TWI228614B - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Abstract

To obtain a liquid crystal alignment agent which is excellent in jetting stability in applying to a substrate by ink jet printing and gives a liquid crystal alignment layer having a uniform thickness by incorporating a block copolymer containing polyimide blocks and polyamic acid blocks into the same. This agent contains a block copolymer comprising polyimide blocks and polyamic acid blocks. The polyimide block comprises at least one kind of repeating units selected from among repeating units represented by formulas I and II. The polyamic acid block comprises at least one kind of repeating units selected from among repeating units represented by formulas III and IV. In the formulas, R1, R4, and R6 are each H or alkyl; R2, R3, R5, and R7 are each a divalent organic group; 1 is 1-4; and n, m, q, and p are each a positive number. The agent can quite satisfy the pretilt angle, voltage retention, and residual image characteristics required of liquid crystal display elements.

Description

A7 1228614 ____ B7_ · V. Description of the Invention (1) Field of the Invention The present invention relates to a molding agent suitable for a liquid crystal alignment film and a liquid crystal display element using the same. In more detail, the present invention relates to a liquid crystal aligning agent with excellent coating stability and film thickness uniformity, and a liquid crystal display using the same when the ink jet printing method is applied to a substrate containing a block copolymer containing a specific structure. element. Liquid crystal display elements currently known in the art such as having a substrate provided with a transparent conductive film, and a polyimide and a liquid crystal display substrate forming a liquid crystal alignment film on the surface, and two substrates disposed in opposition to each other and formed in a gap therebetween. For example, a sandwich structure composed of a nematic liquid crystal layer with positive I anisotropy, and the long axis of the liquid crystal molecules is continuously twisted from one substrate to another substrate to 90 degrees, that is, TN ( Twisted Newatic) type TN type liquid crystal cell. The TN type liquid crystal display element driven by TF T, that is, the TFT liquid crystal panel is currently widely known as a picture tube monitor. The liquid crystal alignment system controlling the liquid crystal element is a liquid crystal alignment film. The liquid crystal alignment film is coated with a polyimide acid solution or a solvent-soluble polyimide solution which is driven by polyimide by an aniline printing method, and then fired. Film formation. However, the recent aniline printing method requires replacement of printing plates in accordance with the substrate, and therefore has a problem of complicated printing maintenance. Therefore, the ink jet printing method has attracted attention. The reason is that the ink jet method does not require a printing plate maintenance process, and can freely set the printing pattern and the liquid crystal aligning agent solution. It can also be a small amount. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) {Please (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

· Ϋ n I ϋ ϋ I n I I an mmmmm ϋ in ϋ d n n · ϋ ϋ II ϋ ϋ in ϋ ϋ ϋ · ϋ I ϋ m I

V -4- 1228614 A7 * _._ B7__ · — V. Advantages of the invention description (2), so it can reduce the cost of the LCD panel and improve the failure rate. (Please read the precautions on the back before filling this page) _Problems solved by the invention Because the inkjet printing method requires the above maintenance process, no suitable liquid crystal alignment agent has appeared, and the current polyimide and polyamic acid are The inkjet printer damage caused by the used solution and the viscosity characteristics of polyimide and polyamic acid solutions make it difficult to maintain a stable printing state. (1) The ink jet printing method requires liquid crystal aligning agent to be ejected at high speed from a fine nozzle. Therefore, the viscosity characteristic of the liquid crystal aligning agent is an important factor. That is, this solution has excellent fluidity with low resistance to strong external forces. In addition, when some organic materials are used in the nozzle material, the liquid crystal aligning agent should avoid infringing on this organic material. Therefore, it is necessary to reduce the content of solvents with strong solubility such as' N-methylpyrrolidone, which is currently used as a solvent for the liquid crystal aligning agent. Therefore, it is suitable for polyamine-based materials with high solubility in various solvents. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (2) In addition, with the increasing performance requirements of liquid crystal alignment films, a certain level of coordination is required for high voltage retention, high tilt angle, and low residual DC of a single material. . The currently known method for solving the coordination problem is to mix polyimide with better low residual DC and polyimide with better high voltage retention and high tilt angle. From the above (1) and (2), it can be presumed that the polyamic acid and the polyimide composite having excellent fluidity and solubility are suitable for ink jet printing. However, according to the inventor's research, it was found that when the polyamic acid and the polyimide were simply mixed, the two were separated due to the burden and heat during ink jet printing, which caused a lack of ejection stability as a liquid crystal alignment film Performance This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) -5- 1228614 A7 · _____ B7_- 5. Explanation of the invention (3) Stability reasons. However, the present invention is compounded by using a block copolymerization method of polyamic acid and polyimide with a completely specific structure, so it can produce excellent discharge stability, liquid crystal alignment film performance stability, and ink stability. Stable liquid crystal aligning agent for spray device. That is, an object of the present invention is to provide a novel liquid crystal aligning agent and a liquid crystal display element using the same. Another object of the present invention is to provide a liquid crystal aligning agent composed of a block copolymer comprising a polyamic acid block and a polyimide block, and a liquid crystal display device using the same. Another object of the present invention is to provide a liquid crystal alignment agent having excellent ejection stability, liquid crystal alignment film performance stability, and stability to an ink ejection device, and a liquid crystal display element using the same. -Other objects and advantages of the present invention are described below. Solution to the Problem The above-mentioned objects and advantages of the present invention can utilize block copolymers containing polyimide blocks of type 1 and polyamidic acid blocks of type 2 in the molecule, and their characteristics (please read the precautions on the back first) (Fill in this page again.) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives in the White List * 1311 types of IX.

R2 base unit is 2 R 2 alkane or proton hydrogen is 1 R Chinese formula is--· ϋ ϋ · 1 mmmmm ϋ «I Bi · —Bi · -1 ϋ ϋϋ n ϋ III -ϋ ϋ ϋ · ϋ ^ 1 ϋ ϋ -ϋ ϋ ϋ 1 · 1 ϋ 1 -ϋ ϋ ϋ ϋ ^ 1 1 ϋ · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1228614 Α7 Β7 V. Description of the invention (4 ) An integer of ~ 4, where η is a positive number of the number of repeated units) and the repeated unit shown in the following formula (2)

... (2) (wherein R3 is a divalent organic group, and m is a positive number of the repeating unit number) The repeating unit of the repeating unit group shown in the type 2 polyamine block contains at least one selected from the group consisting of The following formula (3)

j... (3) (where R6 is an M atom or an alkyl group, R7 is a divalent organic group, and Q is a positive number of repeated units) and the following formula (4) (Please read first (Notes on the back, please fill out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

... (4) (where R4 is a hydrogen atom or an alkyl group, R5 is a divalent organic group, and ρ is a positive number of repeated units) The embedded paper formed by the repeated units of the repeated unit group shown The scale is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 gong). 1228614 A7 B7 The employee property cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the fifth, invention description (5) paragraph copolymer. The present invention will be specifically described below. A liquid crystal aligning agent of the present invention contains a polyimide block of the first type having a repeating unit represented by the above formula (1) and / or formula (2), and the block having the above formula (3) ) And / or a block copolymer of a second type of polyamidic acid block represented by the repeating unit represented by formula (4). In the formula (1), R1 is a hydrogen atom or an alkyl group. The alkyl group may be linear or branched, and an alkyl group having 1 to 30 carbon atoms is preferred. R2 is a divalent organic group. A divalent alicyclic group or a divalent aromatic group is more preferable. Examples of the divalent alicyclic group or divalent aromatic group include divalent residues other than the amine group derived from the alicyclic diamine or aromatic diamine described later. The number of repeating units η is preferably 3,000, and more preferably 3 to 100. In the above formula (2), R3 is a divalent organic group, and a divalent alicyclic group or a divalent aromatic group is more preferable. The specific example is the same as the above-mentioned R2. The number of repeating units m is preferably 3 to 2,000, and more preferably 3 to 100. R7 is a divalent organic group, and is preferably a divalent alicyclic group or a divalent aromatic group. This includes, for example, a divalent residue derived from an amine group of an alicyclic diamine or an aromatic diamine described later. The repeating unit number Q is preferably 2 to 1,000, and more preferably 2 to 100. In addition, R4 in formula (4) is a hydrogen atom or an alkyl group. The alkyl group may be linear or branched, and an alkyl group having 1 to 30 carbon atoms is preferred. ~ R5 is a divalent organic group, and a divalent alicyclic group or a divalent aromatic group. Specific examples thereof may be the same as the above-mentioned R7. The repeating unit number p is preferably 2 to 1,000, and more preferably 2 to 100. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) '&quot; -8-(Please read the precautions on the back before filling this page) -------- Order --- ------ ^ 1 # ----------------------- 1228614 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6) In addition, the weight ratio (Pi) of the polyimide block of the first type in the block copolymer and the weight ratio (P2) of the polyimide acid block of the second type are preferably pi- &lt; P ~ 2, If the viscosity is increased due to a high ratio, it is not suitable for ink jet coating, and even the general flexographic printing method may deteriorate the film thickness uniformity due to poor flatness. <Manufacturing method of a block copolymer> The manufacturing method of the block copolymer of this invention is demonstrated below. The block copolymer of the present invention can be prepared by ① preparing "Step A" of a polyamine prepolymer (A) having an amine group at the molecular end, and ② preparing polyimine having a reactive group derived from a tetracarboxylic acid at the molecular end. "Step B" of the prepolymer (B) and "Step C" of reacting the poly-amidate prepolymer (A) with the polyimine prepolymer (B). The block copolymer of the present invention can be obtained from a polycarboxylic acid prepolymer having a tetracarboxylic acid terminal and a polyimide prepolymer having an amine terminal. Changes over time, so the method containing steps A, B, and C is preferred. Examples A, B, and C will be described below. Step A: In step A, a tetracarboxylic acid having an organic group RA is reacted with a diamine having an organic group Q A as in the following reaction formula 1. The number of moles of diamine used to the number of moles of tetracarboxylic acid is, for example, 1 · 001 ~ 2 times. That is, an excess amount exceeding the equivalent is used to modulate the number of repeating units Θ having an amine group at the end of the molecule. Polyamine prepolymer (A). This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm 1 ~ (Please read the precautions on the back before filling this page)

