables 1 and 2 are as follows. [Diamine] First diamine d-15: Compound d-16 represented by the above formula (A-1-1): Compound d-17 represented by the above formula (A-1-2): Compound d-18 represented by A-1-3): a compound represented by the above formula (A-1-4): a second diamine d-Ι : represented by the above formula (A-2-1-1) Compound d-2: Compound d-3 represented by the above formula (A-2-1-2): Compound d-4 represented by the above formula (A-2-1-3): the above formula (A-2- 1-4) Compound d-5 shown: Compound d-6 represented by the above formula (A-2-2-1): Compound d-7 represented by the above formula (A-2-1-5): Compound d-8 represented by the above formula (A-2-1-6): Compound d-9 represented by the above formula (A-2-1-7): the above formula (A-2-1-8) The compound d-oxime represented by the above formula (A-2-1-9): d-oxime represented by the above formula (A-2-1-10): the above formula (A- Compound d-13 shown in 2-1-11): Compound d-14 represented by the above formula (A-2-1-12): Compound -39 represented by the above formula (A-2-1-13) - 201109367 The third diamine 0-19:11 diallyl-2,4-diaminoaniline fourth diamine d-20: 3,5-diaminobenzoic acid cholesteryl ester [four Carboxylic dianhydride] t-Ι : 3,5,6-tricarboxy-2-carboxymethylnorbornane - 2:3,5:6 · dianhydride t-2 : 2,4,6,8 - Tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride t-3: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride <Synthesis example of other polymers> [Synthesis of Other Polylysine] Synthesis Example OPA-1 98 g (0.50 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 110 g (0.50 mol) as tetracarboxylic dianhydride ) pyrethic acid dianhydride and 200 g (1.0 mol) of 4,4'-diaminophenylmethane as a diamine dissolved in 230 g of N-methyl-2-pyrrolidone and γ-butane In a mixed solvent of 210 μg of the ester, after reacting at 40 ° C for 3 hours, 1,350 g of γ-butyrolactone was added to obtain 10% by weight of polyglycine (ΟΡΑ-1). The solution. The solution viscosity of the polylysine solution was 125 mPa*s. Synthesis Example -PA-2 will be 200 g (1.0 mol) of tetracarboxylic dianhydride, 2,3,4-cyclobutanetetracarboxylic dianhydride and 210 g (1.0 mol) of diamine as a diamine. 2,_Dimethyl_4,4|_diaminobiphenyl dissolved in a mixed solvent composed of 3 70 g of N-methyl-2-pyrrolidone and 3 3 00 g of γ-butyrolactone By reacting 3 hours 201109367 at 40 ° C, a solution containing .10% by weight of polyaminic acid (OPA-2) was obtained. The solution viscosity of the polyaminic acid solution was 160 mPa_s. Example 1 I. Preparation of Liquid Crystal Aligning Agent A polyglycine (PA-1)-containing solution obtained in the above Synthesis Example PA-1 as a polymer and a polydecylamine obtained in the above Synthesis Example OPA-1 A solution of acid (OPA-1) mixed with poly-proline (PA-1): poly-proline (OPA-1) = 20:80 (by weight), to which γ-butyrolactone (BL) is added. , Ν-methyl-2-pyrrolidone (ΝΜΡ) and butyl 赛路苏 (BC), fully stirred to form a solvent composition of BL: NMP: BC = 30:20:50 (weight ratio), solid concentration It is a 3% by weight solution. This solution was filtered through a filter having a pore size of 1 μη to prepare a liquid crystal alignment agent. II. Production of Liquid Crystal Cell The liquid crystal alignment agent prepared above was applied on a transparent electrode surface of a glass substrate having a transparent electrode composed of a film of I Τ 0 by a spin coating method on a hot plate at 8 ° C. After heating for 1 minute (prebaking), the solvent was removed, and the mixture was heated in a 200 t oven purged with nitrogen in a box for 40 minutes (post-baking) to