TWI293392B - - Google Patents

Description

1293392 A7 B7 Ministry of Economic Affairs Intellectual Property Office Employees Consumer Cooperatives Printing V. INSTRUCTION DESCRIPTION (1) [Technical Field of the Invention] The present invention relates to a liquid crystal aligning agent for inkjet printing. More specifically, a liquid crystal aligning agent which exhibits excellent coating stability and film thickness uniformity when applied to a substrate by an inkjet printing method. [Prior Art] At present, a liquid crystal alignment film made of polyimide is formed on the surface of a substrate provided with a transparent conductive film to form a substrate of a liquid crystal display element, and the two sheets are disposed opposite to each other and in the gap therebetween. A so-called TFT liquid crystal panel which forms a layer of a liquid crystal to form a unit of a sandwich structure and is driven by a TFT (Thin Film Transistor) is being widely used in place of the conventional Braun tube monitor. In the liquid crystal display device, it is known that a positive dielectric anisotropic liquid crystal is used as the liquid crystal, and the long axis of the liquid crystal molecules can be continuously twisted by 90 degrees from one substrate to the other substrate. Twisted Nematic, TN type liquid crystal display element of a twisted nematic liquid crystal cell. Further, an STN (Super T wisted Nematic) type liquid crystal display element having a higher contrast ratio (c ο ntrast ) than a TN type liquid crystal display and having a low viewing angle dependency, or a vertical alignment liquid crystal has been developed. Display component. The STN type liquid crystal display element is used as a liquid crystal in a counter-type liquid crystal display in which a Chiral agent which is itself an optically active substance is used, and the long axis of the liquid crystal is used to cover 180 degrees between the substrates. The birefringence effect produced by the above continuous twisting state. In these liquid crystal display elements, the person who controls the orientation of the liquid crystal is (please read the precautions on the back side and then fill in this page). The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- 1293392 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Invention description (2) Liquid crystal alignment film. The liquid crystal alignment film is a liquid crystal aligning agent which is a polyimine acid solution which is a precursor of polyimine or a solvent-soluble polyimine solution, and is coated on a substrate by an aniline printing method, and This was fired to form a resin film, and the liquid crystal orientation energy was imparted thereto. However, in recent years, the inkjet printing method has been attracting attention because the aniline printing method requires a printing plate or the like in accordance with the substrate condition, and the troublesome problems such as the maintenance of the printing plate are highlighted. In the case of inkjet printing, since the printing plate does not require maintenance, the printing pattern can be freely set, and only a small amount of the liquid crystal aligning agent is required, and the cost reduction of the liquid crystal panel and the improvement of the yield can be expected. [Problems to be Solved by the Invention] As the liquid crystal aligning agent, in addition to the alignment regulating force of the liquid crystal, 尙 requires performances such as voltage holding characteristics, afterimage characteristics, and reliability. Further, depending on the type of the liquid crystal display element, an arbitrary pretilt angle (the tilt angle of the liquid crystal molecules to the substrate) is required. Further, in the ink jet printing method, it is necessary to eject the liquid crystal aligning agent at a high speed from a fine nozzle, and the viscosity characteristics of the liquid crystal aligning agent become an important factor. That is, when a strong external force is applied to the solution, it is necessary to have a low impedance and be superior to the fluidity. Further, in order to control the shape of the droplets after the ink is applied to the substrate, the surface tension and viscosity characteristics of the solution will become important factors. If these factors are controlled to be appropriate, the surface uniformity of the film after firing can be ensured, and a liquid crystal alignment film having stable properties can be obtained. The liquid crystal aligning agent is required to control the film thickness after firing according to the purpose and purpose. As the film thickness control, the Chinese National Standard (CNS) A4 specification (210X 297 mm) is applicable to the paper scale (please read the back note first) Fill in this page again) 1293392 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printing V. Invention Description (3) One of the laws, which can be adjusted for the concentration of solid components. The control of the concentration of solid components usually affects the viscosity characteristics and surface tension characteristics, so it is necessary to adjust the solid content concentration while maintaining these characteristics. Further, in the case of the nozzle member used for ink jet printing, some of the organic materials are used, and the liquid crystal aligning agent does not attack the organic material, which is also an important factor. Therefore, it is necessary to reduce the solvent content of a solvent having a high solubility such as N-methylpyrrolidone used as a solvent for a liquid crystal aligning agent, and it is necessary to use a polymer having good solubility and having the above-described viscosity characteristics and surface tension characteristics. From the above, in the present invention, a liquid crystal directional agent excellent in discharge stability in an ink jet printing apparatus is successfully produced by using a polymer having a specific structure and controlling the solid content concentration, viscosity characteristics, and surface tension characteristics. That is, an object of the present invention is to provide a liquid crystal aligning agent which is excellent in the performance of the liquid crystal alignment film, the discharge stability, the performance stability of the liquid crystal alignment film, and the stability to the ink jet apparatus. Other objects and advantages of the invention will be apparent from the description which follows. [Means for Solving the Problems] According to the present invention, the above objects and advantages of the present invention can be made up of a liquid crystal aligning agent characterized by containing a repeating unit represented by the following formula (I-1) and The polymer component of at least one of the repeating units represented by the formula (1-2) and the solvent are obtained. (Please read the notes on the back and fill out this page.) This paper scale applies to Chinese national standards (CNS > A4 specifications (210X297 mm)

1293392 A7 B7 V. Description of invention (4)

HOOC COOHp〆 HNOC CONH —Q1·

1-1)

(wherein P1 is a tetravalent organic group and Q1 is a divalent organic group Q 0

0 〇v Λ (I 2) (Please read the notes on the back and fill out this page) Printed by the 8th Industrial Consumers Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs (where Ρ2 is the organic base of 4 and Q2 is 2 Organic Group.) [Embodiment of the Invention] Hereinafter, the present invention will be described in detail. The liquid crystal aligning agent of the present invention is one which is obtained by dissolving the above polymer component in a solvent. The polymer component of the present invention may be a polyaminic acid having a repeating unit represented by the above formula (1-1), and having a repeating unit represented by the above formula (?_2). a block copolymer of a proline prepolymer having a repeating unit represented by the above formula (1-1) and a quinone polymer having a repeating unit represented by the above formula (1-2) Alternatively, these may be used alone or in combination of two or more. When two or more types are used in combination, it is preferred to mix the polyproline and the ruthenium iodide polymer to use the technology to treat the sore ice 圃 圃 进 ( ( (CNS) Μ specifications (210X297 mm) 1293392 Ministry of Economics wisdom Property Bureau employee consumption cooperative printing A 7 _______B7_5, invention description (5) In the above 1, polyproline can be obtained by reacting tetracarboxylic dianhydride with diamine, and the ruthenium iodide polymer can be made The above polyglycolic acid is dehydrated and closed to obtain. Here, the ruthenium iodide polymer may be a repeating unit having no 100% dehydration ring closure, or may be a ratio of repeating units having a quinone ring in a total repeating unit (hereinafter, referred to as "imidization ratio"). ) is below 100%. <Tetracarboxylic acid dianhydride> Specific examples of the tetracarboxylic dianhydride used for the synthesis of polyproline are, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 -Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3 -dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic acid Acid dianhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2.3.5-tricarboxycyclopentyl acetic acid dianhydride , 3,5,6-tricarbonyl-2-carboxynorbornane-2 : 3,5 : 6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3&amp; 4,5,9 hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthoquinone [ l,2-c]furan-1,3-dione, l,3, 3a,4,5,9b-hexahydro-5-methyl-5(tetrahydro-2.5-dioxo-3-furanyl)-naphtho[1,2-(:]-furan-1,3- Diketone, l,3,3a,4,5,9b-hexahydro-5-ethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2 -c]-furan-1,3-dione, 1,3,3&amp;,4,5,9-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furan -Naphtho[l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5 -dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-7-ethyl (please Read the notes on the back and fill out this page.) This paper scale is used in China National Standard (CNS) A4 size (210x297 mm) 1293392 A7 B7 V. Description of invention (6) Base-5 (tetrahydro-2,5- Dioxo-3-furanyl)-naphtho[l,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3·furanyl)-naphtho[l,2-c]-furan-1,3-dione, l,3,3a,4,5,9b-six Hydrogen-8-ethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]-furan-1,3-dione, l,3,3a ,4,5,9b-hexahydro-5,8-dimethyl-5(tetrahydro-2,5-dioxo-8-furanyl)-naphtho[l,2-c]-furan-1 , 3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]- Octene 2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5 '-Dione), an alicyclic tetracarboxylic dianhydride represented by the following formulas (I) and (II); I---1^---^^^^ (Please read the back note first) Fill in this page again)