V 1228614 A7 B7 V. Description of the invention (5 X O ^^ RA 〇 ♦ NH2—QA—NH, ΤΙ

Step B: In step B, a tetracarboxylic acid having an organic group RB is reacted with a diamine having an organic group Q B as shown in the following reaction formula 2. The number of moles of tetracarboxylic acid to the number of moles of diamine is, for example, 1.001 to 2 times, that is, an excess amount exceeding the equivalent is used to modulate a polymer having a reactive group derived from a tetracarboxylic acid at the molecular end. Amino acid. Next, an imidization treatment described later is performed to obtain a polyimide prepolymer (B) having a repeating unit Mα. ‘Righteousness. ♦ HH5—QB- 〇 〇

(Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Step c: This step C is the same as step A and step B. The polyamine prepolymer obtained in step A (A ) The terminal amine group reacts with a reactive group derived from a tetracarboxylic acid at the terminal of the polyimine prepolymer (B) obtained in step B, as shown in reaction formula 3, and a nuclear atom group RA is prepared with 2 Valence Bonding Group (—C0-NH-) Bonding Organic QA Bonding Compound is Repeated Military Position -------- Order ------- 14 «· ----- ------------------ The private paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) -10 1228614 A7 B7 V. Description of the invention (8) Amidine block (A) and a 'block-copolymer' formed from a polyimide block (b) having the same unit of the nuclear atom group RB and the organic group QB as a repeating unit.

In step C, the obtained block copolymer can be a terminal-modified block copolymer having a molecular weight adjusted by using the following method. In addition, this terminal-modified block copolymer can improve coating characteristics and the like. Such a terminally modified substance can be synthesized by adding an acid monoanhydride, a monoamine compound, a monoisocyanate compound, etc. in the reaction system of Step C. This acid monoanhydride is, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, η-decylsuccinic anhydride, η-dodecylsuccinic anhydride, η-tetradecyl succinic anhydride, η-h hexasuccinic anhydride, and the like. Examples of the monoamine compound include aniline, cyclohexylamine, η-butylamine, η-heptylamine, η-hexylamine, η-heptylamine, η-octylamine, η-nonylamine, and η- Η-ylamine, η-Η-ylamine, η-h diylamine, η-hexadecylamine, η-heptadecylamine, η-octadecylamine, η-icosylamine, 3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 2-Aminopropyltrimethoxysilane, 2-Aminopropyl. Ethyltriethyl This paper size is applicable to Chinese national standards (CNS) A4 specification (210 X 297) ((Please read the notes on the back before filling out this page) Φ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ -rer _1 ϋ ai ϋ II a— I ϋ n ϋ i__i ϋ ϋ I ϋ ϋ I ϋ 1. ^ 1 ϋ ί 1 _1 ϋ ϋ ϋ ϋ -ϋ ϋ -11-1228614 A7 B7 V. Description of the invention (9) Oxygen sand institute, 3-ureidopropyltrimethoxy Shayuan, 3-ureidopropyltriethoxy sandyard, N- (2-aminoethyl) -3-aminopropylmethyl-trimethylsilylsilane, 3-aminopropyldimethyl Ethoxysilane, 3-aminopropylmethyldiethoxy sand, ρ — [N — (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane, N, N —bis [3- (trimethoxysilyl) propyl] ethylenediamine, N —3-trimethoxysilylpropyl-m-phenylenediamine and the like. Examples of the monoisocyanate compound include phenyl isocyanate, naphthyl isocyanate, 3-isocyanate, and 3-isocyanatepropyltriethoxysilane. Monoisocyanate compounds are, for example, phenyl isocyanate, naphthyl isocyanate, 3-isocyanate propyl triethoxy sand urn and the like. The tetracarboxylic acids and diamines used in step A or step B may also be used, and plural compounds of the compounds exemplified below may be used. A method in which one or more polyamine prepolymers and / or polyimine prepolymers obtained in the same step A or B are used to react in step C, or the method is made to react in step C , Can produce block copolymers containing more than three kinds of blocks. In addition, preferable specific examples of the tetracarboxylic dianhydride used in Step A are, for example, 1,2,3,4-monocyclobutanetetracarboxylic dianhydride, and 1,2-dimethyl-1,2,3,4-monocyclic. Butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetra At least one of carboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4 monocyclobutanetetracarboxylic dianhydride and pyromellitic dianhydride. In addition, the preferred specific example of the tetracarboxylic dianhydride used in step B is' This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public «) (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs I · WWW ·! · W ΑΗΒ Μ · * &gt; · a ·· t line --------------------- --12-1228614 A7 B7 V. Description of the invention (1〇) 1, 3,3 a, 4,5,9 b -Hexahydroxy-5 (tetrahydroxy-2,5-dihydroxy-3-furanyl- Naphtho [1,2-c] -furan-1 ~, 3 -dione, 1,3,3a, 4,5,9b-hexahydroxy-5 -methyl-5 (tetrahydroxy-2,5- Dicarbonyl-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydroxy-5-ethyl-5 (Tetrahydroxy-2,5-diamine-3-pyranyl) -Ceido1,2-c) monofuran-1,3-dione, 1,3,3a, 4,5,9b-A Hydroxy-7-methyl-5 (tetrahydroxy-2,5-dicarbonyl-3-furanyl) -naphtho1,2-c) -furan-1,3- Ketone, 1, 3, 3a, 4, 5, 9b —hexahydroxy-7-ethyl-5 (tetrahydroxy-2 y 5-dicarbonyl-3-furanyl) -naphtho [1,2-di-c] — Aromatic 1,3-dione, 1,3,3a, 4,5,9b Hexahydroxy-8-methyl-5 (tetrahydroxy-2,5-dicarbonyl-3furanyl) -naphtho [1,2-c] monofuran-1,3-dione, 1,3,3a, 4,5,9b -hexahydroxy-8-ethyl-5 (tetrahydroxy-2,5-dicarbonyl-3 —Furanyl) mononaphtho [1,2-c] monopyran-1,3-dione, 1,3,3a, 4,5,9b —hexahydroxy-5,8-dimethyl-5 ( Tetrahydroxy-2,5-dicarbonyl-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 2,3,5-tricarboxylic acid cyclopentylacetic dianhydride At least one of them. In addition, within the range not impairing the characteristics of the present invention, the use amount of less than 20 mol% of all the tetracarboxylic dianhydrides in step A and step B is preferably the paper standard applicable to China National Standard (CNS) A4. Specifications (210 X 297 Public Love) (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs I · n · ϋ · ϋ ί ϋ n ϋ 1: 0, * μ ·· a ·· a ··· ΜΜ I ΙΒΙΒ · a ··· II ΜΜ ΜΜ MB ΜΜΙ a ··· am I MB · MB · -13-1228614 A7 ____B7____ V. Description of the invention (), using the above acid dianhydride And tetracarboxylic dianhydride described later. Examples of the tetracarboxylic anhydride used in step A and / or step B include alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride as exemplified below. Examples of the tetracarboxylic dianhydride used in Step B used in Step A and the used amounts of the tetracarboxylic dianhydride used in Step A used in Step B are each preferably 20 mol% or less. Examples of the alicyclic tetracarboxylic dianhydride include 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 &gt;, 4,4 &gt; dicyclohexyltetracarboxylic dianhydride, 3,5,6-tricarboxyoranidine- 2-acetic acid di Anhydride, 2,3,4,5-tetrahydroxyfurantetracarboxylic dianhydride di'5 — (2,5 —dicarbonyltetrahydroxyfuran methylidene) — 1 — 3-methyl — 3 —cyclohexene 1 , 2-dicarboxylic dianhydride, bicyclic [2, 2, 2] 187-7-olefin-2, 3, 5, 6-tetracarboxylic dianhydride, compounds represented by the following formulae (5) and (6) Wait. . · (5) (Please read the notes on the back before filling out this page) Φ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

• (6) (where, R1 and R3 are aromatic divalent organic groups, and R paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm). ---- --- --- line ----------------------- -14- 1228614 A7 _____B7__ 5. Description of the invention (12) is a hydrogen atom or an alkyl group. When R2 and When R4 is plural, it can be the same or different respectively. (Please read the precautions on the back before filling this page) '' 'Aromatic tetracarboxylic dianhydride, for example, 3, 3 /, 4, 4 Acid dianhydride, 3,3 &gt;, 4,4 / -bisphenyl code tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Acid dianhydride, 3,3 &gt;, 4,4 &gt; monobisphenylethertetracarboxylic dianhydride, 3,3 &gt;, 4,4 &gt; monodimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 &gt;, 4,4 &gt; tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4 monofurantetracarboxylic dianhydride, 4, bis (3,4 dicarboxyphenoxy) diphenyl Sulfide dianhydride, 4,4-bis (3,4-dicarboxyphenoxy) diphenyl code dianhydride, 4,4-bis (3,4-dicarboxy'ylphenoxy) diphenyl base Propane dianhydride, 3, 3 &gt;, 4, 4, 1 Peroxoisophthalic dianhydride, 3, 3 &gt;, 4, 4 &gt; bisbenzene printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Tetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide diacid, P-phenylene-bis (triphenylphthalate) dianhydride, m-phenylene-bis (triphenyl) Phthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4 / diphenyl ether dianhydride, bis (triphenylphthalic acid) 4, diphenyl ether dianhydride Bis (triphenylphthalic acid) -4,4 &gt; monodiphenylmethane) dianhydride, ethylene glycol bis (anhydrotrimelate), propylene glycol bis (anhydrotrimelate) ), 1,4-butanediol-bis (anhydrotrimelate), 1,6-hexanediol-double (anhydrotrimelate), 1,8-octanediol-double (Anhydrotrimelate), 2,2-bis (4-monohydroxyphenyl) propane-bis (anhydrotrimelate), compounds represented by the following formulae (7) to (10), and the like. . This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -15- 1228614 A7 _____B7 V. Description of the invention (13)