form a coating film having an average film thickness of 1,000 people. Next, a Hg-Xe lamp and a Glan-Taylor prism were used on the surface of the coating film, and the substrate was inclined at 40 from the substrate normal. In the direction, a polarized ultraviolet line containing a bright line having a wavelength of 3 丨 3 nm was irradiated at 200 J/m 2 to impart alignment property to the liquid crystal to form a liquid crystal alignment film. The same operation was repeated to manufacture a pair of (two pieces) substrates having a liquid crystal alignment film. On the periphery of a surface of the above-mentioned substrate having a liquid crystal alignment film, -41 - 201109367 by epoxy printing an epoxy resin binder having a diameter of 5.5 μm by adding a pair of substrates The liquid crystal alignment film was placed facing each other, and the optical axis of the ultraviolet light of each substrate was pressed against the projection direction of the substrate surface in antiparallel, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, from the liquid crystal injection port, a negative liquid crystal (manufactured by Merck, MLC-6608) was filled in the gap between the substrates, and then the liquid crystal injection port was sealed with an epoxy adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, the liquid crystal cell was produced by heating it to 120 ° C and slowly cooling to room temperature. The liquid crystal cell was evaluated for the liquid crystal alignment 'pretilt angle and voltage holding ratio by the following methods, respectively. The evaluation results are shown in Table 3.评价. Evaluation of liquid crystal cell (1) Evaluation of liquid crystal alignment property When the 5 V voltage is turned ON/OFF (applied and released) at 25 ° C by a polarizing microscope, there is an abnormal region. The case where there is no abnormal region was evaluated as "good" liquid crystal alignment. (2) Evaluation of the pretilt angle according to Non-Patent Document 2 (TJ Scheffer et. al., J. Appl. Phys. v〇l' 48, P 1 783 (1 977)) and Non-Patent Document 3 (F. Nakano, The method described in et. al., JPN. J. Appl. Phys. vol. 19, p. 2013 (1980)) measures the pretilt angle by a crystal rotation method using He-Ne laser. (3) Evaluation of light resistance The liquid crystal cell produced above was subjected to "VHR-1" manufactured by TOYO Technica Co., Ltd., and measured at 701: when applied at 60 microseconds - 42 - 201109367, 167 milliseconds After a voltage of 5 V was applied to the interval, the voltage holding ratio (initial voltage holding ratio (VHIN) was 167 milliseconds after the application was released. Then, a weather resistance meter using a carbon arc as a light source was used for the liquid crystal cell, and 5,000 was performed. After the light is irradiated for a small period of time, the voltage holding ratio (the voltage holding ratio (VHAF) after the irradiation is measured again by the same method as above in the liquid crystal cell after the light irradiation. At this time, the rate of retention of the voltage holding ratio ((VHAF)) When (VHIN) is 90% or more, the light resistance is "good", and when it is less than 90%, the light resistance is "not good". (4) Evaluation of residual DC voltage For the liquid crystal cell produced above, A rectangular wave of 30 Hz and 3 V with a direct current of 5 V was applied for 2 hours at an ambient temperature of 60 ° C, and the voltage remaining in the liquid crystal cell (residual DC voltage) immediately after the DC voltage was cut was obtained by a flash elimination method. This is an