(I) Printed by the Intellectual Property Office of the Ministry of Economic Affairs

II (wherein R3 and R5 represent a divalent organic group having an aromatic ring, R4 and R6 represent a hydrogen atom or an alkyl group, and a plurality of existing R4 and R6 may be respectively applied to the Chinese National Standard (CNS) A4 for this paper size. Specification (210X297 mm) -10- 1293392 V. Description of the invention (same or different.) Aliphatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride; (Please read the notes on the back and fill in the form) Page) Pyromellitic dianhydride, 3,3,,4,4,_diphenyl ketone tetracarboxylic dianhydride, 3'3,4,4, biphenyl terephthalic acid dianhydride, 1,4 , 5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3,4,4,biphenyl ether tetracarboxylic dianhydride, ·3,3' ,4,4, dimethyldiphenylnonane tetracarboxylic dianhydride,-3,3',4,4' tetraphenyl economic ministry intellectual property bureau employee consumption cooperative printing sand yard tetracarboxylic dianhydride, hydrazine '2,3,4•furan tetracarboxylic dianhydride, 4,4, ·bis(34-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'...bis(3,4-dicarboxybenzene Oxy)diphenylphosphonium dianhydride, 4,4,-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3,,4,4 _Perfluoroisopropylidene diacetate dixanthine, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(decanoic acid) phenylphosphine oxide dianhydride, p-phenylene-bis( Triphenyl decanoic acid) dianhydride, meta-phenyl-bis(triphenylphosphonic acid) dianhydride, bis(phenyl decanoic acid) _4,4'-diphenyl ether dianhydride, bis(triphenyl acid) Acid)-4,4,-diphenylmethane dianhydride, ethylene glycol-bis(trimellitic acid vinegar), propylene glycol bis(trimellitic acid ester), 1,4-butanediol-double (bias Benzoic acid ester), 1,6-hexanediol-bis(trimellitic acid ester), 1,8-octanediol _ bis (trimellitic acid ester), 2,2 bis (4-hydroxybenzene) Aromatic tetracarboxylic dianhydride such as propylene-bis(p-benzoic acid ester) or aromatic tetracarboxylic dianhydride having a steroid skeleton represented by the following formulas (1) to (4) These may be used alone or in combination of two or more. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1293392 A7 B7 V. Description of invention (8) 0

0 CH3 CH3 C00

H3C CH(CH2)3CH=C' CH3 XH3 (2)

CH3 I ^ H3C CH(CH2)3CH Ο

Ο

H3C COO

ΌΗ3, CH3 (3) 〇 CH3 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

H3C CH(CH2)3CH

CHZ

CH3 (4) (Please read the notes on the back and fill out this page)

This paper scale applies to Chinese national standards (CNS>A4 specification (210X297 mm) -12- 1293392 A7 ___B7__ V. Invention description (9) (Please read the note on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Office staff consumption In the printing of the cooperative, it is preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3 -dimethyl-1 because it can exhibit good liquid crystal orientation and electrical properties. 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydrofuran)-3-methyl-3-cyclohexene- 1,2-dicarboxylic dianhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6- Tricarbonyl-2-carboxynorbornane-2:3,5 ·6-dianhydride, 1,3,3&amp;,4,5,91)-hexahydro-5(tetrahydro-2,5-dioxo 3--3-furyl)-naphtho[l,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5 (tetrahydrogen) -2,5-dioxo-3-furanyl)-naphtho[1,2-indolylfuran-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5, 8-dimethyl -5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]furan-l,3-dione, bicyclo[2,2,2]-octyl- 7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3,2,l]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran- 2',5'-dione), and the compound represented by the following formula (5) to (7) and the compound represented by the above formula (II) among the compounds represented by the above formula (I): 8) the compound represented, butane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3', 4, 4'-biphenyl-terotetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc., and these may be used alone or in combination of two or more. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -13- 1293392 A7 B7 V. Description of invention (Ψ

This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 1293392 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 B7 ___ _ V. Invention Description (1) 1 <Diamine> Polyproline The diamine used for the synthesis may, for example, be p-phenylenediamine, meta-phenylenediamine, 4,4'-diaminophenylmethane or 4,4'-diaminodiphenylethane. 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3' · dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzimidamide, 4,4'-diaminophenyl ether, 1,5-diaminonaphthalene, 3 ,3-dimethyl-4,4,diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroquinone, 6-amino group -1- ( 4'-aminophenyl)-1,3,3-trimethylhydroquinone, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ketone , 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis[4-(heart (4-aminophenoxy)phenyl) Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexahydropropane, 2,2-bis(4- Aminophenyl)hexafluoropropane, 2,2·bis[4-(4-aminophenoxy)phenyl]milled, 1,4·bis(4-aminophenoxy)benzene, 1,3 - bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2, 7-Diaminoguanidine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-four Chloro-4,4'.diaminobiphenyl, 2,2,dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethyl Oxy-4,4,-diaminobiphenyl, 1,4,4'-(phenylene isopropylidene)diphenylamine, 4,4'-(m-phenylphenylidene)diphenylamine , 2,2'-bis[4:(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4,-diamino-2,2'-bis (three Aromatic diamines such as fluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl; Toluene diamine, 1,3-propane diamine, tetramethylene diamine This paper scale applies to the national standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and refill This page) 1293392 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 ____B7_5, invention description (1) 2, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octopus Diamine, nonamethylenediamine, 4, hexamethylenediamine heptamethylenediamine, i, analdiamine cyclohexane, isophoronediamine, tetrahydrodicyclopentadienyl Diamine, hexahydro-4,7-methanol dihydroindole dimethylene diamine, tricyclo[6·21·〇2,7]-undecene dimethylene diamine, 4,4,_ Aliphatic and alicyclic diamines such as methylene bis(cyclohexylamine); 2,3-diamino acridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2.4- Diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridin, 5,6-diamino-2.4-dihydroxypyrimidine, 2,4-diamino-6-dimethyl Amine 4,3,5-three tillage, 1.4-bis(3-aminopropyl) piperidine, 2,4-diamino-6-isopropoxy-1,3,5-trimorphine, 2 ,4-diamino-6-methoxy-oxime, 3,5-triphthyl, 2,4-diamino-6-amino-1,3,5·trisyl, 2,4-diamine Methyl-symmetric trimorphine, 2,4-diamino 1,3,5-dimorph, 4,6-diamino-2-ethylreservo-pair Triterpenoid, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-one Amino-1,2,4-triu-, 6,9-diamino-2-ethoxyindole decyl lactate, 3,8-diamino-6-phenylphenanthridine, 1, 4-diaminopiperine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, etc. having two first-order amine groups in the molecule and the nitrogen group of the first-order amine group A diamine of an atom; a diamine-based organodecane represented by the following formula (III). These diamines ' can be used alone or in combination of two or more. I. R7 R7 H2N^CH2^Si^〇~Si]^CH2)^NH2 ( III ) ! (Please read the note on the back and fill out this page) This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297) -16- 1293392 Ministry of Economic Affairs, Intellectual Property Bureau, Employees and Consumers Cooperatives, Printing A7 B7 V. Inventions (where R7 represents a hydrocarbon number of 1 to 12 carbon atoms, and a plurality of existing R7 may be the same or Different, p is an integer from 1 to 3, and q is an integer from 1 to 20. In this case, preferably p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4' -diaminodiphenyl sulfide, 2,2'-dimethyl-4,4,diaminobiphenyl, :l,5-diaminonaphthalene, 2,7-diaminopurine, 4, 4. Diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2- Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene dipyridyl) Propyl)diphenylamine, 4,4'-(m-phenylphenyldiisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine) 1,4-double (4- Aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-aminopyridine, 2,4.diamine Pyridine, 3,6-diamino acridine, etc. In order to impart a pretilt angle developability to the liquid crystal aligning agent of the present invention, Q1 in the above formula (1-1) and/or in the above formula (1-2) Part or all of Q2 is preferably at least one group represented by the following formula (Q-1) and the following formula (Q-2), that is, using the following formula (Q-1) or A diamine represented by the following formula (Q-2) (hereinafter, abbreviated as "specific diamine"). (Please read the back note and fill out this page)