\ y

8) (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

9) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -16-1228614 A7 B7 V. Description of the invention (14) The diamine compound used in step A and / or step B, such as aliphatic Diamine compounds, aromatic diamine compounds, and the like. '' Aliphatic diamine compounds such as 1,1-m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethyldiamine, hexamethylenediamine, heptamethyldiamine , Aliphatic diamines such as octamethyldiamine, pentamethylenediamine, 4,4-diamino heptamethylenediamine; 1,4-diaminocyclohexane, isophoronediamine, tetraamine Hydroxybicyclopentadienyldiamine, hexahydroxy-1,7-methyleneindane didimethylene diamine, tricyclic [6 · 2 · 1 · 02 · 7] -undecane dimethyldiamine Amine, 4,4 / monomethylenebis [cyclohexylamine], 1,3-bisaminomethylcyclohexane, 2,5-bis (aminomethyl) bicyclo [2 · 2 · 1] heptane Alicyclic diamines such as alkane, 2,6-bis (aminomethyl) bicyclo [2 '/ 2 · 1] heptane; diamine-based organosiloxanes shown in the following formula (11).

(In the formula, R9 is a hydrocarbon group having 1 to 12 carbons. When R9 is plural, they may be the same or different, r is an integer of 1 to 3, and s is an integer of 1 to 20.) Aromatic diamine compounds such as, p-phenylenediamine, m-phenylenediamine, 4,4 &gt; monodiaminodiphenylmethane, 4, diaminodiphenylethane, 4, diaminodiphenylsulfide , 4,4 &gt; monodiaminodiphenyl code, 4, diaminodiphenyl ether, 3,5-diaminobenzoic acid, 1, hexadecylalkyl-2,4-diamine Benzene, 3 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 cm) (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs • · 1 ϋ ammm ί ί 1 _1 a dj, · n · 1 emt 1 ϋ ϋ II ϋ I ϋ n an ϋ ϋ ϋ ϋ n ϋ n ϋ ϋ ϋ n ϋ ϋ · ϋ ϋ A · A7 1228614 B7_ V. Description of the invention (15), 3, dimethyl-1,4,4-diaminodiphenyl, 4,4 / monodiaminophenylanilide, 4,4 / monodiaminodiphenyl ether, 1,5-(Please (Read the precautions on the back before filling out this page.) , 3-Dimethyl-4,4 &gt; mono-diaminodiphenyl, 5-amino-1- (4-monoaminophenyl) -1,3,3-trimethylbenzyl, 6- Amino-1— (4-aminoaminophenyl) -1,3,3-trimethylindane, 3,1-diaminodiphenyl ether, 3,1-diaminophenylbenzene, 3,1 Diaminophenylbenzene, 4, diaminophenylbenzene, 2,2-bis [4-mono (4-monoaminophenoxy) phenyl] propane, 2,2-bis [4 one (4- Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis-4 monoaminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4 Mono (4-monoaminophenoxy) 'phenyl] code, 1, 4-bis (4-monoaminophenoxy) benzene, 1,3-bis (4-monoaminophenoxy) benzene, 1 , 3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminoaminophenyl) -10-hydroxyanthracene, 2,7-diaminofluorene, 9,9-bis (4 Monoaminophenyl) hydrazone, 4,4 &gt; monomethylene-bis (2-chloroaniline), 2,2 &gt;, 5, 5 / -tetrachloro-4, -diaminodiphenyl, 2,- Dichloro-4,4 / monodiamine-5 5 · &quot; —dimethoxydiphenyl, 3, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 3 &gt; —dimethoxy-4,4 / monodiaminodiphenyl, 3,3 # — Dicarboxy-1,4,4-diaminodiphenyl, 3,3 # —Dihydroxy-1, 4-diaminodiphenyl, 4,4, 1 (P —phenylene diisopropylidene) Diphenylamine, 4, mono (m-phenylene diisopropylidene) diphenylamine, 2, 2 / -bis [4-mono (4-monoamino- 2-trifluoromethylphenoxy) phenyl] hexafluoropropane 4, 4, diamino-1,2, 2'-double (This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -18- Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs 1228614 A7 B7 V. Description of the invention (16) Aromatic difluoride, such as trifluoromethyl) diphenyl, 4,4'-bis [(4-monoamino-2-trifluoromethyl) phenoxy] -octafluorodiphenyl Amine; 2 '3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyridine, 5,6-diaminopyridine 2,3 -Dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2 4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6- Isopropoxy-l, 3,5-triazine, 2,4-diamino-6-phenyl-l, 3,5-triazine, 2,4-diamino-6-methyl One s-triazine, 2,4 diamino group 1,3,5-triazine, 4,6-diamine group 2-vinyl-s-triazine, 2,4 diamine 5-diphenylazole, 2,6-diaminopurine, 5,6-diamine ^ yl-1,3-dimethyluracil, 3,5-diamino-1,2,4- Triazole, 6,9-diamino- 2-ethoxyacridine lactate, 3, 8-diamino-6-phenylphenanthrene, 1,4-diaminopyridine, 3 * 6 —Diamino azine, bis (4-aminoaminophenyl) phenylamine, compounds represented by the following formulae (12) to (13) have two primary amine groups and other nitrogen atoms in the molecule X-Rl ° ... ⑽H2N nh2 (wherein R 1 ^ is a monovalent compound having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine, and piperazine Group, X is a divalent organic group. ） This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) IAW -------- Order ------- —Line ----------------------- -19- 1228614 A7 B7 V. Description of the invention (17)

H2N 0X-RlLX0 NH2 (13) (wherein R11 is a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X is a divalent organic group, When X is plural, they may be the same or different.) Mono-substituted phenylenediamines represented by the following formula (1 4); h2n

Pr13 .. (14) (Please read the precautions on the back before filling out this page) NH, (where YR12 is selected from -0-, -COO-, 10c02,-NHCO-, -CONH-and A co-valent divalent organic group, R13 is a nested skeleton, a monovalent organic group having a group selected from a difluoromethyl group and a fluoro group or an alkyl group having 6 to 30 carbon atoms.) Or the following formula (χ 5) Compounds shown in (27) and the like. Moreover, they can be used individually or in combination of 2 or more types. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs; 0 ------- --Order --------- line 丨 ^^ ---------------- ------- The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) • 20 · 1228614 A7 B7 V. Description of the invention (! 8)

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -21 · 1228614 A7 B7 V. Description of the invention (19) COO-CH2CH2

~ 〇 (20) H2N-V &gt; -NH2 Off-〇 ^ CHCH2V〇-〇-Post (21) H3Cοοο-ύ ^

CH3 H3C CH (CH2) 3CH CH3 CH3 (22) A Η2Ν-\ ^ ~ ΝΗ2 CH3

(23) ^ CH3

------------ # (Please read the notes on the back before filling out this page) Order · — Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