indicator of the afterimage characteristics, which is about 150m. When it is V or less, it is said that the image sticking property is good, and when it is about 50 mV or less, it is called the image sticking characteristic especially. Example 2 - 51 and the comparative example 1 - 12 In addition to the Example 1, the use as a polymer. In the same manner as in Example 1, a liquid crystal alignment agent was prepared in the same manner as in Example 1, and liquid crystal cells were produced and evaluated. The evaluation results are shown in Table 3. -43- 201109367 ε撇 Liquid crystal cell residual DC voltage (mV) vn Os On gov£) v〇00 v〇v〇v〇iTi oo Vi m CN Η CN (N Os cs sr—lightfastness maintenance rate (VIWVHd^) (%) Art (N ON Os m ON cn Os 5; cn 〇\ m On CN Os Os ON Guest CS ON 5^ <N Os ΓΛ Os 落 ^ ^tf Ml· S 织j 陛> m an Os inch rn 〇\ (N Os (N 〇\ cn oi as CN &lt ;N ON <N Os CN tn (N On r- cn Os 窆rn On oo CN ON Ο 00 in ύ ir» cn ON Γ-* cn Os Initial voltage retention rate VHm(%) to On as cs σ; ON CN σ; 〇\ 寸 Os ON 〇\ OS v〇〇\ OS o 〇\ Os 〇\ ON m O; os 〇On ON Ό ON Os 〇\ as cn Os cK On CM On On 〇 〇 \ Os 〇\ 〇 \ νη cK OS in O; OS v〇On ON Pretilt angle (°) ss ss ss o 00 ON 00 ON 00 ON 00 Os 00 Ov 00 On 00 On 〇〇On oo 〇\ oo Os 00 ON 00 〇\ oo Os 00 Os 00 LCD alignment 1 good 1 丨 good 1 1 good I 1 good 1 1 good 1 1 good 1 1 good 1 & -13⁄4 1 good 1 1 good 1 1 good 1 1 good 1 1 good 1 & 1 good 1 1 good 1 1 good 1 1 good 1 i good 1 good" Other polymers for the preparation of liquid crystal alignment agents § ιΜ _ _ g § § gg § § gg 〇〇o 〇om *MS tlmi foot OPA-1 | OPA-1 1 | OPA-1 | OPA -1 | OPA-1 1 | OPA-2 I OPA-2 OPA-2 | OPA-2 1 | OPA-2 1 | OPA-2 1 | OPA-2 1 | OPA-2 1 | OPA-2 1 l OPA -2 1 1 1 1 1 1 械 i: § μ nim «1 〇〇o 〇ooo Usui w PA-1 PA-2 PA-3 PA-4 PA-5 PA-6 PA-7 PA-8 PA- 9 PA-10 PA-11 PA-12 PA-13 PA-14 PA-15 I PA-16 I PA-17 PA-18 PA-19 PA-20 Example 1 Example 2 Example 3 Example 4 Example 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 - inch inch - 201109367 (嗽)) 撇 LCD cell 〇 Q i!! > 1® to S mm in m vn (S Ο vn (N ^r> OO Ο (N m 00 o lightfast) Sex maintenance rate (VHaf/VHin) (%) S falls S: <N as o 〇\ S Os (N 〇\ cs Q\ CN <N Os heart Os On 5; δ; ϋ褂邑陛> ( N 00 (T; 〇\ (N 〇sov〇5: 00 On 00 ON κη «r; Os Ό rn ON »~·Η rn 〇\ (N σ\ 窆(N ON CN έ 〇 inch〇 § 卜 rn Os inch initial voltage retention rate VH!n(%) ma; a\ κη a; Os cK ON (N σ; Os <N σ; as 〇〇\ m 〇\ as as 〇\ 〇〇\ a\ On Cs VO Os 〇\ m σ; Os 卜 Os On (N σ; On 寸 On On 〇〇\ 〇\ »—Η as 〇\ 〇\ κη c> 〇\ inch〇\ OS ^r Os 〇\ pretilt angle (° 〇\ OO s ON 00 s Os OO 00 00 00 00 OO OO 〇〇00 OO OO 00 00 〇〇OO 〇〇00 〇〇〇〇OO 〇〇00 OO 00 00 00 00 00 00 00 00 00 00 00 LCD Orientation & -13⁄4 &&&&&&&&&&&&&&&&&&&&&&&&& Polymers used in polymers other polymers § dM i|〇i _ § § § g § g S § § g § § § § t<mti w 1 OPA-2 1 1 OPA-2 | 1 OPA-2 1 OPA-2 OPA-2 1 OPA-2 1 | OPA-2 | 1 OPA-2 1 | OPA-2 1 | OPA-2 | | OPA-2 I 1 OPA-2 | 1 OPA-2 | OPA-2 1 OPA-2 1 | OPA-2 1 | OPA-2 1 | OPA-2 1 | OPA-2 1 L〇pa-2 I OPA-2 Specific polymer or its comparative polymer § _ η ΐϋ ogom Umij _ PA- 20 PA-20 1 PA-20 1 I PA-20 I PA-21 PA-22 PA-23 t CN t CO έ inch ά s Ό i OO έ Os (3⁄4 PI-10 PI-11 PI-12 PI-13 PI-14 Embodiment 22 Embodiment 23 Embodiment 24 Embodiment 25 Embodiment 26 Embodiment 27 Embodiment 28 Embodiment 29 Embodiment 30 Embodiment 31 Embodiment 32 Example 33 Example 34 Example 35 Example 36 Example 37 Embodiment 38 Embodiment 39 Embodiment 40 Embodiment 41 Embodiment 42 -^- 201109367 (撇籴) ε嗽 liquid crystal residual DC voltage (mV) 〇CN VO v〇v〇cn 〇\ m <N cn OO V〇v〇oo OS in m OO τ—« m 3 〇\ Lightfastness maintenance rate (VHaf/VHTM) (%) m Os CO On 卜Os σ\ 〇\ ΓΟ to oo (N 00 00 00 00 Os 00 VO 00 00 00 Ό 00 (N 00 voltage holding ratio vhaf (%) after irradiation <N Os inch CN σ\ <N ON in v〇Q\ v〇έ 2 σ\ o 〇\rj 〇\ On ... 