(wherein X is a single bond, -〇-, -C〇-, -C〇〇-, -〇C〇., -NHC〇-, -CONH-, -S· or aryl, R1 is carbon A number of 10 to 12 alkyl papers ^ applicable to China National Standard (CNS) A4 specifications (210X297 mm) ' -17- 1293392 Α7 Β7 Ministry of Economic Affairs Intellectual Property Bureau w consumer consumption cooperatives printed five, invention description (you, have a 1-membered organic group of an alicyclic skeleton having 4 to 40 carbon atoms.) A 0-(°-2) (wherein, X is a single bond, -〇-, -C〇-, -COO-, - 〇c〇-, -NHC〇-, -C〇NH-, -S- or an aryl group, and R2 is a divalent organic group having an alicyclic skeleton having a carbon number of 4 to 40.) The above formula (Q- In 1), the alkyl group having 10 to 20 carbon atoms represented by R1 may, for example, be n-decyl, n-dodecyl, n-pentadecyl, n-hexadecyl or n-octadecyl. Further, n-eicosyl group, etc. Further, R1 in the above formula (Q-1) and an organic group having an alicyclic skeleton having a carbon number of 4 to 40 represented by R2 in the above formula (Q-2) In addition, a cyclopentane, a cyclopentane, a cyclohexane, a ring broth, and the like having a alicyclic skeleton derived from a cycloalkane; cholesterol, cholesterol a group having a steroid skeleton such as an alcohol; a group having a bridged alicyclic skeleton such as norbornene or adamantane. The organic group having the above alicyclic skeleton may be a halogen atom, preferably a fluorine atom, or a fluorinated alkyl group. Further, in the above formula (Q-1), the carbon number of 6 to 20 represented by R1 may have a fluorine atom, and may be, for example, an n-hexyl group. a linear alkyl group having 6 or more carbon atoms such as an n-octyl group or a n-decyl group; an alicyclic hydrocarbon group having 6 or more carbon atoms such as a cyclohexyl group or a cyclooctyl group; and an aromatic group having 6 or more carbon atoms such as a phenyl group or a biphenyl group; A part or all of a hydrogen atom in an organic group in an organic group such as a hydrocarbon group is substituted with a fluorine atom or a fluorinated alkyl group such as a trifluoromethyl group.

(Please read the notes on the back and fill out this page)

Packing ', 11 paper size applicable to the national standard (CNS) Α 4 specifications (210Χ297 mm)

Λ Q 1293392 A 7 B7 V. Description of the invention (also, X in the above formula (Q-1) and the above formula (Q-2) is a single bond, -〇·, _C0_, -C〇〇_, _ 〇c〇·, _N: HC〇·, _C〇NH_, or an aryl group, and an extended aryl group: a phenyl group, a tolyl group, a phenyl group, a naphthyl group, etc. In particular, a group represented by -〇-, -C00-, -CO0-. A specific example of the diamine having a group represented by the above formula (Q-1) is preferably: Dodecyloxy-2,4·diaminobenzene, pentadecyloxy-2,4-diaminobenzene, palmadecane-2,4-diaminobenzene, octadecyloxy-2,4 -diaminobenzene, a compound represented by the following formulas (9) to (14). (Please read the back note and fill out this page)

Installation - Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing This paper scale applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 1293392 A7 B7 V. Invention description

This paper scale applies to the national standard (CNS) A4 specification (210X297 mm) -20- 1293392 A7 B7 V. Description of the invention (also, the diamine having the group represented by the above formula (Q-2) Specific examples are preferably two represented by the following formulas (15) to (17).