H2N

OOC- (27). Line 1 ♦ ----------------------- This paper size is applicable to the Chinese national standard Jiege grid (gang ™ 1228614 A7 B7 economy Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau. 5. Description of the invention (20) Among them, 1,4-diaminocyclohexane, isophorone diamine, 1-hexadecyloxy-2, 4-12 Aminobenzene, Tetrahydroxydicyclopentadienediamine, ~ Hexahydroxy-4,7-methyleneindane dimethylene diamine, Tricyclic [6 • 2.1.027] Undecane Dimethyldiamine, 4,4 &gt; monomethylbis (cyclohexylamine), 1,3-bisaminomethylcyclohexane, 2,5-bis (aminomethyl) bicyclo [2 · 2 · 1] heptane, 2,6-bis (aminomethyl) bicyclo [2 · 2 · 1] heptane, 4, monodiaminodiphenylphosphine, 4,4 &gt; monodiaminodiphenyl Base code, 4, diaminodiphenyl ether, 3,5-diaminobenzoic acid, 2,2-bis (4-aminoaminophenyl) -1,1,1,3,3,3- Hexafluoropropane, p-phenylenediamine, 4,4 ^ -diaminodiphenylmethane, 4,4 diaminediphenylethane, 3,3 dimethyl-4,4 ... didiamine two Group, 2,2-bis [4-mono (4-aminoaminophenoxy) phenyl] propane, 1,4-bis (4-aminoaminophenoxy) benzene, 1,3-bis (4-monoamino Phenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminoaminophenyl) ) 10-hydroxyanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminoaminophenyl) fluorene, .3,3 &gt; -dimethoxy-4,4 / monodiamine Diphenyl, 4,4 &gt; mono (p-phenylene diisopropylidene) diphenylamine, 4, mono (m-phenylene diisopropylidene) diphenylamine, 1, 1-m-xylylenedimethyl Amine, 1,3-propanediamine, tetramethylenediamine, pentamethyldiamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4 one two Heptamethylene diamine, preferably the compounds represented by the above formulae (15) to (27), etc. _ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the back Please fill out this page again)-· i · — i_i · 1 1_ * Αϋ 11 1: OJ · ΙΒΒ1 1 n «ϋ ϋ I -line ---------------- ------- -23- 1228614 A7 B7 V. Description of the invention (21) Moreover, these diamines can be used alone or in combination of two or more. The reaction of steps A, B and C is preferably in an organic solvent Medium ~ 20′0 ° 0 :, and again at 0˜100 ° (: better temperature. The organic solvent used in this reaction is one that can dissolve the acid produced, and there is no particular limitation. For example, NN, N-dimethylacetamide, N, N subcode, r-butyrolactone, Methyl urea is a polar solvent; m-cresol, a phenolic solvent printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs of Xylene. The used amount of the organic solvent is preferably 0.1 to the total amount of the reaction solution. These organic solvents may be weak solvents such as alcohols, ketones, ethers, and halides capable of prepolymers. Examples of such weak solvents are alcohol, acetone, methyl ethyl ketone, methyl isopropyl, butyl acetate, diethyl malonate, ether ethylene glycol ethyl ether, ethylene glycol propyl ether tetrahydroxyfuran, Ethyl chloride, chlorobenzene, benzene, etc. In step B, the imidization reaction is to use polyimide after dissolving the substance (polyamidide) in an organic solvent, adding the solution to the ring-closing catalyst, and then heating the solution. The dehydrating agent used is, for example, acid anhydride such as acetic anhydride. The amount of dehydrating agent used is the total amount of polyamidomonomethyl-2-pyrrolidone, dimethylformamide, dimethyl and other inferior phenols, hexamethylphosphorylamine, phenol, halogenated quart Carboxylic acids and diamines ~ 30% by weight. Do not precipitate the generated polyamidated hydrocarbons, hydrocarbons such as ethanol, cyclohexanol, propylene dibutyl ketone, cyclohexanone, ethylene diethyl ether acetate, ethylene glycol, methyl, Ethylene glycol ethyl ether acetate, hexane, heptane, toluene, and dimethyl are formed in the middle of Reaction Formula 2, and a dehydrating agent and a dehydration method are performed if necessary. In addition, the applicable part of step B can be dehydrated and closed-loop reaction. Repeated units of acetic anhydride, propionic anhydride, and trifluoro-p-amino acid 1 This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) Please read the notes on the back first and then fill out this page-24-1228614 A7 B7 V. Description of the invention (22) (Please read the notes on the back before filling out this page) The gram molecule is preferably from 0.01 to 20 grams. Examples of the dehydration ring-closing catalyst used include tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethyl-amine. However, it is not limited to this. The amount of the dehydrating closed-loop catalyst is preferably 0.01 to 10 mol per mol of the dehydrating agent used. As for the organic solvent used in the dehydration ring-closing reaction, the above examples can be exemplified. The reaction temperature of the dehydration ring-closing reaction is generally 0 to 180 ° C, and preferably 10 to 150 ° C. These block copolymers have two or more different types of polyimide-based blocks and polyamic-acid-based blocks, which are different from each other. In addition to the original characteristics of polyimide, it also has the characteristics of multiple types of polyimide or polyimide homopolymer of each block. That is, for example, when different blocks of the first type of polyimide component and the second type of polyimide component coexist in the molecule, the first type of the polyimide homopolymer constituting the first type of block may be present at the same time. Characteristics and the second characteristic of the polyamic acid homopolymer constituting the second type of block. Therefore, the characteristics of the block copolymer may be modified depending on the characteristics of the polyimide homopolymer constituting the block or the characteristics of the polyamic acid homopolymer constituting the other blocks. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs These characteristics cannot be obtained by simply mixing type 1 polyimide and type 2 polyamic acid, and even if any type 1 polyimide and type 2 polyamic acid are manufactured All the tetracarboxylic acids and diamines used could not be obtained by reaction. That is, the block copolymer of the present invention is a copolymer having a plurality of good characteristics which are difficult to obtain by a conventional method. The characteristics of the block copolymer of the present invention may depend on the structure of the repeating units on each block constituting the object and the number of the repeating units or the ratio thereof. Because this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) • 25 · 1228614 A7 B7 V. Description of the invention (23) Therefore, when controlling these factors, the resulting polyimide system can be controlled Characteristics of segmented copolymers. In other words, when selecting the type of tetracarboxylic acid and diamine used for the formation of each block, or adjusting the amount of use, when using the ratio, the type and ratio of the total number of blocks constituting the block copolymer can be controlled, and the final result can be controlled. Characteristics of block copolymers. <Liquid crystal aligning agent> The liquid crystal aligning agent using the above-mentioned block copolymer will be described below. The content rate of the block polymer of the liquid crystal aligning agent of the present invention may be appropriately selected according to viscosity, volatility, etc., but it is preferably 0.1 to 20 weight '_% by weight for the entire liquid crystal aligning agent, and 1 ~ 10% by weight is preferred. That is, when the liquid crystal aligning agent formed by the polymer solution is applied on the surface of the substrate by using the ®Γ method, the spin coating method, and then dried to form a film as an alignment film material, if the polymer content is lower than 0 · At 1% by weight, the film thickness of the film will be too thin to obtain a good liquid crystal alignment film, and when it exceeds 20% by weight, the film will not be able to obtain a good liquid crystal alignment film due to the current thickness, and the liquid crystal alignment will be increased. The viscosity of the agent deteriorates the coating characteristics. The liquid crystal aligning agent used in the present invention is characterized in that it contains a block copolymer having a specific structure. However, without impairing the effects of the present invention, polyamic acid and / or polyimide of other structures can be mixed. '' The organic solvent used to dissolve the polymer is not particularly limited as long as it can dissolve the polymer. For example, it is an example of a synthetic reaction for polyamic acid or a dehydration ring closure reaction. In addition, you can use the appropriately selected paper that can be used in the synthesis of polyamic acid. This paper applies the Chinese national standard Yi Weige (Key 97 public good (please read the precautions on the back before filling this page). · Ministry of Economic Affairs Printed by the Intellectual Property Bureau Employee Cooperatives 0 I ϋ ϋ ϋ ϋ I 1 I ϋ ϋ I ϋ ϋ ί II ϋ ϋ ϋ ϋ ϋ ϋ I ϋ .1 ϋ ϋ ϋ ϋ ϋ 12-1228614 A7 B7 V. Description of the Invention (24 ) An example of a suitable weak solvent. When the liquid crystal aligning agent of the present invention is applied by the ink jet method, the content of N-methylpyrrolidone is preferably 20% by weight or less of the solvent from the viewpoint of suppressing damage to device parts. From the viewpoint of improving the adhesion between the polymer and the surface of the substrate for coating, the liquid crystal aligning agent used in the present invention may be added with a functional silane-containing compound or an epoxy-containing compound. This functional silane-containing compound is, for example, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoaminoethyl) Mono-3-aminopropyltrimethoxysilane, N- (2-aminoethyl ) 3-Aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl S di3-amine Propyltrimethoxysilane, N-ethoxyviolyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxymethyl Silylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triaza Decane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,7-diazanonyl acetate, N-benzyl -3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl Mono-3-aminopropyltriethoxy sand, N-bis (via ethylene) -3-aminopropyltrimethoxysilane, N-bis (hydroxyethylene) -3-aminopropyl Triethoxysilane and the like. Preferred epoxy-containing compounds are, for example, ethylene glycol diepoxypropyl. This paper scale is applicable to Chinese gardeners' standard play format, remuneration) -27 · (Please read the notes on the back before filling in this page) Lu -------- Order-—Employee Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs Printed line I # ----------------------- 1228614 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (25) Ether , Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol di-epoxy diyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1, 3, 5, 6-tetraepoxy Propyl-2,4-hexanediol, 1 ^ ,? ^, 1 ^ /, —tetra-glycidyl-m-xylenediamine, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, n, N, N &gt; , N-tetraepoxypropyl-4,4-diaminodiphenylmethane, 3- (N-allyl-N-epoxypropyl) aminopropyltrimethoxysilane, 3- (N, N-diepoxypropyl) aminopropyltrimethoxysilane and the like. Among them, compounds containing a third-order nitrogen atom in the molecule are more preferable. The addition rate of these compounds is generally less than 40 weight units for the polymer 100 weight unit, and preferably 0. 1 to 30 weight units. <Liquid crystal display element> The liquid crystal display element of the present invention obtained by using the liquid crystal aligning agent of the present invention can be produced by the following method. (1) A liquid crystal aligning agent is applied to a substrate provided with a patterned transparent conductive film on the transparent conductive film side by, for example, a roll coating method, a spin coating method, a printing method, or the like, and then the coated surface is heated to form a composite film. The substrate used can be made of glass such as wide glass, soda lime glass, or plastic films such as polyethylene terephthalate, polybutyl terephthalate, polyether code, polycarbonate, etc. Transparent substrate. The transparent conductive film provided on one surface of the substrate may be a NESA film formed of Sn〇2, an In2〇3-Sn.〇2

The size of the mound paper is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 male H (please read the precautions on the back before filling in this page) Φ 0 ϋ ϋ aHi 1 · a— _1 ϋ ϋ · 1 ϋ ϋ 1_ # · ^ 1 # ----------------------- -28- 1228614 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of Invention (26) Formation I TO film, etc. The patterning of these transparent conductive films can use the photo-etching method, or the method of preparing a mask, etc.-When coating the liquid crystal alignment agent, in order to further improve the adhesion of the substrate and the transparent conductive film to the coating film, A functional silane-containing compound, titanate, etc. are coated on the substrate and the transparent conductive film in advance. The current coating method is mainly the aniline printing method. In addition to the aniline printing method, the liquid crystal aligning agent of the present invention can also use ink. Jet printing method. The drying temperature of the coating film is preferably 80 ~ 250 ° C, and more preferably 120 ~ 200 ° C. The thickness of the formed film is generally 0. 001 ~ l // m, and 0. 005 ～ 0 · 5 # πι is better. The formed film can be used, and it can be wrapped with nylon, rayon or cotton, etc. The rollers of the cloth shaped by the fibers are subjected to a scrubbing treatment in a certain direction to impart orientation energy to the liquid crystal molecules of the film to form a liquid crystal alignment film. In addition, in order to remove the fine powder (foreign matter) generated during the scrubbing treatment to make the film The surface becomes clean, and the formed liquid crystal alignment film can be washed with isopropyl alcohol. In addition to the scrubbing treatment, the surface of the film can be irradiated with polarized ultraviolet rays, ion beams, electron beams, etc. to impart orientation energy. Or, a method of obtaining a film by a uniaxial stretching method, a Lammill projection method, or the like, to form a liquid crystal alignment film. Also, the liquid crystal alignment film formed after the above processing is used, for example, Japanese Patent Application Laid-Open No. 8-234207, The treatment methods disclosed in Kaiping Publication No. 7-168187, JP-A Publication No. 6-222366, or JP-A Publication No. 6-2 8 1 9 3, etc., partially irradiate ultraviolet rays, ion beams, and electron beams to change the inclination angle, or This paper size applies to China National Standard (CNS) A4 specification (210 X 297 cm) (Please read the precautions on the back before filling this page) # Order --------- line 丨 Φ 29 · 1228614 A7 B7 V. Description of the invention (27) JP 5-1 0 7 5 4 4 discloses that after forming a photoresist film on a part of the liquid crystal alignment film which has been subjected to the above-mentioned alignment treatment, the former liquid solution is performed. The orientation method of different orientations in the crystal orientation, and the treatment method of removing the photoresist film to change the orientation energy of the liquid crystal alignment film can improve the visual field characteristics of the liquid crystal display element. (3) Making 2 pieces to form the liquid crystal alignment as above The substrate of the film, and the oblique direction of the liquid crystal alignment film is orthogonal or antiparallel, so that the two substrates face each other with a gap (cell gap) facing each other, and then use a sealant to attach the periphery of the two substrates, and then The liquid crystal is inserted into the cell gap drawn on the surface of the substrate and the sealant area, and the filling hole is sealed to form a liquid crystal cell. Next, the outer surface of the liquid crystal cell, that is, the other side of the respective substrates constituting the liquid crystal cell, is bonded in such a manner that the direction of the 1 is reversed and the liquid crystal alignment film formed on one side of the substrate is aligned or orthogonal A polarizing plate to obtain a liquid crystal display element. The sealant used is, for example, a hardener and an epoxy resin containing aluminum oxide balls as a distance adjuster. The liquid crystal is, for example, a nematic liquid crystal or a butterfly liquid crystal. Among them, nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azo oxide liquid crystals, bisphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, biphenyl liquid crystals, Biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubic liquid crystals, and the like. In addition, for these liquid crystals, for example, cholesteryl liquid crystals such as cholestanol chloride, cholesteryl nonanoic acid vinegar, cholesteryl carbonate, or trade names "C-15", "CB-15" (US Potassium Magnesium, etc., commercially available from Luku). In addition, you can use P-desilabenzyl -P-amine-2-methyl butyl paper size applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back first (Fill in this page again) -------- Order · —Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-line _ ^ -------------------- ---- • 30-1228614 A7 B7 V. Description of the invention (28) Strong dielectric liquid crystal such as cinnamate. In addition, the polarizing plate used on the outer side of the liquid crystal cell is, for example, a polarizing film called a holmium film or a polarizing film formed of a holmium film, which is a cellulose acetate `` protective film '' that holds polyvinyl alcohol to extend the orientation and absorbs iodine. Board etc. Hereinafter, the present invention will be specifically described by examples, but is not limited to this example. In addition, the properties of the liquid crystal aligning agents prepared in the examples and comparative examples and the performance evaluation methods for liquid crystal display devices are as follows. [Solubility of Block Copolymer] A butyl cellosolve as a weak solvent was added to 50 g of a liquid crystal aligning agent of a butyrolactone solution whose solid content concentration was adjusted to 4% by weight, until a precipitate was formed, and The butyl cellolytic dose at this time was taken as the solubility index. The more the amount added, the better the solubility. [Ink Jet Coating Property] Using a device of JET-CM continuous ink jet coating machine (manufactured by Kishu Technology Co., Ltd.), a directing agent solution having a solid content concentration adjusted to 2% by weight was coated on an ITO substrate , So that the dry film thickness of the liquid crystal aligning agent becomes 8 〇 Α. Next, it was dried at 180 ° C, and the unevenness of the dried film was measured with a stylus film thickness meter. The uniformity of the film thickness was evaluated based on the difference between the maximum film thickness and the minimum film thickness. In addition, the film thickness uniformity at the start of ink jet coating and 5 hours after continuous coating were compared to evaluate printing stability, and a difference between the start and 5 hours after the start was considered to be good. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) Φ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

1-0, · ϋ &gt; ϋ I 1 ϋ III ϋ 1 I ϋ ϋ ϋ ϋ &gt; ϋ II t II 1 · 1 n ϋ ϋ ϋ ϋ I ϋ ϋ · ϋ ϋ I Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1228614 A7 __B7___ V. Description of the invention (29) [Liquid crystal directivity] Observe whether there is an abnormal area in the liquid crystal cell when the switching voltage on the liquid crystal display element is observed with a micro-mirror. [Tilt angle of liquid crystal display element] According to the method described in Γ T · J · Schffer, et al., J · Appl. Phys ·, Vol · 19, 2013 (1980), "H The e-N e laser light was measured by the crystal rotation method. [Voltage holding rate of the liquid crystal display element] After applying a voltage of 5 V to the liquid crystal display element at an additional time of 60 microseconds and a time interval of 500 milliseconds, the voltage holding rate after the application of the voltage was released to 500 milliseconds was measured. The measuring device used was VHR-1 manufactured by Dongyang Iron & Steel Co., Ltd., and was performed at 60 ° C. [Residual image erasing time of the liquid crystal display element] After applying a DC voltage of 20 V to the liquid crystal display element for 24 hours, the time until the residual image erasing was visually observed. Synthesis Example 1 <Step A> Preparation of polyfluorinated acid prepolymer 64.14 g of pyromellitic dianhydride, 1, 2, 3, 4 monocyclobutanetetracarboxylic dianhydride 1 34 · 56 and 4, 4 &gt; 198 · 27g of monodiaminodiphenylmethane is dissolved in N-methyl-1-2-pyrrolidone. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before reading) (Fill in this page). 丨 丨 丨 丨 丨 丨 Order · ——— 丨 丨 丨 ·· line— · • 32 _ 1228614 A7 _______B7 _V. Description of the invention (3〇) 1 6 0 〇g, in 2 0 Reaction at ° C for 6 hours. Second, a large excess of acetone is injected into the obtained reaction solution to precipitate the reaction product, and the product is precipitated, separated, washed, and dried to obtain a logarithmic viscosity (π / η) 1 · 8 d 1 / g. Polyamine prepolymer (A-1) 4 0 0 · 3 g 〇 <Step B> Preparation of polyimine prepolymer: 1, 3, 3 a, 4, 5, 9b—hexahydroxy-8—methyl -5-(tetrahydroxy-2,5-dihydroxy-3 -furanenyl-naphtho [1,2-c] pyran-1'3 -monofluorene146 · 48g, ρ-phenylene diamine 46 56g and the compound 6 · 9ig represented by the above formula (16) were dissolved in 800 g of N-methyl-2-pyrrolidone and reacted at 20 ° C for 26 hours. Next, a large excess of acetone was injected into the reaction The solution was used to precipitate a reaction product (polyamine prepolymer). After dissolving 120.0 g of the obtained polyamine prepolymer in 600 g of r-butyrolactone, 44 g of pyridine and 56 g of acetic anhydride were added. Perform dehydration and closed-loop reaction at 60 ° C for 2 hours. Then precipitate, separate, wash, and dry (please read the precautions on the back before filling this page). Fe Cooperative Co., Ltd. prints g, poly 1 pred, amine 6 and 7 poly • ο groups} iF η acid \ with (with terminal end tackon. Count points bo to 2 to get% ·, ο 7 objects 9 9 Yield} Biochemical 1 amine | Anti-sub B 0 '(and γ in solution 8) x -S 1 ο I 2 A) (1 thing I. Poly B pre &lt; amine acid polyamine polyfluorene The pre-polyamine segment is made by the sub-embedding of poly-A, obtained by A &gt; step C, step B, step B- · ϋ n II ί ϋ · * 1— ϋ ϋ ϋ ϋ «I · -1 · I -I ϋ ϋ ϋ 1 · 1 I · 1 ϋ 1.1 i_i i · — ϋ H ϋ .1 H ϋ ϋ ϋ I ϋ-This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) -33 -1228614 Α7 Β7 V. Explanation of the invention (31)-In the butyrolactone, the solid content concentration of the solution is 4% by weight. As a result, the viscosity of the solution is 17mPa · s. Secondly, the reaction at 40 ° C is 24 hours, A solution of the block copolymer was obtained, and the viscosity of the solution after the reaction was 20 mPa · s, and the logarithmic viscosity (; // η) of the obtained block copolymer (1) was 1.64 dl / g. Synthesis Example 2 <Step A> Preparation of polyfluorene prepolymer is the same as step A in Synthesis Example 1 to obtain polyfluorene. Acid prepolymer (A-1) <Step B_> Preparation of polyimide prepolymer-except for changing the raw materials for synthesis to 1, 3, 3 a, 4, 5, 9 b —hexahydroxy-8-methyl One 5 — (tetrahydroxy-2,5-dihydroxy-3-furanenyl-naphtho [1,2, c] furan-1,3-dione 1 3 2. 3 1 g. 4,4 &gt; a Diaminodiphenylmethane 11.92g, P-phenylenediamine 30.35g and compound 2 5 · 4g shown in the above (20). The other steps are the same as in step B of Synthesis Example 1 to obtain the logarithmic viscosity (τ ? / η) 0. 73d Ι / g, polyimide prepolymer (B-2) with an acid anhydride group at the molecular terminal of 94% imidization rate of 2 5 · 3 g. 〈Step C〉 Manufacture of block copolymer. Polyamine prepolymer (A-180 g and paper size applicable to Chinese national standard _Na (Guang Qing) · 34_) (Please read the back first) Note: Please fill out this page again.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 0 · -ir »J · ϋ ml ϋ ϋ ϋ ϋ ϋ I ^ 1 ϋ ϋ« ϋ ϋ I · 1 1 1 ϋ ϋ ϋ ϋ ϋ I ϋ n II ϋ III · 1228614 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (32), 20 g of the polyimide prepolymer (B-2) obtained in step B was dissolved in r-butyl In the lactone, the solid content concentration of the solution is 4% by weight. Result_The viscosity of the solution is 17mPa · s. Secondly, it is reacted at 40 ° C for 24 hours to obtain a solution of the block copolymer. The viscosity of the solution after the reaction It was 20 mPa · s, and the logarithmic viscosity (;? / Η) of the obtained block copolymer (2) was 1.65 dl / g. Synthesis Example 3 <Step A> Preparation of a polyamine prepolymer is the same as Synthesis Example 1 In step A, a polyamine prepolymer (A-1) is obtained. <Step B> The polyimide prepolymer is prepared by converting 1, 3, 3a, 4, 5, 9b to hexahydroxy-8. —Methyl mono 5-(tetrahydroxy_2,5-dihydroxy-1 3-furanenyl-naphtho [1 '2 — c] pyran-1,2-dione 267 · 16g, 2

3,5-tricarboxycyclohexylacetic anhydride 33 · 63g, p-phenylenediamine 72 · lg, 4, diaminodiphenylmethane 47 · 21g, and 24 · 9g shown by the above formula (16) are dissolved It was reacted in 1800 g of N-methyl-2-pyrrolidone at 20 ° C for 26 hours. Next, a large excess of acetone was injected into the obtained reaction solution to precipitate a reaction product (polyamine prepolymer). 30 g of the obtained polyamidic acid prepolymer was dissolved in 150 g of r-butyrolactone, 11 g of pyridine and 14 g of acid anhydride were added, and dehydration and ring closure were performed at 60 ° C. for 2 hours. The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

-35- 1228614 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (33) The steps of precipitation, separation, washing and drying of the reaction products are obtained. Logarithmic viscosity (τ? / Η) 0 · 66d Ι / g, 90% of imidization-polyimide prepolymer (B-3) with acid anhydride group at the molecular end 29 · 3g <Step C> Manufacturing block copolymer The polyamidamine obtained in Step A 80 g of the acid prepolymer (A-1) and 20 g of the polyimine prepolymer (B-3) obtained in step B were dissolved in r-butyrolactone so that the solid content concentration of the solution became 4% by weight to obtain a block. Copolymer solution. The viscosity of the solution after the reaction was 20 mPa · s, and the logarithmic viscosity (τ? / Η) of the obtained block copolymer (3) was 1.61 d 1 / V. … Synthesis Example 4 <Step A> Preparation of Polyamine Prepolymer Same as Step A of Synthesis Example 1 to obtain Polyamine Prepolymer (A — 1) <Step B> Preparation of Polyimide Prepolymer 2,4.2 g of 3,5-tricarboxycyclopentylacetic anhydride, 9 2 · 7 g of P-phenylenediamine and 49 · 78 g of the compound represented by the above formula (16) are dissolved in N-methyl-2-pyrrolidone In 2000g, it was reacted at 60 ° C for 6 hours. Secondly, a large excess of acetone was injected into the obtained reaction solution to make the reaction product (polyamic acid prepolymer: r sink. Lake. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) (Please read the notes on the back before filling this page) _ ·

t rdJ · · ϋ ϋ ϋ n 1 II ϋ · ϋ 1 ϋ · 1 n ϋ ϋ III i_i 1 n II ϋ n ϋ l ϋ I -36- 1228614 A7 B7 V. Description of the invention (34) After polymer 30 · Og was dissolved in 200 g of N-methyl-2-pyrrolidone, 17 g of pyridine and 11 g of acid anhydride were added, and dehydration and ring closure were performed at Ί 1 _0 ° C for 4 hours. Then, the reaction product is subjected to precipitation, separation, washing, and drying steps to obtain a polyimide prepolymer having a logarithmic viscosity (T7 / n) of 0 · 5d 1 / g and an imidization rate of 80% with an acid anhydride group at the molecular terminal. (B-4) 28.3g. <Step C> Production of a block copolymer A polyimide prepolymer (A-1) 80 g obtained in step A and 20 g of a polyimine prepolymer (B-4) obtained in step B were dissolved in r-butyl In the ester, the solid content concentration of the solution was 4% by weight, and the viscosity of the solution was 5 mPa · s. It was allowed to react for 24 W at 40 ° C to obtain a block copolymer solution. The viscosity of the solution after the reaction was 18 mPa · s, and the logarithmic viscosity (;? / Η) of the obtained block copolymer (4) was 1.60 dl / g. Synthesis Example 5 <Step A> Preparation of polyamine acid The polymer is the same as Step A in Synthesis Example 1 to obtain a polyimide prepolymer (A-1) <Step B> Preparation of a polyimide prepolymer is the same as Step B in Synthesis Example 1 to obtain a polyimide prepolymer ( B-1). This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs; 0 ------ --Order --------- line 丨 ----------------------- -37 · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1228614 A7 B7 V. Description of the invention (35) <Step C> Production of block copolymer The polyimide prepolymer (A — 1) obtained in step A 60 g; S :, polyimide obtained in one step 40 g of the prepolymer (B-1) was dissolved in 7-T lactone so that the solid content concentration of the solution was 4% by weight, and the viscosity of the solution was 18 mPa · s. The reaction was carried out at 40 ° C for 24 hours to obtain a block copolymer solution. The viscosity of the solution after the reaction was 23 mpa # s, and the logarithmic viscosity (τ? / Η) of the obtained block copolymer (5) was 1 · 7 0 d 1 / g. Synthesis Example 6 <Step A> Polyamine prepolymer was prepared in the same manner as in step A of Example 1 to obtain a polyamine prepolymer (a_γ). 〈Step B〉 Polyimide prepolymer was prepared in the same way In Step B of Synthesis Example 1, a polyimide prepolymer (B-1) was obtained. <Step C> Production of a block copolymer. 30 g of the polyamine prepolymer (A-1) obtained in step A and 70 g of the polyimine prepolymer (B-1) obtained in step B were dissolved in r-butyl In the lactone, the solid content concentration of the solution was 4% by weight. As a result, the viscosity of the solution was 16 m P a · s. The reaction was carried out at 40 t for 24 hours. The log viscosity (τ? / Η) of the obtained block copolymer (6) was 1.60 0 d 1 / g. ·. This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Φ

^ eJ · 1 n I ί -ϋ ϋ ϋ I ϋ · ϋ n ϋ n · ϋ I 1 ϋ ϋ ϋ ϋ ϋ ϋ 1 I β— · 1 1 · mmmt H ϋ I • 38-Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative 1228614 Δ7

Pit B7 V. Explanation of the invention (36) Synthesis Example 7-<Step A> Preparation of polyfluorinated acid prepolymer Pyromellitic dianhydride 5 1 · 88 g and 4, 4 &gt; Monodiaminodiphenylmethane 48.12 g was dissolved in 600 g of N-methyl-2-pyrrolidone, and then reacted at 20 ° C for 6 hours. Next, a large excess of acetone was injected into the obtained reaction solution to precipitate the reaction product, and the reaction product was subjected to the steps of precipitation, separation, washing, and drying to obtain a log viscosity (/? / Η) of 1.4 d / g. Polyamine prepolymer (A — 2) with an amine group at the molecular end 9 5 g 0 <Step 'B _> Preparation of polyimide prepolymer ... Same as step B of Synthesis Example 1 to obtain a polyimide prepolymer (B — 1). <Step C> Production of a block copolymer The polyimide prepolymer (A-2) 80g obtained in step A and 20g of the polyimine prepolymer (B-1) obtained in step B were dissolved in r-butyl In the ester, the solid content concentration of the solution was 4% by weight. As a result, the viscosity of the solution was 15 mPa · s. It was allowed to react for 24 hours at 40 ° C to obtain a block copolymer solution. The viscosity of the solution after the reaction was 18 mPa · s, and the logarithmic viscosity (;? / Η) of the obtained block copolymer (7) was 1.55 dl / g. Synthesis Example 8 *. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 public love) (Please read the precautions on the back before filling this page) i ^ w -------- Order- --------Line ----------------------- -39- 1228614 A7 B7 V. Description of the invention (37) <Step A> Modulation Polyamic acid prepolymer is the same as Step A in Synthesis Example 1 to obtain a poly (amino acid) prepolymer (A-1). (Please read the precautions on the back before filling this page) <Step B — 1> Preparation One kind of polyimide prepolymer was obtained in the same manner as in step B of Synthesis Example 1 to obtain a polyimide prepolymer (B-1). <Step B-2> Preparation of the second kind of polyimide prepolymer is the same as step B of Synthesis Example 4 to obtain a polyimide prepolymer (B-4). <Step C> Manufacturing of block copolymers. Intellectual property of the Ministry of Economic Affairs Bureau Consumer Consumption Co., Ltd. will print &gt; 80 g watts of polyimide prepolymer (A-1) obtained in step A, 15 g of polyimide prepolymer (B-1) obtained in step B-1, step B a 5 g of the obtained polyimide prepolymer (B-4) was dissolved in r monobutyrolactone so that the solid content concentration became 4% by weight, and the viscosity of the solution was 16 mPa · s. It was allowed to react at 40 ° C for 24 hours to obtain a ternary block copolymer solution. The viscosity of the solution after the reaction was 19 mP a · 8, and the logarithmic viscosity (π / η) of the obtained block copolymer (8) was 1.70 dl / g. Synthesis Example 9 <Step A — 1> Preparation of the first polyamic acid prepolymer is the same as Step A of Synthesis Example 1, and a polyamino acid prepolymer (A — 1) is obtained. Specifications are heart-warming) · 1228614 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (38) <Step A-2> Preparation of the second type of polyamide prepolymer — 2, 3, 5 -tricarboxycyclopentylacetic anhydride 22 4. 1 7g 'bis [4 mono (4 monoaminophenoxy) phenyl] sulfonic acid 432 · 5g was dissolved in 6000g of r-butyrolactone and reacted at 60 ° C 6 hours. Secondly, a large excess of acetone was injected into the obtained reaction solution to precipitate the reaction product, and the reaction product was subjected to precipitation, separation, washing, and drying steps to obtain a logarithmic viscosity (.τ? / Η) 1 · 5d Ι / g of 650 g of polyfluorinated acid prepolymer (A-3) with an amine group at the molecular end. <Step B> Preparation of polyimide prepolymer In the same manner as in Step B of Synthesis Example 1, a polyimide prepolymer (B-1) was obtained. _ <Step C> Production of block copolymer The polyamine prepolymer (A-1) 60 g obtained in step A-1 and the polyamine prepolymer (A-3) obtained in step A-2 ) 20 g, 20 g of the polyimide prepolymer (B-1) obtained in step B was dissolved in r-butyrolactone to make the solid content of the solution concentrated to 4% by weight, and the viscosity of the solution was 18 mPa · s. It was allowed to react at 40 ° C for 24 hours to obtain a ternary block copolymer solution. The viscosity of the solution after the reaction was 20 mPa * s, and the logarithmic viscosity (/? / Η) of the obtained block copolymer (9) was 1.63 dl / g. Synthesis Example 1 0 This paper size is in accordance with China National Standard (CNS) A4 specifications (210 X 297 male «〉 &lt; Please read the precautions on the back before filling this page) Φ m · ϋ ϋ ϋ ί I · ϋ 1_1 ^ eJ · Βϋ I 1 1 I ϋ 1 I line ----------------------- • 41 · 1228614 A7 B7 V. Description of the invention (39) &lt; Step A 〉 Preparation of polyfluorinated acid prepolymer: 26.37 g of pyromellitic dianhydride, 1,2,3,4 monocyclic-butane 19 carboxylic acid dianhydride 23.71 g and 4,4 &gt; monodiamine dibenzene 49.92 g of a base acid was dissolved in 900 g of N-methyl-2-pyrrolidone and reacted at 6 ° C for 20 hours. Secondly, a large excess of acetone was poured into the obtained reaction solution to precipitate the reaction product, and the reaction product was subjected to precipitation, separation, washing, and drying steps to obtain a logarithmic viscosity (77 / n) 1 · 6 d 1 / The g-polyamine prepolymer (A-4) 9 6 · 3 g with an amine group at the molecular end. <Step B> Preparation of polyimide prepolymer: hydrazone ,, 3, 3 a, 4, 5, 9 b-hexahydroxy-8-methyl-yl-5-(tetrahydroxy-2,5-dihydroxy-3 —Furalkenyl mononaphtho [1,2-c] furan-1,3-dione 52.778 g, 2 '3' 5 -tricarboxycyclopentylacetic dianhydride 6. 6 g, p-phenylene di 12.44 g of amine, 23.13 g of 4, ((P-phenylene diisopropylidene) diphenylamine) and 5.01 g of compound represented by the above formula (16) were dissolved in N-methyl-2-pyrrolidone In 800g, react at 20 ° C for 26 hours. Next, a large excess of acetone was injected into the obtained reaction solution to precipitate the reaction product (polyamine prepolymer). The obtained polyamine prepolymer 100 〇g was dissolved in 900 g of r-butyrolactone, and then 6 2 g of pyridine and 14 1 g of acetic anhydride were added, followed by dehydration and ring closure at 60 ° C for 2 hours. Next, the reaction product was precipitated, separated, washed, and dried. In step, logarithmic viscosity (7? / Η) 0 · 7 3 d 1 / g_, imidized This paper size is applicable to Chinese National Standard (CNS) A4 (210 χ 297 mm *) (Please read the notes on the back first (Fill in this page again) -------- Order --------- line 丨 # Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs • 42 · 1228614 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Explanation (40) A polyimide prepolymer (B-2) having an acid anhydride group at the molecular terminal at a rate of 90% 9 7 · 2 g ° <Step C> Production of a block copolymer The polyamine obtained in Step A 7 5 g of the acid prepolymer (A-4) and 2 5 g of the polyimine prepolymer (B-5) obtained in step B were dissolved in r-butyrolactone so that the solid content concentration of the solution became 4% by weight As a result, the viscosity of the solution was 20 mPa · s. After being allowed to stand at 30 ° C for 48 hours, a block copolymer solution was obtained. After the reaction, the viscosity of the solution was 27 m P a · s. The obtained block copolymer (1 0 The logarithmic viscosity (77 / η) is 1 · 8 d 1 / g. Synthesis Example 1 1 <Step A &gt; Preparation of Polyamine Prepolymer A 1,2,3,4 monocyclobutanetetracarboxylic acid di Anhydride 4 0 · 7 2 g and 4, 4 &gt; monodiaminodiphenyl ether 5 1 · 28 g were dissolved in 900 g of N-methyl- 2-pyrrolidone and reacted at 20 ° C for 6 hours. Secondly, it will greatly exceed Amount of acetone was poured into the obtained reaction solution The reaction product is precipitated, and the reaction product is subjected to the steps of precipitation, separation, washing, and drying to obtain a poly (amino acid) prepolymer having an amine group at the molecular end of a logarithmic viscosity (77 / n) 1 · 6 d Ι / g. (A — 5) 93g. <Step B> Preparation of polyimide prepolymer: 1,3,3a, 4,5,9b -Hexahydroxydi 8-methyl This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling this page) Φ

一 seJ · I · 1 ϋ ί * 1 * I Λ— ϋ n mmMaw n 1_1 ϋ §Mam tmf i · — II tt— nn · ϋ n MmmM9 in · ϋ ϋ an I -43- 1228614 Employee of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperative A7 B7 V. Description of the invention (41) 5-(tetrahydroxy-2,5-dihydroxy-3-furanenyl-naphtho [l, 2-c] furan-1,3-dione 59.19g, 2, _3, ~ 5-tricarboxycyclopentylacetic dianhydride 4.69g, -phenylenediamine 13.44g, 2,2-bis (4-aminoaminophenyl) -1,1'1, 10.39 g of 3,3,3-hexafluoropropane, 3.04 g of 4,4 ^ -diaminodiphenylmethane and 3.25 g of the compound represented by the above formula (16) were dissolved in N-methyl-2-pyrrolidone In 300 g, the reaction was carried out at 20 ° C for 26 hours. Next, a large excess of acetone was poured into the obtained reaction solution to precipitate a reaction product (polyamine prepolymer). The obtained polyamino acid prepolymer was precipitated. 1 0 0 · 0 g was dissolved in 900 g of 7-butyrolactone, 65 · 2 g and acetic anhydride 84 · 2 g were added, and dehydration and ring closure were performed for 2 hours at 60 ° C. Next, the reaction product was precipitated, separated, washed, Drying step, logarithmic Degree (τ? / Η) 0.95 d 1 / g, 94% of a polyimine prepolymer (B-6) having an acid anhydride group at the molecular end of the imidization rate of 9 5%. <Step C> Manufacturing a block copolymer Polymer: 75 g of the polyfluorene prepolymer (A-5) obtained in step A and 2 5 g of the polyimine prepolymer (B-6) obtained in step B were dissolved in r-butyrolactone to make a solution. The solid content concentration became 4% by weight. As a result, the viscosity of the solution was 14 m P a · s. The solution was reacted at 50 ° C for 4 hours to obtain a block copolymer solution. The viscosity of the solution after the reaction was 21 m P a · s, the log viscosity (π / η) of the obtained block copolymer (1 1) is 1 · 6 d 1 / g. · This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) ________ Order · ________ Line — -44- 1228614 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (42) Comparative Synthesis Example 1 — 黹 1,3,3 a, 4,5,9b —hexahydroxy-5-(tetrahydroxy-2,5-dihydroxy-3-furanyl) -naphtho [1,2, c] furan-1 , 3 -dione 34 · 7g, p-phenylenediamine 10.41g, 1-hexadecyloxy-2,4-diaminobenzene 3.84 and 3-aminopropylmethyldiethoxysilane 1.05g dissolved in N In 200 g of —methyl-2-pyrrolidone, the reaction was carried out at 20 ° C. for 24 hours. Next, a large excess amount of acetone was poured into the obtained reaction solution to precipitate a reaction product. 50.0 g of the obtained polymer was dissolved in 450 g of r-butyrolactone, 5.0 g of pyridine and 10.8 g of anhydride were added, and dehydration and ring closure were performed at 50 ° C: 3 ° C for 3 hours. The reaction product was then precipitated, separated, washed, and dried to obtain a soluble polyimide polymer (b) 4 7 g with a logarithmic viscosity (τ? / Η) of 0 · 72d 1 / g and an imidization rate of 90%. . Comparative Synthesis Example 2 <Step A> Preparation of Polyamine Prepolymer Same as Step A-2 of Synthesis Example 10 to obtain Polyamine Prepolymer (A-3) 〇 <Step B> Preparation of Polyimide Prepolymer The polymer was the same as Step B in Synthesis Example 1 to obtain a polyimide prepolymer (B-1). (Please read the precautions on the back before filling this page) # --- LINE 丨 Climbing 丨 This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) -45- 1228614 A7 B7 Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 5. Description of the invention (43) <Step C> Manufacturing of block copolymers 80 g of polyamine prepolymer (A-3) obtained in step A and- 20 g of the substance (B-1) was dissolved in r-butyrolactone so that the solid content concentration of the solution became 4% by weight. As a result, the viscosity of the solution was 15 mPa · s. It was reacted at 4 CTC for 24 hours to obtain a block copolymer solution. The viscosity of the solution after the reaction was 18 mPa · s, and the logarithmic viscosity (7 // η) of the obtained block copolymer (丨) was 1.50 dl / g. Example 1 The block copolymer (1) obtained in Synthesis Example 1 was dissolved in r-butyrolactone so that the solid content concentration of the solution was 4% by weight, and then the solution was filtered using a pore 1 / m filter. After filtering, a liquid crystal aligning agent was prepared. The butyl-based cellosolve was added to 50 g of the liquid crystal aligning agent until a precipitate was formed. As a result, the butyl-based cellosolve amount was 20 g, so the resulting block copolymer had excellent solubility. In addition, after the solid content concentration of the obtained liquid crystal aligning agent was diluted to 2% by weight, and the ink jet printer was used for printing, the difference between the maximum film thickness and the minimum film thickness (film thickness uniformity) was 70 A, so it was good. Film thickness uniformity. Next, the continuous ink jet printability was tested. As a result, there was no poor paintability, and the film thickness uniformity (continuous printability) from the beginning to the end of printing was 30A, so it was very stable. Use a liquid crystal alignment film coating printer to apply a liquid crystal alignment agent on the transparent electrode surface of a glass substrate with a transparent electrode formed by an I TO film (please read the precautions on the back before filling this page) # ii • 线 丨-This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 cm) -46-1228614 A7 B7 V. Description of the invention (44) 'Formed on a hot plate at 180 ° C for 10 minutes Dry the film with an average film thickness of 600 A. A washing machine with a rayon-wound roller was used to perform a washing process on a film with a number of roller revolutions of 4 0 r pm, a class moving speed of 3 cm / sec, and a hair foot pressed into a length of 0.4 mm. This orientation film-coated substrate was immersed in isopropanol for 1 minute, and then both substrates were dried on a hot plate at 1000 ° C for 5 minutes. Next, an epoxy resin adhesive with alumina of 5 · 5 // m in diameter was spin-coated on the outer edge of each of the liquid crystal alignment films having a pair of aligned liquid crystal substrates, and then a pair of substrates were held. The liquid crystal substrate is overlapped and pressed so that the liquid crystal alignment film faces face each other and the washing direction is orthogonal to each other, and the adhesive is hardened. Thereafter, a nematic liquid crystal (ML-5081, manufactured by Meruku Corporation) was inserted between the pair of substrates through a liquid crystal injection port, and the liquid crystal injection port was sealed with an acrylic light curing adhesive, and then a polarizing plate was attached. A polarizing plate whose polarization direction is the same as the washing direction of the liquid crystal alignment film of each substrate is obtained as a liquid crystal display element. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Assess the liquid crystal orientation, tilt angle, voltage retention, and afterimage erasure time of the obtained liquid crystal display elements. The result is a good liquid crystal. Orientation, the afterimage erasure time is as low as 1 minute, so it meets the characteristics requirements of a liquid crystal alignment film. The results are shown in Tables 1 and 2. Examples 2 to 1 2. Comparative examples 1 to 4 The liquid crystal alignment agents using the polymers and additives obtained in Synthesis Examples 2 to 11 and Comparative Synthesis Examples 1 to 2 were prepared in accordance with the conditions shown in Table 1. The liquid crystal is changed to MLC-2012, and other papers are the same as those in this embodiment. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). ―47- 1228614 A7 _ B7_ V. Description of the invention (45) 1. The same as the liquid crystal display element of Example 1. The liquid crystal orientation of the obtained liquid crystal display element, the afterimage erasing time, and the like were evaluated. The results are shown in Tables 1 and 2. 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^ TO ^ t ^^ (CNS) A4 ^ (21〇x297 ^ _ 1228614 A7 B7 V. Explanation of the invention (47) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 2 Tilt angle (°) Voltage retention rate (%) Afterimage removal time (minutes) Example 1 5 9 8 1 Example 2 4 9 7 1 Example 3 5 9 8 1. 5 Example 4 8 8 9 8 2 Example 5 7 9 8 4 Example 6 7 9 8 6 Example 7 6 9 7 2 Example 8 4 9 7 7 Example 9 8 9 8 2 Example 1 0 5 9 8 10 Example 1 1 5 9 9 0.5 Example 1 2 5 9 9 0. 3 Comparative example 1 3 9 9 15 Comparative example 2 5 9 9 1 Comparative example 3 1 8 5 5 Comparative example 4 8 9 9 13 (Please read the precautions on the back before filling out this page) Φ ------- Γ Order · Γ -Line ----------------------- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -50 -1228614 A7 B7 V. Explanation of the invention (48) The effect of the invention can be obtained from the above contents. Examples 1 to 12 and Comparative Examples 1 to 4 have the following effects. That is, using polyamic acid and polyimide monomers Or simply mix the two liquid crystal aligning agents, with poor coating and poor print position when ink jet printing The performance of the crystal display element and other issues, and the ink jet printability of the block copolymer of the present invention, and the characteristics of the liquid crystal display element all meet high standards. Therefore, the present invention can improve the pass rate of the liquid crystal panel and correspondingly reduce costs. Ink jet printing meets the high standards of tilt angle, voltage retention, and afterimage characteristics required for liquid crystal display elements. Therefore, in addition to TN and STN liquid crystal display elements, it can also be used according to the choice of liquid crystal. For SH (Super Homeotropic) type, I p S (In-piaiie Switching) type, strong dielectric and anti-ferroelectric liquid crystal display elements, etc. In addition, the block copolymer used in Example 12 ( 1 1) Because of its excellent transparency, it is suitable for use in reflective LCDs, projectors, etc. In addition, the liquid crystal display element with a liquid crystal alignment film prepared according to the method of the present invention can be effectively used in various devices, such as desktop computers, Display devices such as watches, timers, coefficient display boards, word processors, personal computers, LCD TVs, etc. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 male *) (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

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Claims (1)

1228614 A8 B8 C8 D8 ^ —Six application patent scope No. 8 8 1 1 85 1 0 Chinese patent application scope amendment December 10, 1992 g amendment 1 · A liquid crystal aligning agent, which contains In the molecule: a block copolymer of a type 1 polyimide block and a type 2 polyamidic acid block, and the type 1 polyimide block system contains the following formula (1) ' -R2- • · ⑴ (where R1 is a hydrogen atom, a straight or branched chain alkyl group having 1 to 30 carbon atoms, R2 is a divalent carbon group having 3 to 9 alkyl groups, and a divalent carbon number The alicyclic group-containing group of 6 to 1 3, the organic polysiloxy group-containing group having 2 to 6 carbon atoms, or the aromatic group-containing group having 6 to 51 carbon atoms having divalent carbon is 1 An integer of ~ 4, where η is a positive number of repeating units) The repeating unit shown below and the following formula (2) Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (2) (In the formula, R3 is a divalent alkyl group having 3 to 9 carbon atoms, a divalent carbon number is 6 to 1 3, an alicyclic group-containing group, and a divalent carbon number is 2 to 6 Basic paper size containing organic polysiloxy group or divalent carbon number 6 ~ 5 1 Basic paper containing aromatic group Applicable to China National Standard (CNS) A4 specification (210X 297 mm) (please read the back of the order first) (Notes to fill out this page) 1228614 8 8 8 8 ABCD VI. Patent application scope, m is a positive number of repeating units) At least one repeating unit in the repeating unit group shown. The second type of poly (amino acid) block system contains the following formula (3 ) (In the formula, R6 is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, R.7 is a divalent alkyl group having 3 to 9 carbon atoms, and a divalent carbon number is 6 to 1 3 alicyclic group-containing group, divalent carbon number 2 to 6 containing organic polysiloxy group-containing group, or divalent carbon number 6 to 5 1 having aromatic group-containing group, q is heavy The positive unit number of the overlapping unit) and the following unit (4) (In the formula, R4 is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, R5 is a divalent alkyl group having 3 to 9 carbon atoms, and a divalent carbon number is 6 to 1 3 The Ministry of Intellectual Property Bureau's Employee Cooperative Cooperative printed alkane as oxygen P sand, the base-based machine has a base containing family fragrance 6 fragrant ~ containing 2 of the number 1 carbon 5 of the ~ valence 6 2 number, carbon-based valence 2 formula Or cyclic, lipid-based groups containing the single-layered species IX as small as the middle group single-layered repeat shows the N) y number of the single-layered. Reposition (Please read the notes on the back before filling this page) Ns C / — 'I quasi I standard I family one country one country in use; suitable for 1¾ feet per piece, paper