00 On oo § o ss (N g IT) od oo CO ... OO ss On ... 00 00 rn 00 00 00 Initial voltage retention ΥΗπ^ί%) Ο αί Os <J\ CO a; 〇\ V〇〇\ 〇\ <N <> ON On Os in a; On (N cK ON O 〇\ 〇\ fN 〇\ a\ CS 〇< On CM 〇\ inch 〇\ 〇\ *Ti Os a\ us a; On inch On Os (N On vs σ\ On fS cK ON inch ON Os CO 〇< On ΟΟ 00 00 00 〇〇oo 00 00 OO 00 00 00 On oo 00 00 00 00 Os oo On oo 〇\ 00 ON 00 Os oo σ\ OO 00 oo 00 00 00 00 00 00 00 00 00 00 Liquid Crystal Alignment & Good Good & Good Good Good Good Good Good Good Good Good & Good Good Good Good and good preparation of polymers for liquid crystal alignment agents. Other polymers § __ « § oggg § g § § § § gggggg Type 0ΡΑ-2 丨1 OPA-2 1 丨 OPA-2 1 | OPA-2 1 | OPA- 2 1 | OPA-2 | | OPA-2 | | OPA-2 | | OPA-2 1 OPA-2 | OPA-2 | ! OPA-2 1 OPA-2 OPA-2 OPA-2 OPA-2 OPA-2 OPA-2 OPA-2 OPA-2 OPA-2 Age Pine 4Π 4π齩mm Bully $ φ|ιιΜ _ o Type PI-14 PI-14 PI-14 PI-14 PI-15 PI-16 PA-24 PI-17 PI-18 RPA-1 RPA-2 RPA-3 | RPA-4 ! RPA-5 RPA-6 RPI-1 RPI-2 RPI-3 RPI-4 RPI-5 RPI-6 1 Embodiment 43 丨 Example 44 I Embodiment 45 Example 46 Example 47 1 Example 48 1 Example 49 1 Example 50 1 Example 51 Comparative Example 1 "Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 1 Comparative Example 11 Comparative Example 12 • 9 inch — 201109367 [Simple diagram description] te 〇/>\\ [Main component symbol description] 〇 / » -47

Claims (1)

201109367 VII. Patent application scope: 1. A liquid crystal alignment agent comprising polyphthalic acid selected from the reaction of tetracarboxylic dianhydride and diamine, and polypyridae formed by dehydration of the polyamic acid. At least one polymer of the group consisting of amines, wherein the diamine comprises a first diamine and a second diamine having a photoreactive structure, the first diamine being represented by the following formula (A-0) , H2N\/==\ X^Ring^x-·-Ring2^-CcHaFp _ (A-0) In the formula (AO), X1 represents a single bond 'methylene group, and the alkyl group having 2 or 3 carbon atoms ' *-〇_ ' * - C 00- ' * - Ο C Ο - ' * - X, -R 1 -, * - R 1 - X ' - or where X' means +_〇_, +- COO- or +-OCO-, where "+" means that the bond with it is in the left direction toward the formula (A-Ο), and R1 is an alkyl group having a carbon number of 2 or 3, respectively, with a "connection" The bond is bonded to a diaminophenyl group, and Ring1 and Ring2 are each independently a cyclohexyl group or a phenyl group, and X" is a single bond, +-〇-, +-C00_ or +_〇C〇-, wherein The connection key with it is directed to the left direction of the direction (A-o), a is 0 or 1 b is an integer of 0 to 3, and when b is 2 or more, a plurality of X's and Ring2 existing may be the same 'may be different', and when a is 0, the leftmost X' of the formula (A_0) is a single bond. 'c is an integer from 0 to 20, and α and β are integers of 〇~2c+l, respectively, where a + f = 2c + l, and a + b = 〇, c is not 〇. -48- 201109367 2 . The liquid crystal alignment agent of claim 1 of the patent scope, wherein the first one is selected as »οι The CcH2c+1 diamine is a compound h2n (A-1) h2n represented by the following formula (A-1). In the formula (A-ι), X1 is *-〇-, *-C〇〇- or *-〇C 〇_, wherein the bond of the band is bonded to the diaminophenyl group, & is 0 or 1 'b is an integer of 0 to 2, and c is an integer of 1 to 20. 3. The liquid crystal alignment agent of claim 1 wherein a + b is an integer of 2 to 4 in the above formula (A - 0). 