This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -21 - 1293392 Α7 Β7 V. Invention Description (These are the best ones: the above formulas (9), (10), Compounds represented by ( 1 3 ), ( 14 ) and ( 15 ) (Please read the notes on the back and then fill out this page) The ratio of the use of specific diamines to the amount of all-diamines, although as desired The pretilt angle varies depending on the size of the TN type and STN type liquid crystal display element, and is preferably 0 to 5 mol% in the case of the vertical alignment type liquid crystal display element. Synthesis of Amino Acids > The ratio of the tetracarboxylic dianhydride to the diamine used for the synthesis reaction of polyproline, and the equivalent of the amine group of the diamine is preferably the anhydride group of the tetracarboxylic dianhydride. 2·2 to 2 equivalents, more preferably 〇.3 to 1.2 equivalents. The synthesis reaction of polyproline is in an organic solvent, usually -20 ° C to 150 ° C, preferably 0 to 1 It is carried out under the temperature conditions of 〇〇 ° C. The Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative, printed here, in the case of organic solvents, The polylysine synthesized is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and An aprotic polar solvent such as methyl aristotle, butyrolactone, tetramethylurea or hexamethylphosphonium triamine; a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The amount of the solvent used (α) is preferably such that the total amount of the tetracarboxylic dianhydride and the diamine compound (/3) can be from 0.1 to 30% by weight based on the total amount (α + /3 ) of the reaction solution. Here, the above organic solvent may use an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, or a hydrocarbon which is a weak solvent of polyproline in a range in which the produced proline does not precipitate. For the specific example of such a weak solvent, the Chinese National Standard (CNS) Α4 specification (210 X 297 mm) can be used on the paper scale. -22- 1293392 A7 B7 V. Invention Description (1) 9 (Please Read the precautions on the back and fill out this page. Example: methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), B Glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol-methyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexyl Ketone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol Methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol acetate acetate, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol-methyl ether, diethylene glycol-diethyl ether, diethylene glycol-methyl ether acetate, diethylene glycol-diethyl ether acetate, tetrahydrofuran, dichloromethane, 1 , 2-dichloro, 1,4 - dichlorobutyl, trichloroethylene, chlorobenzene, o-dichlorobenzene, hexanyl, Gengyuan, octane, benzene, toluene, xylene, etc. In the above manner, a reaction solution obtained by dissolving polyproline is obtained. Then, the reaction solution is poured into a large amount of a weak solvent to prepare a precipitate, and the resultant is dried under reduced pressure to be much more proline. Further, the polyproline is re-dissolved in the organic solvent, and then the process of precipitation using a weak solvent is carried out once or in multiple times to purify the polyproline. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. <Synthesis of hydrazine-polymerized polymers> The ruthenium-imidized polymer can be synthesized by partially or completely dehydrating one or more of the above-mentioned prolyl acids. The preferred hydrazine imidation ratio is 40% by mole or more, and particularly preferably 70% by mole or more. A liquid crystal aligning agent capable of forming a liquid crystal alignment film having a short afterglow time can be obtained by using a polymer having a ruthenium iodide ratio of 40 mol% or more. This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) -. 1293392 A7 B7 V. Invention description (20 (please read the note on the back and fill out this page) Dehydration ring closure of polyamine The method may be carried out by (i) heating the polyproline, or (ii) dissolving the polyglycolic acid in an organic solvent, and adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, if necessary, by heating. The reaction temperature in the method of heating the polyproline (i) is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. If the reaction temperature is below 50 ° C, the dehydration ring closure reaction cannot be charged. If the reaction temperature is above 200 °C, the molecular weight of the ruthenium iodide polymer may decrease. Printed by the Intellectual Property Intelligence Bureau of the Ministry of Economic Affairs, on the other hand, in the above (ii) In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used depends on the desired imidization ratio. Different, but repeated for polyproline Further, it is preferably 0.01 to 20 mol. Further, as the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. Here, the amount of the dehydration ring-closing catalyst used is preferably 0 to 01 to 10 mol for the dehydrating agent 1 used. The more the dehydrating agent and the dehydration ring-clogging agent are used, the more Here, the organic solvent used for the dehydration ring-closure reaction is an organic solvent exemplified for the synthesis of polyglycolic acid, and the reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. Further, as in the solution obtained in this manner, the obtained ruthenium iodide polymer can be purified in the same manner as in the purification method of polyproline. <End-Modified Polymer> The polymer used in the present invention can be a modified molecular weight end-modified paper scale. National Standard (CNS) A4 Specification (210X297 mm) 1293392 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention Ming (2) type. By using such a terminal modified type polymer, the coating property of the liquid crystal aligning agent can be improved without affecting the effect of the present invention. Such a terminal modified type polymer is In the case of synthesizing polyglycine, an acid anhydride, a monoamine compound, a monoisocyanate compound, or the like may be added to the reaction system to synthesize it. Here, the acid anhydride may, for example, be maleic anhydride, phthalic anhydride, or clothing. And anhydride, n-decyl boroic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. Further, as the monoamine compound, aniline and ring may be exemplified. Hexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, positive ten Tetraalkylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. Further, the monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. <Logarithmic Viscosity of Polymer> The polymer obtained as above has a logarithmic viscosity (7?u) of preferably 0.05 to 10 dl/g, more preferably 0.05 to 5 dl/g. In the logarithmic viscosity (77 in) of the present invention, N-methyl-2-pyrrolidone is used as a solvent, and the viscosity is measured at a concentration of 0.5 g/l 〇〇ml at 30 ° C, and The person sought by the formula (i). =ln (time of solution flow / time of solvent flow) (weight concentration of polymer) <block copolymer> (Please read the note on the back and fill out this page)

Book i# This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) -25- 1293392 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau 8 Workers Consumption Cooperative Printed 5, Invention Description (Because of the polymer composition of the present invention When the above block copolymer is used, 'a proline prepolymer having an amine group or an acid anhydride group at the terminal' and a ruthenium imine having an acid anhydride group or an amine group at the terminal are respectively synthesized, and each pre-polymer is prepared. The block copolymer can be obtained by combining the amine group at the end of the polymer with the acid anhydride group. The synthesis method of the proline prepolymer is the same as the synthesis method of the above polyamine, and the synthesis of the quinone imine The method is the same as the above-mentioned synthesis method of the ruthenium-imiding polymer. Further, the selection of the functional group at the terminal 'the amount of the tetracarboxylic dianhydride and the diamine which can be synthesized by the poly-proline <Liquid Crystal Orienting Agent> The liquid crystal aligning agent of the present invention is one in which the above polymer component is dissolved and contained in a solvent. The solvent can be an organic solvent. The temperature at which the liquid crystal aligning agent of the present invention is prepared Usually, it is 〇 ° C to 200 ° C, preferably 20 ° C to 60 ° C. The organic solvent constituting the liquid crystal aligning agent of the present invention can be used as a synthetic reaction of polyglycine. The solvent to be exemplified may be appropriately selected and used as a weak solvent exemplified for use in the synthesis reaction of polyproline. In particular, it is preferred to use r-butyrolactone and/or butyl cellosolve. It is particularly preferable to use both of them. The total content of r-butyrolactone and butyl cellosolve is preferably 90% by weight or more, and particularly preferably 95% by weight or more, based on the total amount of the solvent. Then, the mixing ratio thereof is preferably 50 to 1% by weight, particularly preferably 90% by weight or more, based on the total amount of T-butyrolactone and butyl cellosolve. (Please read the back first. Note: Please fill in this page) This paper scale applies to China National Standard (CNS) A4 specification (210X; 297 mm) -26- 1293392 A 7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (in addition Because the liquid crystal aligning agent of the present invention may erode the inkjet printing method The organic material such as the nozzle member needs to reduce the content of the solvent such as N-methyl-2-pyrrolidone. The content of the organic solvent is preferably 5% by weight or less based on the entire solvent. The solid component concentration may be selected in consideration of viscosity, volatility, etc., but is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate to form In the film coating film of the liquid crystal alignment film, if the solid content concentration is 1% by weight or less, the film thickness of the coating film is too small, and it is difficult to obtain a good liquid crystal alignment film, and when the solid content concentration is 10% by weight or more, Then, the film of the coating film becomes too large to be easily formed into a liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent is increased to become a poor coating property. <Adhesive Aid> The liquid crystal aligning agent of the present invention may contain a compound containing a functional decane or a compound containing an epoxy group from the viewpoint of improving the adhesion to the surface of the substrate. Such a compound containing a functional decane may, for example, be 3-aminopropyltrimethoxy decane, 3-aminopropyltriethoxy decane, 2-aminopropyltrimethoxy decane or 2-amino group. Propyltriethoxyoxane, N-(2-aminoethyl)-3-aminopropyltrimethoxyoxane, N-(2-aminoethyl)-3-aminopropyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxyoxane, N-ethoxycarbonyl-3-aminotrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxy Decane, N-triethoxymethyl decyl propyl trivinyl diamine, N-trimethoxy methoxyalkyl trivinyl diamine, 10-trimethoxy methoxyalkyl _ (please read the precautions on the back) Fill in this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -27- 1293392 A7 ____B7 V. Invention description (2&gt; (Please read the note on the back and fill in this page) 1,4 ,7-triazanonane, 1〇-triethoxymethyl decyl-1,4,7-triazinane, 9-trimethoxymethyl oxime-3,6-diazadecyl acetate , N-Germanyl-3-aminopropyltrimethoxy decane, Ν-benzyl-3-amino Triethoxy oxane, fluorenyl-phenyl-3-aminopropyltrimethoxy decane, fluorenyl-phenyl-3-aminopropyltriethoxy decane, hydrazine bis(hydroxyvinyl)-3-amino Further, propyltrimethoxy decane, hydrazine-bis(hydroxyvinyl)-3-aminopropyltriethoxy decane, etc. Further, in the case of the compound containing an epoxy group, a glycol condensate is preferred. Glycerol ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol condensed water Glycerol ether, glycerol diglycidyl ether, 2,2-dibrominated neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, hydrazine, hydrazine, Ν',Ν'-tetraglycidyl-m-xylyleneamine, 1,3-bis(indole, hydrazine-diglycidylaminoethyl)cyclohexane, Yishan 1^', 1^-tetraglycidyl -4,4'-diaminodiphenylmethane, etc. The compounding ratio of the compound containing a functional decane or the compound containing an epoxy group is usually 40 parts by weight or less, preferably 40 parts by weight or less, based on 100 parts by weight of the polymer. 0 to 1 to 30 weight Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives, <Liquid Crystal Display Element> The liquid crystal display element produced by using the liquid crystal aligning agent of the present invention can be manufactured by the following method, for example. One surface of the substrate of the conductive film is coated with the liquid crystal aligning agent of the present invention by an inkjet printing method, and then the coated surface is heated to form a coating film. Here, the substrate may be, for example, a float glass. This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) -9R - 1293392 A 7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (for), soda glass (soda glass), etc. Glass; such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate and other transparent substrates made of plastic. For a transparent conductive film provided on one surface of a substrate, a NESA film of tin oxide (Sn02) (registered trademark of PPG, USA) and ITO (indium) made of indium oxide-tin oxide (In23-Sn02) can be used. A tin oxide film, and for the pattern constitution of the transparent conductive film for this purpose, a photoresist method or a mask method in advance is used. When the liquid crystal aligning agent is applied, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a compound containing a functional decane may be preliminarily coated on the surface of the substrate, and a compound containing a functional titanium may be applied. Wait. The heating temperature after application of the liquid crystal director will be 80 to 300 ° C, preferably 12 to 25 ° C. Here, the liquid crystal aligning agent of the present invention containing polyglycolic acid removes the organic solvent after coating to form a coating film for the oriented film, but can be reheated to make the dehydration ring closed. The imidized coating film. The film thickness of the formed coating film is usually 0.001 to 1/z m, preferably 0.005 to 0.5/ΖΠ1. (2) A rubbing treatment is performed on the formed coating film surface by using a roll of a cloth made of a fiber such as nylon, crepe or cotton to rub in a certain direction. Thereby, the orientation energy of the liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film. Further, the liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention is subjected to a partial irradiation of ultraviolet rays disclosed in, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. The treatment of the horn, or the rubbing treatment disclosed in Japanese Patent Laid-Open Publication No. Hei No. Hei No. 5-107544 (please read the notes on the back and fill out this page)

Packing paper size general national standard (CNS) eight 4 specifications (210X297 mm) _ OQ _ 1293392 A7 _B7_ five, invention description (2) fe (please read the back of the note before you fill out this page) The surface of the liquid crystal alignment film partially forms a photoresist film, and after removing the photoresist film in a different direction from the previous rubbing treatment, the photoresist film is removed to perform a process of changing the liquid crystal orientation energy of the liquid crystal alignment film, that is, the liquid crystal can be improved. (3) The two substrates on which the liquid crystal alignment film is formed are formed as described above, and the two substrates are interposed by gaps according to the direction in which the rubbing direction of each liquid crystal alignment film can be perpendicularly intersected or anti-parallel. And disposed in the opposite direction, and the peripheral portion of the two substrates is bonded by using a sealant, and the liquid crystal is injected into the surface of the substrate and the cell gap cut by the sealant, and the injection hole is sealed to constitute a liquid crystal cell. a liquid crystal formed on the outer surface of the liquid crystal cell, that is, on the other surface side of each of the substrates constituting the liquid crystal cell, in which the polarizing plate can be formed in one direction of the polarizing plate and one surface of the substrate A liquid crystal display element can be obtained by bonding the film in such a manner that the rubbing direction thereof is uniform or perpendicularly intersected. Here, as the sealing agent, for example, an epoxy resin containing a curing agent and an alumina ball as a spacer can be used. In addition, a nematic liq uid crystal and a smectic liquid crystal may be mentioned, and among them, a silk-type liquid crystal intellectual property bureau employee consumption cooperative printed liquid crystal is preferable, for example, Schiff base is a liquid crystal, an oxynitride-based liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a bitrino liquid crystal, a biphenyl cyclohexane liquid crystal, or a pyrimidine system. Liquid crystal, a faculty LCD, Shuanghuan Xinyuan liquid crystal, Cubane liquid crystal, etc. Further, cholesteric liquid crystal such as chlorinated cholesterol, cholesteryl citrate or cholesterol carbonate may be added to the liquid crystal or For example, the product name "C-15" "CB-15" (made by the company) is used by Chiral. This paper size is suitable for the consumer (CNS) A4 threat (21GX297 mm). ~~ ~ 1293392 A7 _ B7

5. Description of the invention (A, such as a strong dielectric liquid crystal such as p-oxybenzylidene-p-amino-2-methylethylcinnamate.) (Please read the precautions on the back and fill in In this case, the polarizing plate to be bonded to the outer surface of the liquid crystal cell is a polarizing film called a ruthenium film which is obtained by stretching polyvinyl alcohol and absorbing iodine, and is protected with cellulose acetate. A polarizing plate sandwiched by a film or a polarizing plate made of a film itself. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. The evaluation method is as follows: [Inkjet coating property of liquid crystal aligning agent] The JET-CM continuous inkjet printer (Jizhou Technology Industrial Co., Ltd.) is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the apparatus, a liquid crystal aligning agent prepared to have a solid concentration of 3% by weight was applied, and a dry film thickness was applied to the ruthenium substrate to a liquid amount of 60 nm. Then, it was dried at 23 ° C, and a thimble film thickness was used. Measuring the unevenness of the dried film and maximizing the film thickness and minimum When the difference in thickness is 7 nm or less, it is judged to be good. The liquid amount and the coating pressure are constant, and the adjustment of the dry film thickness is carried out by adjusting the solid content concentration of the liquid crystal aligning agent. [Measurement of surface tension] The surface tension measuring device of CBUP surface tension meter A1 (Concord Scientific Co., Ltd.) is used for measurement. The paper size is applicable to the national standard (CNS) A4 specification (210X297 mm) -31 - 1293392 A7 ______B7 V. Invention Description ([Polylination rate of polymer] After drying the polymer under reduced pressure at room temperature, it was dissolved in dihydrogenated dimethyl saponin and tetramethyl decane was used as a reference material, and iH- was measured at room temperature. NMR (nuclear resonance) is obtained by the formula of the following formula (ii): oxime imidization ratio (%) = (i-aVa^ α ) X 100 (ii) A1 : origin of the proton-derived peak of the NH group値 area (lOppm) A2: other proton-derived peak area α: in the polymer precursor (polyproline), the ratio of the number of other protons of a proton of the NH group [liquid crystal orientation Sexual observation using a polarizing microscope to turn the voltage on the liquid crystal display element - 〇 FF (applied/released), the presence or absence of an abnormality field, and the case where there is no abnormal field is judged to be good. [Voltage retention ratio of liquid crystal display element] The application time of the liquid crystal display element is 60 microseconds, 1 67 After a voltage of 5 V (volts) was applied to the span of milliseconds, the voltage holding ratio after 16 milliseconds after the application was released was measured. The measuring device was made using Dongyang Teknana VHR-Bu [afterimage disappearance time]. This paper size applies to the national standard (CNS) A4 specification (210 X 297 mm) ----·---^---- (please read the notes on the back and fill out this page) Ministry of Intellectual Property Bureau employee consumption cooperative printing -32- 1293392 A7 _ _B7 V. Invention description (2)0 After applying a DC voltage of 10 V to the liquid crystal display element for 2 hours, the application of the voltage is released, and the surface is visually observed. The time from the application of the release voltage to the disappearance of the afterimage on the screen is measured. <Synthesis Examples 1 to 62> In the N-methyl-2-pyrrolidone, the compounds shown in Tables 1 to 4 were subjected to the molar ratios shown in the arcs, and the diamines and tetracarboxylic dianhydrides were used. The order was added, and in Synthesis Examples 53, 54, 57, 59 and 62, the reaction was carried out for 6 hours at room temperature according to the solid concentration of 20%, and the other synthesis was carried out at 30 ° C according to the solid content of 30%. 6 hours. Next, the reaction solution was concentrated using an evaporator, and the &amp; methyl-2-port is substituted with 7-butyrolactone by the operation of adding r-butyrolactone, and the results are shown in Tables 1 to 4. Polyproline solution PAA-1 to PAA-62. (Please read the notes on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumer Cooperatives, Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210X297 mm) -- 1293392 V. Invention Description (Ice [Table 1] Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Synthetic Anhydride Diamine Polymer 1 TCA(50) PDA(50) PAA-1 2 TCA(50) PDA(50) PAA-2 3 CB(50 ) PDA (50) PAA-3 4 PMA (50) PDA (50) PAA-4 5 TCA (50) PDA (25), DDM (25) PAA-5 6 PMA (25), CB (25) PDA (25 ), DDM(25) PAA-6 7 CH(50) PDA(25), BAPP(25) PAA-7 8 CH(50) DDM(25), BAPP(25) PAA-8 9 CB(50) DDE( 50) PAA-9 10 CB(50) MDB(50) PAA-10 11 PMA(25), TCA(25) BAPP(50) PAA-11 12 PMA(50) PDA(50) PAA-12 13 PMA(50 DDE(50) PAA-13 14 TCA(25), MTDA(25) PDA(43.75), FDB(5), Diamine 4 (〇.5), ODA(0.75) PAA-14 15 TCA(25) , MTDA (25) PDA (43.75), PTS (0.5), Diamine 4 (〇.5), ODA (0.75) PAA-15 16 TDA (50) PDA (45), HDA (5) PAA-16 17 PMA (40), TCA (10) BAPP (50) PAA-17 18 PMA (40), TCA (10) BAPP (10), DDM (40) PAA-18 19 PMA (40), TCA (1) 0) BAPP(10), DDE(40) PAA-19 20 PMA(40), TCA(10) BAPP(10), DDM(39.5) Diamine 1(0.5) PAA-20 21 PMA(40), TCA (10) BAPP(10), DDM(39.5) Diamine 1(0.5) PAA-21 (Please read the back note first and then fill out this page)

Order # This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) -34- 1293392

7 B V. Description of Invention (3) [Table 2] Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Synthetic Example Anhydride Diamine Polymer 22 PMA(40), TCA(10) BAPP(10), DDM(39.5) Diamine 1 (0.5) PAA-22 23 PMA (40), CB (10) BAPP (50) PAA-23 24 PMA (40), CB (10) BAPP (10), DDM (40) PAA-24 25 PMA (40), CB (10) BAPP (10), DDE (40) PAA-25 26 PMA (40), CB (10) BAPP (10), DDM (39.5) Diamine 1 (0.5) PAA-26 27 PMA (40), CB (10) BAPP (10), DDE (39.5) Diamine 1 (0.5) PAA-27 28 PMA (40), CB (10) BAPP (25), DDM (24.5) Binary Amine 1 (0.5) PAA-28 29 PMA (25), CB (25) BAPP (50) PAA-29 30 PMA (25), CB (25) BAPP (10), DDM (40) PAA-30 31 PMA ( 25), CB(25) BAPP(10), DDE(40) PAA-31 32 PMA(25), CB(25) BAPP(10), DDM(39.5) Diamine 1(0.5) PAA-32 33 PMA (25), CB (25) BAPP (10), DDE (39.5) Diamine 1 (0.5) PAA-33 34 PMA (25), CB (25) BAPP (10), DDM (39.5) Diamine 1 (0.5) PAA-34 35 PMA (25), CH (25) BAPP (50) PAA-35 36 PMA (25), CH (25) BAPP (10), DDM (40) PAA-36 37 PMA (25) ,CH(25) BAPP(10),DDE(40) PAA-37 38 PMA(25),CH(25) BAPP(10)?DDM(39.5) Diamine (0.5) PAA-38 (please read the Notes on the back to fill out this page)

Loading and setting paper size applicable to national standard (CNS) A4 specification (210X297 mm) 1293392

7 B V. Description of invention (绅 [Table 3] Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed synthetic acid anhydride diamine polymer 39 PMA (25), CH (25) BAPP (10), DDE (39.5) Monoamine 1 (0.5) PAA-39 40 PMA (25), CH (25) BAPP (10), DDM (39.5) Diamine 1 (0.5) PAA-40 41 PMA (25), DMCB (25) BAPP ( 50) PAA-41 42 PMA (25), DMCB (25) BAPP (10), DDM (40) PAA-42 43 PMA (25), DMCB (25) BAPP (10), DDE (40) PAA-43 44 PMA (25), DMCB (25) BAPP (10), DDM (39.5) Diamine 1 (0.5) PAA-44 45 PMA (25), DMCB (25) BAPP (10), DDE (39.5) Diamine 1(0.5) PAA-45 46 PMA(25), DMCB(25) BAPP(25), DDM(24.5) Diamine 1(0.5) PAA-46 47 PMA(40), TCA(10) PDA(47.5) , Diamine 1 (2.5) PAA-47 48 PMA (25), CH (25) DDE (47.5), Diamine 1 (2·5) PAA-48 49 PMA (25), CH (25) DDE ( 47.5), Diamine 1 (2.5) PAA-49 50 CB (50) BAPP (50) PAA-50 51 TCA (50) PDA (47.5), Diamine 1 (2.5) PAA-51 52 TCA (50) DDM (49.5), diamine 1 (0.5) PAA-52 53 TCA (50) PDA (45), diamine 2 (10) PAA-53 54 PMA (25), CB (25) DDM (50) PAA -54 55 TCA(50) PDA(4〇), Diamine 2 (10) PAA-55 56 TCA(50) PDA(37.5), Diamine 2 (12.5) PAA-56 57 PMA(25), CB(25) DDE(50) PAA-57 (Please read the back of the note first) Please fill out this page again)

Binding. The cost of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -36- 1293392 A7 B7 V. Inventive Note (绰lm 4 Synthesis Example J Anhydride Diamine Polymer 58 TCA(50) PDA (35), Diamine 2 (12.5) PAA-58 PTS (2.5) 59 TCA (50) PDA (45), Diamine 1 (5) PAA-59 60 TCA (50) PDA (37.5) PAA-60 Diamine 1 (12.5) 61 TCA (50) PDA (20), Diamine 3 (30) PAA-61 62 CB (50) MDB (50) _PAA-62 One ~~——— (Please read the back first Note: Please fill in this page) 1# Refill Ί Install TCA: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride CB: 1,2,3,4-cyclobutane tetracarboxylic dianhydride DMCB : 1,2-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride PMA: pyromellitic dianhydride CH: 1,2,4,5-cyclohexanetetracarboxylic acid Anhydride 1 ^ butyl 0 8 : 1,3,3 &amp;, 4,5,91)-hexahydro-5-methyl-5 (tetrahydro-2,5-di &gt; ^, '~oxo-3, Π 喃 ))-naphtho[l,2-c]-furan-1,3-dione butyl 0:1,3,3&amp;,4,5,913-hexahydro-5 (tetrahydro-2,5 -dioxo 7 π'3-furyl)naphtho[l,2-c]-furan-1,3-dione' PDA : p-phenylenediamine DDM : 4,4 , diaminodiphenylmethane BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propanil DDE: 4,4'-diaminodiphenyl ether MDB: 2, 2'-Dimethyl-4,4'-diaminobiphenyl paper size applicable to China National Standard (CNS) A4 specification (210X 297 mm), 11 # Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing -37 - 1293392 A7 B7 V. INSTRUCTIONS (ODA: Octadecyloxy-2,4·diaminobenzene HDA: Hexadecyloxy-2,4-diaminobenzene (please read the precautions on the back) Fill in this page) PTS: bisaminopropyltetramethyldioxane (diamine represented by the above formula (III)) Diamine 1: a diamine diamine represented by the above formula (9) 2: a diamine diamine represented by the above formula (10): a diamine diamine represented by the above formula (13): a diamine represented by the above formula (15) < Synthesis Example 63 〉 Add p-phenylenediamine, 4,4′-diaminodiphenylmethane, pyromellitic dianhydride, ι, 2, 3 in Ν-methyl-2-pyrrolidone according to the molar amount. , 4-cyclobutane tetracarboxylic dianhydride' was prepared as a solution having a solid concentration of 30%. The solution was reacted at room temperature for 8 hours. Next, the reaction solution is concentrated using an evaporator, and Ν-methyl-2-pyrrolidone is substituted with r-butyrolactone by adding r-butyrolactone to obtain a polymer having the same repeating unit as PAA-6. Polyproline PAA-63. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Employees' Cooperatives Co., Ltd. <Synthesis Examples 64 to 80> The polyglycine shown in Table 5 was diluted with N-methyl-2-pyrrolidone to a solid concentration of 5% by weight for each of the polyamines. The diamine used in the synthesis of the acid is added with pyridine 5 mol and acetic anhydride 3 mol of the imidization catalyst per 1 mol, and stirred at 110 ° C for 4 hours to synthesize the solvent soluble ruthenium imidization. Polymers PI-1 to PI-17. The polymer solution is concentrated using an evaporator, and the paper size is applied to the national standard (CNS) A4 specification (2丨0X 297 public celebration)-----38- 1293392 A7 B7. V. Description of invention (add r - In the operation of butyrolactone, N-methyl-2-pyrrolidone is substituted with r-butyrolactone to prepare a ruthenium-imiding polymer solution. The ruthenium imidization ratio of the obtained ruthenium iodide polymer is combined. It is shown in Table 5. (Please read the note on the back and then fill out this page.) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed This paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -39 - 1293392 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 5, Inventions (Ball 5) Synthetic Example Polyamine hydrazide imidized polymer 醯 imidization rate (%) 64 ΡΡΑ-1 ΡΜ &gt;90 65 ΡΡΑ-2 ΡΙ-2 &gt;90 66 ΡΡΑ-4 ΡΙ-3 60 67 ΡΡΑ-11 ΡΙ-4 &gt;90 68 ΡΡΑ-14 ΡΙ-5 &gt;90 69 ΡΡΑ-15 ΡΙ-6 &gt;90 70 ΡΡΑ -16 ΡΙ-7 &gt;90 71 ΡΡΑ-51 ΡΙ-8 &gt;90 72 ΡΡΑ-52 ΡΙ-9 &gt;90 73 ΡΡΑ-53 ΡΙ-10 &gt;90 74 ΡΡΑ- 55 ΡΙ-11 &gt;90 75 ΡΡΑ-56 ΡΙ-12 &gt;90 76 ΡΡΑ-57 ΡΙ-13 &gt;90 77 ΡΡΑ-58 ΡΙ-14 60 78 ΡΡΑ-59 ΡΙ-15 &gt;90 79 ΡΡΑ-60 ΡΜ6 &gt;90 80 ΡΡΑ-61 ΡΙ-17 &gt;90 (Please read the notes on the back and fill out this page)

Packing -

, 1T This paper scale applies to China National Standard (CNS) Α4 specification (210X297 mm) -40- 1293392 A7 __ B7 V. Invention description (sentences <Examples 1 to 3> Use according to the weight ratio shown in Table 6 below The polylysine obtained in Synthesis Example 6 and Synthesis Example 63 and the ruthenium-imided polymer obtained in Synthesis Example 68 were dissolved in the solid content concentration (TSC) shown in Table 6 as shown in Table 6. Mixing ratio (weight ratio) of r-butyrolactone (BL) / butyl cellulolytic (BC) mixed solvent. This solution was filtered using a filter having a pore size of 1 / m to prepare a liquid crystal aligning agent of the present invention. The viscosity and surface tension of the solution at this time are indicated. Using the TET-CM continuous ink jet printer (manufactured by Kishu Technology Co., Ltd.), the obtained liquid crystal aligning agents are coated on a glass substrate with ITO. The film was dried at 230 ° C for 10 minutes to obtain a coating film. The coating property of the liquid crystal aligning agent was evaluated, and the film thickness of the obtained coating film was measured. The results are shown in Table 6 (see reading first). Note on the back and fill out this page)

Installation----- Ministry of Economic Affairs, Intellectual Property Office, Employees, Consumer Cooperatives, Printed Paper Scale Applicable to China National Standard (CNS) Eight 4 Specifications (210 X 297 mm) 1293392 A7 B7 V. Invention Description (3矣[Table 6] Solid polymer TSC Solvent solution Physical film thickness Coating property PAA PI (%) BL BC Viscosity surface tension (nm) Example (mPa*s) (dyn/cm) 1 PAA-6(80) PI- 5 (10) 5 97 3 15 43 120 Good 2 PAA-6(40) PI-5(20) 3 97 3 16 42 60 Good PAA-63(40) 3 PAA-63(80) PI-5(20) 1.5 97 3 15 43 30 Good (please read the notes on the back and fill out this page)

^ϋ··— «Bn— ·ϋι_— IT-----Line. Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210X 297 mm) -49 - 1293392 A7 B7 V. INSTRUCTIONS (Evaluation Example) Using a friction machine having a roller with a roll of a roll, the number of rotations of the roller is 400 rpm, the moving speed of the stage is 3 cm/sec, and the length of the fluff is inserted. The rubbing treatment was carried out under the conditions of 4 mm. The substrate was immersed in ultrapure water for 1 minute, and then dried on a hot plate of 1 ° C for 5 minutes to form a liquid crystal alignment film. Secondly, a coating diameter of 5.5/zm was applied. After the epoxy resin adhesive containing alumina beads is attached, a pair of liquid crystal clamping substrates are pressed against the liquid phase to adjust the surface of the film to cure the bonding agent. Then, a liquid crystal injection port is used in one After filling the substrate between Nematic liquid crystals (MLC-622 1 manufactured by Meike Co., Ltd.), the liquid crystal injection port was sealed with an acrylic photoinitiated curing adhesive, and the polarizing plate was attached to both sides of the substrate. To produce a liquid crystal display element. The resulting liquid crystal display Orientation shall be regarded as a good person, and the voltage retention rate is showing 99% of high-Zhi. Also, I like to disappear for 10 seconds (matters Please read the back of the note and then fill in this page)

Printed and ordered by the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives. <Reference Example> The liquid crystal display element was produced in the same manner as the evaluation example except that the coating method was the spin coating method. The orientation of the obtained liquid crystal display element was good, and the voltage retention enthalpy was 99% high. Also, the afterimage disappearance time is 10 seconds. Therefore, the liquid crystal display element obtained in the evaluation example has the same performance as the liquid crystal display element obtained in the reference example. <Examples 4 to 66> In addition to the use of the polyglycine and the ruthenium-based polymer shown in Tables 7 to 9, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1293392 A7 B7 In the same manner as in Example 2, a liquid crystal aligning agent was prepared in the same manner as in Example 2, and a liquid crystal display element was produced in the same manner as in the evaluation example. The coating properties are all good, and the orientation of the liquid crystal display elements is also good. The combination of the liquid crystal alignment agents in Tables 7 to 9 indicates the viscosity and surface tension of the liquid crystal alignment agent, and the film thickness of the coating film. Note: Please fill out this page again) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed in this paper scale applicable National Standard (CNS) A4 Specification (210 X 297 mm) -44- 1293392

7 B V. INSTRUCTIONS (4) Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives [Table 7] Example Polymer Composition Solution Physical Thickness Multi-Glutamine Imine Polymer Viscosity Surface Tension (nm) (mPs# s) (dyn/cm) 4 — PI-1 13 44 60 5 PAA-2 — 11 41 60 6 — PI-2 13 43 60 7 PAA-4 — 11 41 60 8 PAA-5 — 16 43 60 9 — PI -3 14 42 60 10 PAA-6 — 13 41 60 11 PAA-6 PI-1 15 42 60 12 PAA-7 — 15 42 60 13 PAA-8 — 16 44 60 14 PAA-9 PI-6 13 41 60 15 PAA-9 PI-4 14 44 60 16 PAA-10 PI-6 15 41 60 17 PAA-10 PI-4 10 42 60 18 PAA-17 — 18 44 60 19 PAA48 A 17 41 60 20 PAA-19 — 15 41 60 21 PAA-20 — 16 42 60 22 PAA-21 — 14 41 60 23 PAA-22 — 18 42 60 24 PAA-23 — 15 43 60 25 PAA-24 — 15 43 60 (Please read the notes on the back first. Fill in this page) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 1293392

V. Description of the invention (Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives [Table 8] Example Polymer Composition Solution Physical Thickness Multi-Glutamine Imine Polymer Viscosity Surface Tension (Dirty) (mPs*s) ( Dyn/cm) 26 PAA-25 — 17 44 60 .27 PAA-26 — 16 ' 43 60 28 PAA-27 — 14 44 60 29 PAA-28 — 10 44 60 30 PAA-29 — 11 44 60 31 PAA-30 — 12 44 60 32 PAA-31 — 15 42 60 33 PAA-32 — 18 44 60 34 PAA-33 — 17 41 60 35 PAA-34 — 18 41 60 36 PAA-35 — 11 41 60 37 PAA-36 A 14 41 60 38 PAA-37 — 11 44 60 39 PAA-38 — 16 43 60 40 PAA-39 — 15 41 60 41 PAA-40 — 12 41 60 42 PAA-41 — 10 41 60 43 PAA-42 — 18 44 60 44 PAA-43 — 18 42 60 45 PAA-44 — 14 42 60 46 PAA-45 — 11 42 60 47 PAA-46 — 18 44 60 48 PAA-17 PI-8 15 44 60 (Please read the notes on the back first) Fill in this page again. This paper size applies to the national standard (CNS) A4 specification (210 X 297 mm) -- 1293392

A

7 B V. Description of invention (4 Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative [Table 9] Example Polymer composition solution Physical film thickness (nm) Polyphosphonium imide polymer viscosity (mPs*s) Surface Tension (dyn/cm) 49 PAA-17 PI-9 14 43 60 50 PAA-48 — 12 42 60 51 PAA-49 — 12 44 60 52 PAA-54 PI-12 16 44 60 53 PAA-54 PI-10 13 43 60 54 PAA-54 PI-11 16 41 60 55 PAA-57 PI-13 15 43 60 56 PAA-57 PI-14 17 44 60 57 PAA-57 PI-15 18 42 60 58 PAA-57 PI-16 10 41 60 59 PAA-57 PI-17 10 41 60 60 PAA-62 PM3 16 44 60 61 PAA-62 PI-14 12 42 60 62 PAA-54 PI-12 14 43 60 63 PAA-62 PI-13 14 44 60 64 PAA-53 — 15 41 60 65 PAA-56 — 12 44 60 66 PAA-58 — 15 44 60 (Please read the notes on the back and fill out this page)

Packing paper size is applicable to national standard (CNS) A4 size (210 X 297 mm) -47 - 1293392 A7 B7 V. Description of invention (Example 67) In addition to being used as a substrate, ITO is attached. In the same manner as in Example 2, a liquid crystal display device was produced in the same manner as in Example 2. The film thickness of the coating film was 60 nm, and the coating property was good, and the orientation of the liquid crystal display device was good. According to the present invention, an ink jet printing method can be used to produce an excellent liquid crystal display element. The liquid crystal display element having the liquid crystal alignment film of the present invention is useful in addition to TN type, STN type, and VA type liquid crystal display elements. In addition, if you choose the liquid crystal used, you can also use SH (Super Homeotropic) type, IPS (In-plane Switching) type, ferroelectric (ferroelectric) and antiferroelectricity. Further, the liquid crystal display element having the liquid crystal alignment film of the present invention can be effectively used in various devices, such as a desktop computer, a watch, a clock, and a coefficient display meter. Display device for text automatic processor, personal computer, LCD TV, etc. This paper size is applicable to China National Standard (CNS) A4 specification (2丨0&gt;&lt;297 mm) il·丨-^丨_装! (Please first Read the notes on the back and fill out this page. Printed by the Intellectual Property Office of the Ministry of Economic Affairs

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Claims (1)

Α8 Β8 C8 D8 Patent Application No. 9 1 1 3 7 1 7 Patent Application No. 1 Revision of the Chinese Patent Application No. November 22, 1995 Revision 1. A liquid crystal aligning agent for inkjet printing, characterized by a polymer component having at least one selected from the group consisting of a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2), and a r-butyrolactone as a solvent and At least one of butyl cellosolve, the total content of which is 90% by weight or more based on the total amount of the solvent, and the solid content concentration is in the range of 1 to 10% by weight. (Please read the back of the note before completing this page) HOOQ , COOH HNOC CONH—Q1 1-1) Ordered by the Intellectual Property Office of the Ministry of Economic Affairs (In the formula, P1 is a tetravalent organic group and Q1 is a divalent organic group) (1-2) (wherein P2 is a tetravalent organic group and Q2 is a divalent organic group). 2. The liquid crystal aligning agent for ink jet printing according to the first aspect of the invention, wherein the viscosity is in the range of 5 to 20 mPa*s, and the surface tension is in the range of 35 to 45 dyn/cm. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) Φ.