4. The liquid crystal alignment agent of claim 2, wherein in the above formula (A-1), a + b is 2 or 3. The liquid crystal alignment agent of any one of the above-mentioned second diamines, wherein the photoreactive structure in the second diamine is a structure represented by the following formula (A_2), (A-2) In the formula (A-2), d is 0 or 1, and A1 and A2 are each an alkyl group having a carbon number of 1 to 6, an alkoxy group having a carbon number of 1 to 6 or a halogen atom or a cyano group. , 6 and f are integers of 0 to 4, respectively, and "+" represents a connection key. 6. The liquid crystal alignment agent of claim 5, wherein the structure represented by the above formula (A-2) is selected from the structures represented by the following formulas (A-2-1) and (A-2-2), respectively. At least one structure, -49- 201109367 ^-x11—(Rm)hj—(X1,,)J——R1 (A-2-1) rh 十 χπ (A-2-2) In the formulas (A-2-1) and (A-2-2), A1, A2, d, e, and f are the same as defined in the above formula (A-2), respectively, and R1 and R11 is an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 4 to 30 carbon atoms having an alicyclic structure, and X11 and X111 are -0-, -CO-, respectively. , -CO-O-, -O-CO-, -NR-'-NR-CO-, -CO-NR-, -NR-CO-O-, -0-C0-NR-, -NR-CO- NR- or - O-CO-O-, wherein R is a hydrogen atom or an alkyl group having a carbon number of 1 to 4, and Rm is a methylene group, an aryl group, a divalent alicyclic group, and -Si (CH3), respectively. 2, -CH = CH- or - C=C-' wherein one or more of the hydrogen atoms possessed by Rni may be substituted by a cyano group, a halogen atom or an alkyl group having 1 to 4 carbon atoms. h is an integer of 1 to 6, and i is an integer of 0 to 2. When a plurality of the above X11 and Rm are present, they may be the same or different, j is 0 or 1, and "+" represents a connection key. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the tetracarboxylic dianhydride comprises a compound selected from the group consisting of 2,3,5-tricarboxycyclopentylacetic acid 2, 201109367, 3, 5, 6-Tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride and 2,4,6,8-tetracarboxybicyclo[3.3.0]octane_2:4,6: At least one of the groups consisting of 8-dianhydride. The liquid crystal alignment agent of any one of the first to fourth aspects of the invention, wherein the diamine further comprises a third diamine represented by the following formula (A-3). In the formula (A-3), R111 is each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and RIV and Rv are each independently a hydrogen atom or a methyl group. The liquid crystal alignment agent according to any one of claims 1 to 4, further comprising a polyamic acid selected from the group consisting of a tetracarboxylic dianhydride and a diamine not containing the second diamine. At least one polymer of the group consisting of polyamidene formed by dehydration of the polyamic acid. A liquid crystal alignment film comprising a liquid crystal alignment agent according to any one of claims 1 to 9 of the invention. A liquid crystal display element comprising the liquid crystal alignment film of claim 10 of the patent application. 12. A poly-proline acid obtained by reacting a tetracarboxylic dianhydride with a diamine, wherein the diamine comprises a first diamine represented by the above formula (A-0) and having light A second diamine of reactive structure. 13. A polyimine which is formed by dehydration of a polyamic acid which is obtained from a tetracarboxylic dianhydride and a diamine trans-51-201109367, wherein the diamine comprises the above formula (A) -0) a first diamine as shown and a second diamine having a photoreactive structure. -52- 201109367 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: