TW498090B - Polyamide compounds and liquid crystal aligning agents containing the same - Google Patents

Abstract

An object of the present invention is to provide a polyamide compound which can achieve totally and with good balance the improvement in various properties including a pre-tilt angle, alignment property and electrical properties such as residual charge, a voltage holding ratio, image sticking, and so on, which are desired for a liquid crystal aligning agent. The compound has a structure that at least one of R2 is selected from the group consisting of organic residues having side chain groups of three or more carbon atoms in formula (1): wherein R1 is a divalent organic radical derived from a dicarboxylic acid and R2 is a divalent organic residue derived from a diamine, with the proviso that at least one of R1 and R2 is a divalent organic residue having a side chain group of three or more carbon atoms; R3 and R4 are each independently hydrogen or a monovalent organic group, with the proviso that the content of the monovalent organic group is 30 mole % or more based on the total amount of R3 and R4 and n is a natural number.

Description

498090 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (1) Technical Field The present invention relates to novel polyamide compounds. More specifically, it relates to the use as a liquid crystal aligning agent. Polyamide compound with excellent electrical characteristics (voltage holding ratio, residual charge, baking) and a moderate pretilt angle. The polyamide compound of the present invention is preferably used in combination with other polymer components such as polyamic acid or soluble polyimide, so that the above characteristics related to the liquid crystal aligning agent are further improved, and the liquid crystal aligning agent is improved. Other applications in the field of electronic materials, such as application to insulating films or protective films, are also possible. 2. Description of the Related Art Liquid crystal display elements are mainly nematic liquid crystals. For example, TN type liquid crystal elements that twist liquid crystal molecules by 90 ° are used. Generally, STN type liquid crystal elements that have been twisted 180 ° have used thin film transistors. So-called TFT-type liquid crystal elements, and horizontal electric field type IPS-type liquid crystal elements and the like which have improved viewing angle characteristics, and display elements obtained by various methods have been put into practical use. The progress of the liquid crystal display element is not only the progress of these methods alone, but also the improvement of the characteristics of the liquid crystal display element and the improvement of its surrounding materials are also vigorously carried out. A type of liquid crystal aligning agent for the peripheral material is one of the important elements related to the display quality of the liquid crystal display element. However, as the quality of the display element is required, its role is becoming increasingly important. At present, the main liquid crystal aligning agents used are polyfluorinated polyacrylic acid and polyfluorinated polyacrylic acid, soluble polyfluorinated polyimide, etc. The paper size of this paper applies Chinese National Standard (CNS) A4 Specifications (210 X 297 public love) (Please read the note on the back? Matters before filling out this page) ----- l · --- Order ---- Line «» 498 090 Α7 __ Β7 V. Description of the invention (2) Amine-based directing agent. In the case of the prior literature, various polymer-based aligning agents are also being reviewed, but no matter whether they are heat-resistant, chemical-resistant (liquid crystal), coatability, electrical properties, display characteristics, or orientation of liquid crystal molecules, Isopoints are inadequate and practically not practical. In addition to polyimide-based directional agents, polyamines such as polyamines or polyamines which have hydrogen atoms bonded to them (C 0 N Η) are also under review. There are problems with the electrical characteristics of the liquid crystal element. There are also liquid crystal alignment agents that use polymer materials that have been blended with multiple polymers and block copolymerized polymer materials. However, in terms of baking, residual charge, and retention, there are problems in the current situation. . As such, the conventional liquid crystal alignment agents have not been comprehensive and well-balanced to meet necessary characteristics. DISCLOSURE OF THE INVENTION The purpose of the present invention is to eliminate the disadvantages of the conventional techniques described above, in particular to provide various characteristics such as the forward tilt angle or orientation expected by a liquid crystal aligning agent, and the electrical characteristics such as residual charge, voltage retention, and baking. The improvement can be a comprehensive and well-balanced polyamine compound for liquid crystal alignment agents. The above topics are described in further detail. Liquid crystal display elements can be used in various fields. However, with this situation, those who require higher performance are also being formed. As for these requirements, the requirements for the orientation of the liquid crystal represented by the previous tilt angle of the liquid crystal, the requirements for the electrical characteristics of the liquid crystal element such as current consumption, voltage retention, and residual charge, or the like Long-term paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling this page) ----- Order ---- Consumption by the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative-5- 498090 A7 _ B7 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (3) Requirements for the reliability of use, and the display of residual image development and uneven display of liquid crystal display elements. Grade requirements, etc. Among these required characteristics, the front tilt angle of the liquid crystal is described first, and the previous tilt angle varies depending on the driving method of the liquid crystal element. For example, a liquid crystal display element with a twist of 90 ° for a T N type liquid crystal display element or a T F T type liquid crystal display element is about 1 to 6 degrees. For a S T N type liquid crystal display element with a large twist angle, a tilt angle of about 3 to 8 degrees is necessary. However, the required forward tilt angle varies slightly depending on the application. Recently, even S-N liquid crystal display elements have been required to be 2 to 3 degrees or 8 degrees or more. On the other hand, in the I P S-type device, the liquid crystal molecules move in a horizontal direction with respect to the substrate, so there is no need to increase the forward tilt angle. The forward tilt angle is good [] at about 1 °. In addition, not only such a forward tilt angle, but also about the uniformity of orientation, orientation stability, or the anglrng energy of the liquid crystal to the film interface, and other characteristics called the orientation of the liquid crystal are also larger than the performance of the liquid crystal element. Relevance, so it's more important. Furthermore, in the manufacturing steps of liquid crystal display elements, the process margin of these characteristics is also important. The forward tilt angle or liquid crystal is caused by the drying conditions of the solvent after the application of the alignment agent or the annealing treatment conditions after the liquid crystal is implanted. The situation that the orientation changes is a big problem. For the S T N type liquid crystal display element, especially for the low voltage type used in the field of mobile devices, since the driving voltage of the liquid crystal display element is relatively low, it is important to improve the current consumption. That is, if the current consumption of the liquid crystal element 値 becomes larger, the voltage related to the liquid crystal will be relatively reduced, and the tendency of low voltage will be strengthened, so the rise of the liquid crystal molecules becomes insufficient, so please read the precautions on the back first (Fill in this page again) ----- Order ---- Line «· This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -6-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 498090 A7 --- B7 V. Explanation of the invention (4) The ratio is caused by the decrease. Also, in low-voltage type liquid crystal display elements, the change (reliability) of the consumption current 値 generated during long-term use of the liquid crystal display element is also important. In the S T N type display element, ON-0 F F is displayed with a small potential difference. Therefore, if the element's current consumption 値 changes, the voltage applied to the liquid crystal also causes a change, and it becomes a failure to drive normally. In extreme cases, the phenomenon that the image connected to the liquid crystal display element is not displayed at all by long-term driving may occur. On the other hand, T F T type liquid crystal display elements are particularly important in terms of voltage retention or residual charge requirements. If the voltage holding ratio is low, the voltage applied to the liquid crystal during the electric field period is lowered, which causes a problem that the contrast is lowered. When the residual electric charge is large, even after the voltage is applied to 0 F F, the electric charge remains in a state where the image to be erased remains as an afterimage. In the TFT liquid crystal display device, this afterimage phenomenon is one of the most important problems. In addition, with the reduction of the driving voltage of liquid crystals in recent years and the use of liquid crystals with a large dielectric anisotropy, with this trend, the fine V th unevenness occurring in the face of the display is regarded as problem lies in. In particular, if the washing process is performed by removing cutting chips generated during the polishing process of the oriented film, the washed traces remain as V t h unevenness (water unevenness), which is a big problem. To achieve the foregoing object, the present invention adopts the following constitutions. (1) According to the formula (1), this paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) (Please read the note on the back? Matters before filling out this page) •-^ 1 Pack- -l · --- Order ---- 498090 A7 B7 V. Description of the invention (5

S1.2. C -R1——CO—N——R2 ~ -N——〇〇⑴. (In the formula, R 1 represents a divalent organic residue derived from a dicarboxylic acid, and R 2 represents not derived from di An amine monovalent organic residue, but at least one of them is a divalent organic residue having a side chain group having 3 or more carbon atoms, and R 3 and R 4 represent independent hydrogen or a monovalent organic group However, the content of the monovalent organic group is based on the polyamine compound represented by the total amount of R 3 and R 4 being 30 mol% or more, η is a natural number, and R 2 is a formula (2_1) to (2 A 4)

(2-1)

(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

(2-3)

(In each formula, R5, R16, and R17 represent hydrogen or an alkyl group having 1 to 12 carbon atoms, Υ represents an early bond or C Η 2, 哀 A represents a benzene ring or a cyclohexane ring, Z represents a single Bonding, CH2, CH2CH2 or oxygen, r means 0 ~ 3 f -8 * · This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 498090 A7 B7 V. Description of the invention (6), s means 0 ~ 5, t represents each positive integer of 0 ~ 3, but when t is 2 ~ 3, each Z may be the same or different. The hydrogen on any benzene ring or cyclohexane ring may also be a lower alkane It is replaced by a radical. However, any ring of the steroid backbone of formula (2-2) and formula (2-3) can be reduced, enlarged or cracked, bicyclic ring, unsaturated bond at any position. It can be an increase or decrease, and can also be a group selected from a group of organic residues having a side chain group of 3 or more carbon atoms represented by a hydrogen atom at any position or an alkyl group substituted by an arbitrary monovalent organic group). The polyamide compound. (2) According to the formula (1) (please read the note on the back? Matters before filling out this page) Installation · ---- T f -R1——CO—N——R2——N——0C- 订 Order · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (wherein R 1 represents a divalent organic residue derived from a dicarboxylic acid, and R 2 represents a divalent organic residue derived from a diamine, but among these At least one of them is a divalent organic residue having a side chain group having a carbon number of 3 or more, and R 3 and R 4 represent an M or a monovalent organic group that is independent of each other, but the content of the monovalent organic group is based on R3 And the total amount of R4 is 30 mol% or more, η is a natural number), and R 2 is a formula (3)

⑶ (In the formula, X1 means single bond, CH2 or CH2CH2, R6 and this paper size are applicable to China National Standard (CNS) A4 specifications (210 X 297 male f) -9-498090 Α7 B7 V. Description of the invention (7) R7 Represents each independent chlorine or carbon number of 1 to 12 or a perfluorinated group. However, at least one of these means an alkyl group or a perfluoroalkyl group having a carbon number of 3 or more, u is 0 to 3, but When u is 2 to 3, each X1 may be the same as or different from each other. Also, the hydrogen on any benzene ring may be substituted by a radical.) The organic residue of a side chain group having a carbon number of 3 or more is characterized. The polyamide compound. (3) According to formula (1) f f -R1—GO—N——R2——N——〇C- ⑴

Page Please read the note on the back first. I I Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

-R10 (In the formula, R 1 represents a divalent organic residue derived from a dicarboxylic acid, and R 2 represents a divalent organic residue derived from a diamine, but at least one of them has a carbon number of 3 or more. R 3 and R 4 represent independent hydrogen or monovalent organic groups, but the content of the monovalent organic group is 30 mol% based on the total amount of R3 and R4 In the above, η is a natural polyamine compound, and R 2 is a formula (4) ⑷ -R8-X3- (wherein, X 2 and X 3 represent each independent single bond, 〇, C〇〇 This paper size applies to China National Standard (CNS) A4 (210 X 297 meals) -10- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

498090 A7 --- B7 V. Description of the invention (8), 0C0, NH, CONH or (CH2) n, R8 and R9 represent each independent single bond or aromatic ring and / or alicyclic ring 1 The ~ 3 ring contains a divalent group, R 1 ^ represents hydrogen, F, a hydrocarbon group, a fluorinated hydrocarbon group, an alkoxy group, a cyano group, or an 0H group, and η is an integer of 1 to 5. Weiji-X2-ruler 8- and 3-119-111. It is not a hydrogen atom, any of alkyl alkoxyalkyl or trifluoromethyl having 1 to 8 carbon atoms. Polyamine compounds characterized by organic residues of side chain groups having a carbon number of 3 or more. (4) Formula (1)

(In the formula, R1 represents a divalent organic residue derived from a dicarboxylic acid, and R2 represents a divalent organic residue derived from a diamine, but at least one of these is a side chain group having a carbon number of 3 or more. For bivalent organic residues, R 3 and R 4 represent independent hydrogen or monovalent organic groups, but the content of the monovalent organic group is based on the total amount of R3 and R4 being 30 mol% or more, and η is Polyamine compounds represented by natural numbers, where R2 is formula (5) (5) (where Ai represents a hydrogen atom, or a straight or branched chain with a carbon number of 1 to 12; this paper's dimensions apply Chinese national standards (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) · «» Installation ----- i · — II ϋ ϋ aamM · ϋ n .4. -11- 498090 A7 -------— B7 _ ^ _ V. Description of the invention (9) (Please read the notes on the back before filling this page) One of the courtyards or two adjacent ones Any of the above methylene groups may be substituted by an oxygen atom. A 2 represents a single bond or an alkylene group having 1 to 5 carbon atoms. One of the alkylene groups or two or more adjacent methylene groups Can be replaced by an oxygen atom m is 〇~3, n is 1 ~ 5) than an organic residue group of a side chain of 3 carbon atoms represented by compounds characterized by polyamide. (5) Polyamine compound represented by formula (1), wherein r 3 and R 4 represent mutually independent hydrogen or a monovalent organic group having a carbon number of 5 or less, and the content of the monovalent organic group is based on R 3 and R 4 The polyamine compound according to any one of (1) to (4), characterized in that the total amount is 50 mol% or more. (6) A polyamine compound represented by formula (1), wherein R 3 and R 4 represent mutually independent hydrogen or a monovalent organic group selected from a respective alkyl group or oxygen-containing alkyl group having a carbon number of 5 or less, the The content of the valence organic group is the polyamidamine compound according to any one of (1) to (5), based on the total amount of R3 and R4 being 70 mol% or more. (7) A liquid crystal aligning agent containing the polyamidoamine compound according to any one of (1) to (6). The preferred form adopted by the invention was printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, which printed the polyamine compound of the present invention, which is represented by formula (1) and is essentially an N-substituted polyamine (hereinafter referred to as a single term The N-substituted polyamine) has a main characteristic when R 2 selected from a group of organic residues having a side chain group having 3 or more carbon atoms is limited to a specific one. As for the more suitable examples of R 2 related to the above limitation, it can be expressed that the above 1) ~ (2-4), formula (3), formula (4), and formula (The paper standard applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) -12- 498090 A7 ______ B7 V. Description of the invention (10) 5) Represented organic residues. The polyamine compound of the present invention is added with the above definition of R 2. R 3 and R 4 each represent a hydrogen or a monovalent organic group having a carbon number of 5 or less. The content of the monovalent organic group is based on R 3 and When the total amount of R 4 is 50 mol% or more, it is more preferable that it is 70 mol% or more. In addition, the above-mentioned R3 and R4 are each a monovalent organic group substituted for a hydrogen atom in the amidine bond (C0NΗ) portion. When the polyamine compound of the present invention having such a structure is used as a component of a liquid crystal compounding agent, the object of the present invention, that is, the forward tilt angle or orientation expected by the liquid crystal aligning agent, the residual charge, the voltage holding ratio, Improvements in various characteristics such as electrical characteristics such as baking can be achieved in a comprehensive and well-balanced manner. The polyamine compound represented by the formula (1) can achieve the object of the present invention to a certain extent if a side chain group having 3 or more carbon atoms is introduced into any one or more groups of R 1 to R 4. Known. Examples of the introduction method include a method performed on R 3 or R 4 (first method), a method performed on dicarboxylic acid in advance (second method), or a method performed on diamine in advance (third method). . Among these introduction methods, the third method is the most preferable because it is easy to limit R 2 as described above. However, the first method is to increase a monovalent organic group to a general carbon number of 6 or more with the introduction of a side chain group. Due to the fragility and the orientation of the liquid crystal, it is not appropriate, and the second method is not necessarily enough to achieve the invention, so when this method is combined with the third method and implemented More appropriate. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the phonetic on the back? Matters before filling out this page) ----- l · --- Order ---- Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives -13- Wai 8090 A7 B7 V. Description of the invention (n) In the polyamine compound represented by formula (1) of the present invention, R 1 = carboxylic acid belongs to the aromatic family ( Contains heterocyclic system), alicyclic system (containing heterocyclic system) or aliphatic system (non-cyclic) can also be any group, but those who have a ring structure, from the good orientation of the liquid crystal molecules More appropriate. Therefore, when using non-cyclic aliphatics, it is advisable to use them in combination with alicyclics and / or aromatics, and the amount used should be in a range that does not adversely affect orientation. Inside. In addition, R 1 is preferably an oxygen- or sulfur-free structure such as an ester group or an ether group, which is likely to cause a reduction in the electrical properties of the liquid crystal element, but even if it has such a structure, it is not limited to such characteristics This will not cause any problems. Specific examples of the dicarboxylic acids to be administered as R 1 include the following. Malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, adipic acid, 2-methyladipic acid, trimethyladipic acid , Aliphatic dicarboxylic acids such as pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid, 1,1 cyclopropanedi Carboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1 monocyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,1 monocyclobutanedicarboxylic acid, 1,2-cyclobutane Ethanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutane Dicarboxylic acid, 3,4-bis (2-carboxyphenyl) -1,2-cyclobutanedicarboxylic acid, 2,4-bis (2-hydroxyphenyl) -1,3-cyclobutanedicarboxylic acid Acid, this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) «Packing ---- l · --- Order ---- Printed by the Employees 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -14- Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 498090 A7 B7_ V. Description of the invention (12) 1 Cyclobutene—1,2-dicarboxylic acid, 1—Cyclobutene—3,4—Dicarboxylic acid, 1,1—Cyclopentanedicarboxylic acid, 1,2— Cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid , 1,4-monocyclohexanedicarboxylic acid, 1,4-mono (2-orbornene) dicarboxylic acid, orthobornene 2,3-dicarboxylic acid, bicyclic [2 · 2 · 2] octane-1, 4-dicarboxylic acid, bicyclic [2. 2 · 2] octane-2, 3-dicarboxylic acid, 2, 5-dioxy-1, 4-bicyclo [2 · 2 · 2] octanedicarboxylic acid , 1,3-adamantane dicarboxylic acid, 4,8-dioxy-1,3-adamantane dicarboxylic acid, 2,6-spiro [3 · 3] heptane dicarboxylic acid, 1,3-adamantane Alicyclic dicarboxylic acids such as alkane diacetic acid and camphoric acid, phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid Formic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalate Acid, 1,4-naphthalenedicarboxylic acid, 2 ', 5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracene dicarboxylic acid 1,4-anthraquinonedicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4 / -biphenyldicarboxylic acid, 1,5-biphenylphenyldicarboxylic acid, 4,4 〃 Triphenyldicarboxylic acid, 4,4 > Biphenylmethanedicarboxylic acid, this paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -------- ---- Equipment ----- ： ---- Order ---- (Please read the precautions on the back before filling in this page) Stupid -15-498090 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs B7 V. Description of the invention (13) 4,4 > monodiphenylethanedicarboxylic acid, 4,4 / diphenylpropanedicarboxylic acid, 4,4 > monodiphenylhexafluoropropanedicarboxylic acid, 4,4 —diphenyl ether dicarboxylic acid, 4,4 / —bibenzyl dicarboxylic acid, 4,4 —stilbene dicarboxylic acid, 4,4 / —diphenylacetylene dicarboxylic acid, 4 , 4 / -carbonyldibenzoic acid, 4,4 > monosulfodibenzoic acid, 4,4 > dithiothiobenzoic acid Diacetic acid, 3,3 > -p-phenylene dipropionic acid, 4-monocarboxycinnamic acid, p-phenylene diacrylic acid, 3,3 >-{4,4 > (methylene di-p —Phenylene)} dipropionic acid, 4.4 / 1 [4,4 > mono (oxydi-p-phenylene)] dipropionic acid, 4.4 / — [4,4 > — —oxydione P-phenylene)] dibutyric acid, (isopropylidene one to one phenyleneoxy) dibutyric acid, bis (p-carboxyphenyl) dimethylsilane, 1,5 — (9 —oxyl Radical) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, 1,2,5-thiadiazole-3 4,4-dicarboxylic acid, 1,2,5-pyridadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid Aromatic dicarboxylic acids such as acids, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, and 3,6-pyridinedicarboxylic acid, but such dicarboxylic acids The acid system may be an acid dihalide. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public hairpins Ί 16- (Please read the precautions on the back before filling this page) • Packing -----. 498090 A7 -—._____ B7 5. Description of the invention (14) The above dicarboxylic acids or their acid dihalides (hereinafter referred to as dicarboxylic acids) 'especially the dicarboxylic acids of polyamines which can impart a linear structure maintain the orientation of liquid crystal molecules Among these, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, pyridinedicarboxylic acid, naphthalenedicarboxylic acid, and 1,4-anthracenedicarboxylic acid are preferred. , 4,4 > monobiphenyldicarboxylic acid, 4,4 〃 triphenyldicarboxylic acid, 4,4 > -diphenylmethanedicarboxylic acid, 4,4 > monodiphenylethane Dicarboxylic acid, 4,4 > diphenylpropanedicarboxylic acid, 4,4 > -diphenylhexafluoropropanedicarboxylic acid and 4,4 > diphenyl ether diunic acid, or the The acid difluoride and the like are preferably used. In order to improve the adhesion between a part of these dicarboxylic acids and the substrate, etc., a cyclohexanedicarboxylic acid or an acid dicarboxylic acid represented by the formula (6) is also used at the same time. chloride Can be. (Read the back of the note Pou? Matters to fill out this page) loaded set ---- ---- l · ---

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (In the formula, R11 and R12 are selected from methyl, ethyl, phenyl and cyclohexyl, v, w, x are 1 to 5). In addition, in order to increase the inclination angle of the liquid crystal molecule, as an example of a dicarboxylic acid to which R 1 having a side chain group having 3 or more carbon atoms has been introduced, those shown in Table τ such as Formula (7) or (8) can be shown. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -17- 498090 Α7 Β7 V. Description of the invention (15 HOOC-

-R13; ω

-COOH (In the formula, X4 represents a single bond, 〇, C〇〇, ΝΗ, an alkyl group having 1 to 6 carbon atoms, 〇CO, NHCO, CONH, S or CH2, and r13 represents a carbon number of 3 Hydrocarbon groups or perfluoroalkyl groups or substituents of ~ 20 can also be steroid groups. As the backbone of this steroid, cholesterol groups, androstyl groups, / 3-cholesteryl groups, epiandrost, ergosterol Alcohol, estradiol-hydroxymethyl sterol group, progesterone group, lanosterol group, piperyl alcohol group, methyl sterol group, contraceptive group, pregnanol ketone group, A-sitosterol group , Lauryl alcohol, sterol or cholesterol acetate, etc.). HOOCX ^

^ yCOOH ⑻

Order II Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (In the formula, R14 and R15 represent independent alkyl groups of 1 to 12 carbons, but the total carbon number is 4 or more.) Related to the present invention The dicarboxylic acid is not limited by these, and of course, it can exist in various other forms within the range which can achieve the object of the present invention. These dicarboxylic acids are used alone or in combination of two or more. Second, the diamine compound given to R 2 is the same as the case of the aforementioned dicarboxylic acid, and may also belong to the aromatic system (including heterocyclic system), alicyclic system (including heterocyclic system), or aliphatic system (non-cyclic). Any one of the groups, but the Chinese national standard (CNS) A4 specification (210 X 297 mm) is applicable to this paper size. • 18-498090 A7 — B7 V. Description of the invention (16) Those who have a ring structure are well maintained. Orientation of the liquid crystal molecules is more suitable. OR 2 is the same as above, and it is suitable to use a structure that does not contain oxygen or sulfur, such as an ester group or an ether group, which causes a decrease in the electrical properties of the liquid crystal element. This kind of structure is also limited to not affect these characteristics, so it does not become a problem. 0 The polyamine compound of the present invention needs to have the function of imparting a forward tilt to the liquid crystal, so at least the component of R1 or the component of R2 has carbon. Necessary for a side chain group of 3 or more. The former, that is, in the case where R 1 derived from a dicarboxylic acid has been introduced into a side chain group of 3 times in carbon number, it is possible to give the diamine compound of R 2 by referring to the already mentioned. When the dicarboxylic acid has a side chain group having 3 or more carbon atoms, it may be a diamine compound having no side chain. However, in this case, it is also preferable to use a diamine compound having a side chain group having 3 or more carbon atoms in combination. On the other hand, when a dicarboxylic acid having a side chain group having a carbon number of 3 or more is not used for the component of R 1, a diamine compound having a side chain group having a carbon number of 3 or more is required. As for the side chain group of the diamine compound, an aliphatic hydrocarbon group having a carbon number of 3 or more, a hydrocarbon group containing an alicyclic structure, an aromatic hydrocarbon group, a siloxane group, a steroid backbone group, or the like And so on. When the side chain agent is a cyclic structure such as a cyclohexane group, its carbon number is expressed based on the number of carbons constituting the ring. The above-mentioned side chain agent may be replaced by a part of the hydrocarbons such as oxygen, but the oxygen-containing atom which does not contain 0, C0, or C〇〇 is recommended. This paper applies Chinese national standard (CNS) A4. Specifications (210 X 297gt) (Please read the phonetic on the back? Matters before filling out this page) Pack ----- 丨 Order i Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives-19-498090 Intellectual Property Bureau of the Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 B7 V. The base of invention description (17), the base of sulfur atom such as S or S 02. However, in the case where the side chain group contains an alicyclic structure hydrocarbon group or an aromatic hydrocarbon group, these types of substituents may include an alkyl group, an alkoxy group, a halogen or a fluorenyl group. As for the diamine compound having such a side chain group having a carbon number of 3 or more, R2 is represented by the formulas (2-1) to (2-4), formula (3), formula (4), or formula described above. (5) Any one of the organic residues represented by the diamine compound. In addition, as for the steroid backbones of the above formulae (2-2) to (2-3), there are cholesterol groups, androstyl groups, / 3-cholesteryl groups, epiandrostyl ergosterol groups, and female Alcohol group, 11 ^ monomethylol sterol group, 1 1 α-progesterone group, lanosterol group, piperitol group, methyl sterol group, contraceptive group, pregnanolone group, / 3 -Nestrol, dodanol, sterol or cholesterol acetate. As specific examples of such a diamine compound, those represented by the formulae (2-1) to (2-4) include the following. When Z = oxygen, r = 0, and t = 1: 1,1-bis [4- — (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- — (4-amine Phenylphenoxy) phenyl] -4 4-fluorenylcyclohexane, 1,1 bis [4-mono (4-aminophenoxy) phenyl] 4-ethylcyclohexane, 1,1 one Bis [4-mono (4-aminophenoxy) phenyl] -4 4-n-propylcyclohexane, this paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) ----- ------- install ----- r --- order ---- (Please read the precautions on the back before filling out this page)-^--20- Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation 498090 A7 B7 V. Description of the invention (18) 1,1 bis [4 one (4-aminoaminophenoxy) phenyl] 4 4-n-butylcyclohexane, 1,1-bis [4 one ( 4-aminophenoxy) phenyl] -4 4-n-pentylcyclohexane, 1,1-bis [4- (4-aminoaminophenoxy) phenyl] -4-n-hexylcyclohexane, 1,1 bis [4- (4-aminoaminophenoxy) phenyl] -4 4-n-heptylcyclohexane, 1,1-bis [4-mono (4-aminoaminophenoxy) Phenyl] -4 -n-Leptylcyclohexane, 1,1 -bis [4-(4 -aminoaminophenoxy) phenyl] -4 -n-nonylcyclohexane, 1,1 -bis [4 Mono (4-aminophenoxy) phenyl] -4 4-n-decylcyclohexane, 1,1 bis [4- (4-aminophenoxy) phenyl] -4-n-eleven Cyclohexane, 1,1-bis [4- mono (4-aminoaminophenoxy) phenyl] -4 4-n-dodecylcyclohexane, 1,1-bis [4- — (4-monoamino Phenoxy) phenyl]-4 -n-tridecylcyclohexane, 1,1 -bis [4-(4-aminoaminophenoxy) phenyl] -4 -n-tetradecylcyclohexane 1, 1, 1 bis [4 1 (4 aminoaminophenoxy) phenyl] 4 4 n-pentadecylcyclohexane, This paper size applies to China National Standard (CNS) A4 (210 X 297) Li) (Please read the notes on the back before filling out this page) __Installation ---- l · --- Order ---- -21-498090 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs _ 5 Explanation of the invention (19) When r, t = 0, 1,1 bis (4-aminophenyl) cyclohexane, 1,1 Bis (4-monoaminophenyl) -4 monomethylcyclohexane, 1,1-bis (4-monoaminophenyl) -4-ethylcyclohexane, 1,1-bis (4-monoamino Phenyl) -4-n-propylcyclohexane, 1,1-bis (4-aminoaminophenyl) -4-n-butylcyclohexane, 1,1-bis (4-aminophenyl)- 4-n-pentylcyclohexane, 1,1-bis (4-aminoaminophenyl) -4-n-hexylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-heptyl Cyclohexane, 1,1-bis (4-aminoaminophenyl) -4 4-n-octylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-nonylcyclohexane, 1,1—bis (4-aminoaminophenyl) -4—n-decylcyclohexane, 1,1—bis (4-aminoaminophenyl) —4—n-undecylcyclohexane, 1,1 One bis (4-aminoaminophenyl) one 4 -n-dodecylcyclohexane, 1,1 One bis (4-aminoaminophenyl) -4 one n-tridecylcyclohexane, 1,1 one double (4-Aminophenyl) -4 -n-tetradecylcyclohexane, 1,1 -bis (4-Aminophenyl) -4 -n-pentadecylcyclohexane. When A = hexyl, r = l, s't = 0 · 1,1 bis (4-aminoaminophenyl) -4 4-cyclohexylcyclohexane, 1,1-bis (4-aminobenzene Group) —4 mono (4-methyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminoaminophenyl) -4— (4-ethyl—trans-cyclohexyl) cyclohexane, 1 , 1—bis (4-aminophenyl) —4— (4-n-propyl-trans) —This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first Please fill in this page for matters) · _ Pack! · Order ----- Qin- -22- Printed by the Employees' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 498090 A7 B7 V. Description of the invention (20) Cyclohexyl) cyclohexane 1,1-bis (4-aminophenyl) -4— (4-n-butyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4— (4— N-pentyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminoaminophenyl) -4- (4-n-hexyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4 —Aminophenyl) —4— (4—n-heptyl-trans—cyclohexyl) ring Hexane, 1,1 bis (4-aminoaminophenyl) -4 (4-n-octyl-trans-cyclohexyl) cyclohexane, 1,1 bis (4-aminoaminophenyl) -4 — (4-n-nonyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-decyl-trans-cyclohexyl) cyclohexane, 1 1,1-bis (4-aminoaminophenyl) -4- (4-n-undecyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminoaminophenyl) -4 4- (4- N-dodecyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-tridecyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminoaminophenyl) -4 4- (4-n-tetradecyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-monoaminophenyl) -4- (4-n-pentadecyl) In contrast, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the precautions on the back before filling this page) «Packing ----- Order --- 23- Ministry of Economy Wisdom Printed by the Consumer Cooperative of the Property Bureau 498090 A7 _B7 ___ V. Invention Description (21) Cyclohexyl) cyclohexane. When A = Hexyl, Z = Oxygen, r = l, s = 〇 't = l. 1,1 bis [4 ((4-aminoaminophenoxy) phenyl]-4-(cyclohexyl ) Cyclohexane, 1,1 bis [4-mono (4-monoaminophenoxy) phenyl] -4 ((4-methylcyclohexyl) cyclohexane, 1,1 bis [4 one (4 Monoaminophenoxy) phenyl] -4 4-((4-ethylcyclohexyl) cyclohexane, 1,1-bis [4-mono (4-aminophenoxy) phenyl] -4-(4 -Propylcyclohexyl) cyclohexane, 1,1-bis [4-mono (4-monoaminophenoxy) phenyl] -4- (4-butylcyclohexyl) cyclohexane, 1,1-bis [4- — (4-aminoaminophenoxy) phenyl] -4— (4-pentylcyclohexyl) cyclohexane, 1,1-bis [4 -— (4-aminoaminophenoxy) phenyl] —4 mono (4-hexylcyclohexyl) cyclohexane, 1,1-bis [4-mono (4-monoaminophenoxy) phenyl] -4 — (4-heptylcyclohexyl) cyclohexane, 1 1,1-bis [4- (4-aminoaminophenoxy) phenyl] -4- (4-octylcyclohexyl) cyclohexane. When A = cyclohexyl, Y = CH2, r, s = 1, and t = 〇: 1,1 bis (4-aminophenyl) -4— (cyclohexylmethyl) cyclohexyl, 1,1 One bis (4-aminoaminophenyl) — 4 — [(4-methylcyclohexyl basic paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) ---------- --Shang ----- r --- Order ---- (Please read the notes on the back before filling this page) -24- 498090 A7 B7 V. Description of the invention (22)) Methyl) cyclohexane , 1,1 bis (4-aminoaminophenyl) -4 ([(4-ethylcyclohexyl) methyl) cyclohexane, 1,1 bis (4-aminophenyl)-4-1 [ (4-propylcyclohexyl) methyl) cyclohexane, 1,1 bis (4-aminophenyl) -4-((4-butylcyclohexyl) methyl) cyclohexane, 1,1 One bis (4-aminoaminophenyl) -4 — [(4-pentylcyclohexyl) fluorenyl) cyclohexane, 1,1—bis (4-aminophenyl) —4 — [(4-hexyl Cyclohexyl) methyl) cyclohexane, 1,1-bis (4-aminophenyl) -4 — [(4-heptylcyclohexyl) methyl) cyclohexane, 1,1 a (4-aminophenyl) - 4 - [(4 - cyclohexyl octyl-yl) methyl) cyclohexane. When A = phenyl, Y = CH2, Z = oxygen, r, s, t = 1, 1,1 bis [4- — (4-aminoaminophenoxy) phenyl] -4 — (phenylmethyl ) Cyclohexane, 1,1-bis [4 -— (4-aminophenoxy) phenyl] -4 — [(4-methylphenyl) methyl] cyclohexane, 1,1-bis [ 4- (4-aminophenoxy) phenyl] -4 mono [(4-monoethylphenyl) methyl] cyclohexane, 1,1-bis [4-mono (4-monoaminophenoxy) Phenyl] -4 [[4-propylphenyl) methyl] cyclohexane, This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) (please read the precautions on the back first) (Fill in this page) Pack — l · --- Order —— Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy -25- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 498090 A7 B7 V. Description of the Invention (23) 1 , 1-bis [4-mono (4-aminophenoxy) phenyl] -4-[(4-butylphenyl) methyl] cyclohexane, 1,1-bis [4-mono (4-monoamine Phenoxy) phenyl] -4 [[(4-pentylphenyl) methyl] cyclohexane, 1,1 One bis [4-mono (4-aminophenoxy) phenyl] -4 4-[(4-hexylphenyl) methyl] cyclohexane, 1,1-bis [4 -— (4-aminoaminophenoxy) (Phenyl) phenyl] -4-[(4-heptylphenyl) methyl] cyclohexane, 1,1 -bis [4-((4-aminoaminophenoxy) phenyl] -4-[(4 Monooctylphenyl) methyl] cyclohexane. When A = phenyl, Y = CH2, r, s = 1, t = 〇: 1,1 bis (4-aminoaminophenyl) -4 4- (phenylmethyl) cyclohexane, 1,1 One bis (4-aminoaminophenyl) —4 — [(4-methylphenyl) methyl) cyclohexane, 1,1—bis (4-aminophenyl) —4 — [(4-ethyl Phenyl) methyl] cyclohexane, 1,1-bis (4-aminoaminophenyl) -4-((4-propylphenyl) methyl] cyclohexane, 1,1-bis (4 —Aminophenyl) —4 — [(4-butylphenyl) methyl] cyclohexane, 1,1—bis (4-aminophenyl) —4 — [(4-pentylphenyl) Methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4 — [(4-hexylphenyl) methyl] cyclohexane, This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the phonetic on the back? Matters and then fill out this page) Order ----… -26- 498090 Printed by A7 _B7 _5, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs (24) 1,1-bis (4-aminoaminophenyl) -4-[(4-heptylphenyl) Group] cyclohexane, 1,1-bis (4-aminoaminophenyl) -4 4-[(4-octylphenyl) methyl] cyclohexane. A = phenyl, Y = CH2, Z is CH2, r, s, t = l 1,1 bis {4 -— ((4-aminoaminophenyl) methyl] phenyl} —4— (benzene Methylmethyl) cyclohexane, 1,1-bis {4-mono [(4-monoaminophenyl) methyl] phenyl} 4- 4-[(4-methylphenyl) methyl] cyclohexane, 1,1 bis {4-[[4-aminophenyl) methyl] phenyl} — 4 — [(4-ethylphenyl) methyl] cyclohexane, 1,1—bis {4 — [(4-Aminophenyl) methyl] phenyl} 4- 4-[(4-propylphenyl) methyl] cyclohexane, 1,1-bis {4-a [(4-aminophenyl ) Methyl] phenyl} -4-[(4-butylphenyl) methyl] cyclohexane, 1,1 -bis {4-[(4-aminophenyl) methyl] phenyl}- 4-[(4-pentylphenyl) methyl] cyclohexane, 1,1-bis {4-[(4-aminophenyl) methyl] phenyl} 4-4-[(4-hexylbenzene (Yl) methyl] hexamethylamine, 1,1 bis {4-[(4-aminophenyl) methyl] phenyl} -4-[(4-heptylphenyl) methyl] cyclohexyl Alkanes, 1, 1— {4 - [(4-aminophenyl) methyl] phenyl} - 4 - [(4-octylphenyl) methyl] cyclohexane. When Z = C Η 2. R = 〇, t = l: 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) ----- Qin | -27- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 498090 A7 B7 V. Description of the invention (25) 1, 1 double {4 1 [(4 monoaminophenyl) methyl] Phenyl} cyclohexane, 1,1 bis {4-[(4-monoaminophenyl) methyl] phenyl} _4-methylcyclohexane, 1,1-bis {4 — [(4- Aminophenyl) methyl] phenyl} -4-monoethylcyclohexane, 1,1-bis {4-mono [(4-monoaminophenyl) methyl] phenyl} -4 monopropylcyclohexyl Alkanes, 1,1 bis {4-mono [(4-aminoaminophenyl) methyl] phenyl} — 4-butylcyclohexane, 1,1-bis {4-mono [(4-aminoaminophenyl) ) Methyl] phenyl} -4-pentylcyclohexane, 1,1 bis {4-mono [(4-aminoaminophenyl) methyl] phenyl} -4 4-hexylcyclohexane, 1,1 One bis {4 _ [(4-aminophenyl) methyl] phenyl} one 4-heptylcyclohexane, 1,1-bis {4 one [(4 — Yl) methyl] phenyl} a 4 - octyl cyclohexane. A = cyclohexyl, Y = CH2, Z = CH2, r, t = l, s = 2: 1,1-bis {4-[(4-aminoaminophenyl) methyl] phenyl} — 4-[ 2 — (cyclohexylethylcyclohexane, 1,1 bis {4 — [(4-aminophenyl) methyl] phenyl} — 4— [2 — (4-methyl-trans-cyclohexyl ) Ethyl) Cyclohexane, This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) Installation — l · — 订 — -28- 498090 A7 B7 Five 'invention description (26) 1' 1-bis {4 — [(4-aminoaminophenyl) methyl] benzyl 丨 -4 ~ [2- (4-ethyl-trans-cyclohexyl) ethyl Group) cyclohexane, 1 '1-bis {4-mono [(4-aminophenyl) methyl] phenyl 丨 4- 4 ~ [2- (4-propyl-trans-cyclohexyl) ethyl) cyclohexyl Alkane, 1 '1-bis {4- — [(4-aminophenyl) methyl] phenyl} — 4 to [2-((4-butyl-trans-cyclohexyl) ethyl) cyclohexane, 1' 1-bis {4-[[4-aminophenyl) methyl] benzyl 4 -— [2 — (4-pentyl-trans-ring ) Ethyl) cyclohexane, 1,1 bis {4 -— ((4-aminophenyl) methyl] phenyl 丨 4-4- [2- (4-pentyl-trans-cyclohexyl) ethyl Group) cyclohexane, 1,1-bis {4- mono [(4-aminoaminophenyl) methyl] phenyl 丨 4- 4- [2- (4-hexyl-trans-cyclohexyl) ethyl) cyclohexane , 1 '1 bis {4 -— ((4-aminophenyl) methyl] benzyl} —4— [2— (4-heptyl-trans-cyclohexyl) ethyl) hex {1, 1, 1—bis {4-[[4-aminoaminophenyl) methyl] pentyl} —4— [2- (4-octyl-trans-cyclohexyl) ethyl) cyclohexane, 1,1—bis { 4-([4-aminophenyl) methyl] pentyl 丨 4- (2- (4-nonyl-trans-cyclohexyl) ethyl) cyclohexane, 1,1-bis {4 one [( 4-monoaminophenyl) methyl] phenyl 丨 4- 4- [2- — (4-dodecyl-trans-cyclohexyl) ethyl), and diphenyl compounds. For these diamine compounds, r is 0 ′ When R 5 is a fluorene group of a short chain, the rake angle is small, and when r is 1 to 5 (the side chain is 2 to 6) 'R, even if it is hydrogen, the rake angle becomes large. When the rake angle is small, it is suitable for IPS components. The rake angle is 3 ~ This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 meals ") (Page)-% Packing ---- l · --- Order ---- Printed by the Consumer Consumption Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs -29- 498090 Α7 Β7 V. Description of Invention (27) 8. It is suitable for TN type T F T element. In the case of the S T N element, there may be a case in which a large forward tilt angle is required, but at this time, a longer component of the side chain group may be used. Next, a diamine compound shown below is mentioned for the person represented by Formula (3). When X 1 = C Η 2, u = 1: 2 '2-bis {4-[(4-monoaminophenyl) methyl] phenyl} pentane, 2,2-bis {4-[(4 —Aminophenyl) methyl] phenyl} hexane, 2,2-bis {4--[(4-monoaminophenyl) methyl] phenyl} pentane, 2,2-bis {4-[ (4-aminoamino) methyl] phenyl} heptane, 2,2-bis {4--[(4-aminoaminophenyl) methyl] phenyl} nonane, 2 '2-bis {4 -[(4-monoaminophenyl) methyl] phenyl} decane, 2,2-bis {4--[(4-monoaminophenyl) methyl] phenyl} undecane, 2,2- Bis {4-[(4-aminoaminophenyl) methyl] phenyl} dodecane, 2,2-bis {4-([4-aminoaminophenyl) methyl] phenyl} thirteen, 2,2-bis {4-[(4-aminoaminophenyl) methyl] phenyl} tetradecane, 2,2-bis {4-[(4-aminoaminophenyl) methyl] phenyl} Pentadecane, 2,2-bis {4--[(4-monoaminophenyl) methyl] phenyl} hexadecane, 2,2-bis {4-[(4-monoaminophenyl) methyl ] Phenyl} heptadecane, 2,2-bis {4--[(4-monoaminophenyl) methyl] phenyl} octadecane, 2,2-bis {4-[ (4-monoaminophenyl) methyl] phenyl} nonadecane, 2,2-bis {4-mono [(4-monoaminophenyl) methyl] phenyl 丨 perfluoropentane, 2,2- — Bis {4-mono [(4-aminophenyl) methyl] phenyl} perfluorohexane, this paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first (Please fill in this page for matters) • 9—— Order —— Printed by the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economics -30- Printed by the Employees’ Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 498090 A7 B7 , 2-bis {4-mono [(4-monoaminophenyl) methyl] phenyl} perfluoroheptane, 2,2-bis {4-mono [(4-monoaminophenyl) methyl] phenyl} Perfluorooctane, 2,2-bis {4-mono [(4-monoaminophenyl) methyl] phenyl} perfluorononane, 2,2-bis {4-mono [(4-monoaminophenyl) Methyl] phenyl} perfluorodecane, 2,2-bis {4- — [(4-monoaminophenyl) methyl] phenyl} perfluoro ^ *, 2,2-bis {4-a [( 4-monoaminophenyl) methyl] phenyl} perfluorododecane, 2,2-bis {4 a [(4 a Phenyl) methyl] phenyl} perfluorotridecane, 2,2-bis {4-mono [(4-monoaminophenyl) methyl] phenyl} perfluorotetradecane, 2,2-bis {4-mono [(4-monoaminophenyl) methyl] phenyl} perfluoro15, 2,2-bis {4-mono [(4-monoaminophenyl) methyl] phenyl} perfluorodeca Six courts, 2,2-bis {4-mono [(4-aminophenyl) methyl] phenyl} perfluoroseminarium, 2,2-bis {4-mono [(4-monoaminophenyl) methyl Base] Phenyl} Perfluoro18, this paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) ------------ pack ----- r. (Please read the notes on the back before filling this page) 0 -31-A7

i 'Explanation of the invention (29) < ' ' 2-Bis [4-mono [(4-aminophenyl) methyl] phenyl} perfluoro nineteen courts. Moreover, the above are examples of 2,2-bimeric compounds, but depending on the carbon numbers of R 6 and R7, they are 1,1-bimeric, 3,3-bisimial, 4,4-bisimple, or 5,5 -Of course, double compounds can also be represented in the same way. Next, for those represented by the formula (4), the following diamine compounds may be listed: 4 to [3- (4-biphenyloxy) propoxy] -1, 3-diamine, 4 to [8 -(4-Biphenyloxy) octyloxy] -1,3-Febrenylbenzene, 4 ~ [3- (4-Cyanobiphenyl-4 > monooxy) propoxy ] -1,3-diaminobenzene, 4-a [1 2-(4-monocyanobiphenyl-4 / -oxy) dodecyloxy] -1,3-diaminobenzene, 4-a [6- — (4-methoxybiphenyl-4- > monooxy) hexyloxy] -1,3-diaminobenzene, 4- [3- (4-fluorobiphenyl-1 / 4 (Oxy) propoxy] -1,3-diaminobenzene, 2 '4-diaminobenzoate dodecyl, 2' 4-diaminooctyl octyl ester, 1,5-diamine-2 -Octyloxycarbonylaminobenzene, and diamine compounds having various steroid-based substituents as described in the formulae (2-2) to (2-3). In addition, 1,4-diamino-3-{4-mono (4-alkylcyclohexyl) paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back first (Fill in this page again) Packing ----- Order ·-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy -32- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 498090 A7 B7 V. Description of the invention (3〇) _) Cyclohexyloxy} benzene, i, 4-diamino- 3-{4- — (4-monoalkylphenyl) cyclohexyloxy} benzene, hydrazone, 4-diamino- 3-{(4-monoalkane Diphenyltriphenyl) oxy} benzene, 2-monoalkyloxy-1,4-diaminobenzene, and diamine compounds having a steroid-based side chain in phenylenediamine. Examples of the formula (5) include diamine compounds shown below. 1-cyclohexyl-4 4- (4-aminobenzyl-2-aminophenyl) cyclohexane, 1- (4-methylcyclohexyl) -4 4- (4-limylfluorenyl-2 -monthly female) Phenyl) cyclohexyl, 1- (4-propylcyclohexyl) -4- (4-monoamino; aryl-2-aminophenyl) cyclohexane, 1- (4-pentylcyclohexyl) 4- (4-aminoaminobenzyl-2-aminophenyl) cyclohexane, 1- (4-octylcyclohexyl) -4- (4-aminoaminobenzyl-2-aminophenyl) Cyclohexane, 1— (4-decylcyclohexyl) —4— (4-aminoaminobenzyl-2—aminophenyl) cyclohexane, 1— (4-dodecylcyclohexyl) —4— (4-aminobenzyl-2-aminophenyl) cyclohexane, 1-cyclohexyl-4 ((3-aminobenzyl-2-aminophenyl) cyclohexane, 1- (4-monomethyl) Cyclohexyl) 4- 4 (3-Aminobenzyl 2- 2-Amine This paper is sized for China National Standard (CNS) A4 (210 X 297 mm)) (Please read the note on the back? Matters before filling out this page ) Equipment --- 1 l · --- Order ---- -33- 498090 A7 B7 Member of Intellectual Property Bureau, Ministry of Economic Affairs Printed by a consumer cooperative V. Description of the invention (31) _Phenyl) cyclohexane, 1 ~ (4-propylcyclohexyl) -4 ~ (3-Aminopyridyl-2-aminophenyl) cyclohexane , I- (4-pentylcyclohexyl) -4— (3-aminobenzyl-2-aminophenyl) cyclohexane, 1 ~ (4-octylcyclohexyl) -4— (3-amine Benzyl-2-aminophenyl) cyclohexane, 1- (4-decylcyclohexyl) -4— (3-aminobenzyl-2-aminophenyl) cyclohexane, 1- ( 4-undecyl (hexyl)-4-(3-amino; 2-aminoaminophenyl) cyclohexane. After all, the above are only specific examples of the diamine compounds represented by the formulae (2-1) to (2-4), (3), (4), or (5). The diamine compounds related to the present invention are not limited by these, and there are of course various other aspects within the scope of the attainable object of the present invention. These diamine compounds may be used alone or in combination of two or more. In the above aspect, it is possible to use a carbon having an inclination angle that increases the liquid crystal molecules mentioned in the formulae (2-1) to (2-4), (3), (4), or (5). A diamine compound having a side chain group of 3 or more (hereinafter referred to as a first diamine compound) and a diamine compound without a side chain (hereinafter referred to as a second diamine compound) may be used. As for the second diamine compound, for example, the following aromatic diamine compounds, alicyclic diamine compounds, or aliphatic diamine compounds may be mentioned. The paper size applies to Chinese National Standard (CNS) A4. (210 X 297 mm) (Please read the notes on the back before filling this page) ------ Order ---- Line I · -34- 498090 A7 B7 V. Description of the invention (32) Aromatic II Amine compounds: p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, p-xylenediamine, m-xylenediamine, p-xylenediamine, m-xylenediamine Amine, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylene Phenylenediamine, 3,3 > -diaminodiphenylmethane, 4,4 > -diaminodiphenylmethane, 3,3 > -diaminodiphenylethane, 4,4 & gt -Diaminodiphenylethane, 1,3-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2 · bis (3-amine Phenyl) propane, 2,2-bis (4-aminophenyl) perfluoropropane, 2.2-bis (3-aminophenyl) perfluoropropane, bis (4-amino-3-methyl) Phenyl) methylamine, bis (4-amino-2-methylphenyl) methylamine, 1,2 · bis (4-amino-3-methylphenyl) ethane, 1.3-bis (4- Amino-3-methylphenyl) propane, 1.2-bis (4-amino-2-methylphenyl) ethane, 1.3-bis (4-amino-2-methylphenyl) propane, bis [(4-aminophenyl) methyl] benzene, M-bis [(3-aminophenyl) methyl] benzene, M-bis [(4-aminophenyl) ethyl] benzene, M- Bis [(3-aminophenyl) ethyl] benzene, 1.4-bis [(4-amino-3-methyl-phenyl) methyl] benzene, M-bis [(4-amino-3- Methyl-phenyl) ethyl] benzene, bis-[(4- (4-aminophenylmethyl) phenyl] methane, bis-[(4- (4-aminophenylmethyl) phenyl ) Ethane, bis-[(4- (3-aminophenylmethyl) phenyl) methane, this paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the back Note for refilling this page) Reprint ---- l · --- Order ---- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-35- A7 —_____ B7_ Description of the invention (33) Double '[(4- (3-aminophenylmethyl) phenyl) ethane, 2'2 > -bis-[(4- (4-aminophenylmethyl) phenyl ) Propane, 2.2 bis-[(4- (3-aminophenylmethyl) phenyl] propane, 2.2 bis-[(4- (3-aminophenylmethyl) phenyl] perfluoropropane, bis (4-Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2 · bis (4-aminophenoxy) propane, bis [4- (4- Aminophenoxy) phenyl] methane, 2,2-bis [4- (4-aminophenoxy) phenyl] ethane, M-bis [4- (4-aminophenoxy) Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bisμ- (4-aminophenoxy) phenyl] propane, 2, 2 · bis [4- (2-aminophenoxy) phenyl] perfluoropropane, 2.2-bis [4- (3-aminophenoxy) phenyl] perfluoropropane, 2.2-bis [4- (4-Aminophenoxy) phenyl] perfluoropropane, 2.2-bis [4- (4-aminophenoxy) phenyl] butane, 4〆 / -diaminobiphenyl, 3,3 / -Dimethylbenzidine, 3.3 / -dimethoxybenzidine, 1,4-bis (4-aminophenyl) benzene, 4.4 > -bis (4-aminophenyl) biphenyl, 4 , 4 > -diaminobitriphenyl, 3,3 \ dimethyl-4,4 / -diaminobiphenyl, 1,3 · bis [4- (4-aminophenoxy) Phenyl] benzene, 1,4-bis [4- (4-aminobenzene (Oxy) phenyl] benzene, 4,4-bis [4- (4-aminophenoxy) phenyl] biphenyl, 1,2-bis [4- (4-aminophenoxy) benzene Group] cyclohexane, 1.3-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,4-bis [4- (4-aminophenoxy) phenyl] cyclohexyl The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first? Please fill in this page for matters) Packing ---- l · --- Order ---- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 36 · A7 " -----__ B7 ___ Description of the invention (34) Amine group Naphthalene, 2,6-diaminonaphthalene, 2,7-diaminomanganese, 9,9 · bis (4-aminophenyl) manganese, 9,9-bis (4-aminophenyl) -1 〇-Anthracene, 4.4 (p-phenylene diisopropylidene) bisaniline, 4.4 > m-phenylene diisopropylidene) bisaniline, 4.4 > -diamino N-benzylidene, 3,3-diaminobenzophenone, 3,4… -diaminobenzophenone, 4,4 'diaminobenzophenone, 3.3 \ diaminodiphenylbenzophenone, 4,4 bis (4-aminophenoxy) diphenyl ketone, 3.3 > -diaminodiphenylsulfide, 4,4 > -diaminodiphenylsulfide, bis (4- (4-amine Phenoxy) phenyl) sulfide, 3,3 > -diaminodiphenyl, 4,4 > -diaminodiphenyl, bis [4- (4-aminophenoxy) Phenyl], 3,3 / -diamino diphenyl ether, 4,4 > -diamino diphenyl ether, 3,4 / -diamino diphenyl ether, bis-(4-amine Phenyl) diethylsilane, bis- (4-aminophenyl) diphenylsilane, bis- (4-aminobenzene oxide) ) Ethylphosphine, 2.2-bis [4- (3-aminomethylamidino-4-aminophenoxy) phenyl] perfluoropropane, 2.2-bis- (3-aminesulfonyl-4-amine Phenyl) perfluoropropane, 2.2-bis- (3-carboxy-4-aminophenyl) perfluoropropane, 2.2-bis [4- (3-aminesulfonyl-4-aminophenoxy) Phenyl] perfluoropropane, 2.2-bis- (4-3-carboxy-4-aminophenoxy) phenyl] perfluoropropane, 1,3-bis [2- [4- (4-aminophenylbenzene) (Oxy) phenyl] perfluoroisopropyl] benzene, 2,4-bis (/ 3-amino-third butyl) toluene, bis (¥ inch- / 3-methyl-T-aminopentyl ) Benzene, this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) ---- l · --- Order ---- Line ·· Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-37- 498090 A7 B7 V. Description of the invention (35) Bis-p- (1,1-dimethyl-5-aminopentyl) benzene, bis ( P- / 3-amino-tertiary-butylpentyl) ether, bis (4-aminophenoxy) methane, bis (4-aminophenoxy) ethane, bis (4-aminophenoxy) Propyl) propane, bis (4-aminophenoxycyclohexane, 2.3-di Pyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2.4-diaminopyridine, diaminoimididine, diaminopiperine, bis- (4-aminophenyl- N-butylamine, N, N-bis- (4-aminophenyl) -N-methylamine, N- (3-aminophenyl) -4-aminobenzidine and the like. Alicyclic diamine compounds: 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, isofluoro Ketone diamine, orthobornane diamine, 4,4 / monodiaminodicyclohexylmethane, bis (2-methyl-1,4-aminocyclohexyl) methane, tetrahydrocyclodiamine cyclopentene Diamine, hexahydro-4,7—methaneindane dimethylenediamine, tricyclic [6.2.1,02,7] —undecyl dimethyldiamine, 4,4> —methylene Bis (cyclohexylamine), 2,5-bis (aminomethyl) -bicycloheptane, 2,6-bisaminomethyl-biscycloheptane, 2,3-diamine ring [2,2, 1] heptane, 2,5-diaminobicyclo [2,2,1] heptane, 2,6-diaminobicyclo [2,2,1] heptane, Chinese paper standards apply to this paper (CNS) A4 specification (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) Order ---- Line ·· Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy -38- Ministry of Economy Printed by the Consumer Cooperative of the Property Bureau 498090 A7 B7 Explanation (36) 2,7-diaminobicyclo [2,2,1] heptane, 2,3-diamino-7-azacyclo [2,2,1] heptane, 2,5- Diamino-7-azacyclo [2,2,1] heptane, 2,6-diamino-7-aza [2,2,1] heptane, 2,3-diamino-7 -Thiabicyclo [2,2,1] heptane, 2,5-diamino-7-thiabicyclo [2,2,1] heptane, 2,6-diamino-7-thiabicyclo [2,2,1] heptane, 2,3-diaminobicyclo [2,2,2] octane, 2,5-diaminobicyclo [2,2,2] octane, 2, 6-Diaminobicyclo [2,2,2] octane, 2,5-diaminobicyclo [2,2,2] octane-7-ene, 2,5-diamino-7- Azacyclo [2,2,2] octane, 2,5-diamino-7-fluorenebicyclo [2,2,2] octane, 2,5-diamino-7-thiabicyclo [ 2,2,2] octane, 2,6-diaminobicyclo [3,2,1] octane, 2,6-diaminoazabicyclo [3,2,1] octane, 2 , 6-Diaminopyrimidine [3,2,1] octane, 2,6-Diaminothiabicyclo [3,2,1] octane, 2,6 —Diamino [3,2,2] nonane, 2,6-diaminobicyclo [3,2,2] nonan-8, 2,6-diamino-8-azacyclo [3,2,2] nonane, 2,6-diamino-8-fluorenebicyclo [3,2,2] nonane, 2,6-diamino-8-thiabicyclo [3,2 , 2] nonane and the like. Aliphatic diamine compounds: 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)

-39- 498090 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the Invention (37) Ethylenediamine, Trimethylenediamine, Propylenediamine, Tetramethylenediamine, Pentamethylenediamine, Hexaline Methylenediamine, heptaethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diamino heptaethylenediamine, and alkylene diamines having an oxygen atom among the alkylene groups Diamine compounds such as amines. The above second diamine compound is not limited by these, and of course, there are various other forms within the scope of the present invention. These diamine compounds can be used alone or in combination of two or more. Among these second diamine compounds, if a large amount of aliphatic diamine compound is used in combination, it will have a bad influence on the orientation of liquid crystal molecules, so its use amount should be set to avoid the related bad effects. Within range. In order to avoid a reduction in the electrical properties of the liquid crystal element, it is preferable for the second diamine compound to have a structure containing no oxygen or sulfur group such as an ester group or an ether group. For the diamine compound given R 2, the ratio of the first diamine compound and the second diamine compound is not uniform according to the type and the required forward tilt angle, but generally the first diamine compound / second diamine The compound (mole%) is expressed as 100/0 to 1/99, preferably 100/0 to 10/90, and more preferably 100/0 to 20/80. Next, in the N-substituted polyfluorene of the present invention represented by the formula (1), R3 and R4, as already described, represent mutually independent hydrogen or a monovalent organic group having a carbon number of 5 or less, and the content of the monovalent organic group The amount is based on the total amount of R 3 and R 4 being 50 mol% or more, and preferably 70 mol% or more. However, these may be used in combination with most kinds. By introducing such a monovalent organic group, the obtained polyamine is particularly capable of significantly improving electrical characteristics when used as a liquid crystal aligning agent. And the one-price organic (please read the precautions on the back before filling this page) Packing ----- Order ---- ♦ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)- 40- 498090 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (38) In the case of those with more carbon numbers (higher flexion), the orientation of the liquid crystal will be extremely deteriorated. The organic group having a number of 5 or less is preferably an alkyl group having 5 or less carbons or an oxygen-containing alkyl group. R 3 and R 4 are organic groups with unsaturated chains or rings, organic groups with aromatic rings, organic groups with steroid backbone, and halogen, nitrogen, silicon, or phosphorus if the liquid crystal orientation is not a problem. Organic groups and the like are also acceptable. These organic groups may have a substituent in the structure. Examples of the monovalent organic group imparting such R 3 or R 4 include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Base, n-nonyl, n-decyl, n-undeyl, n-twelve, n-thirteen, n-four-twelve, n-fifteen, n-hexat , N-nonyl, n-icosyl, isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl, third pentyl, 1 methylpentyl, 2 --Methylpentyl, 3-methylpentyl, 4-methylpentyl, isohexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 4-ethylpentyl Or 2,4-dimethylhexyl, 2,3,5-triethylheptyl and other linear or branched alkyl groups, having vinyl, 1-propenyl, 2-propenyl, 2-butane Alkenyl, 1,3-butadienyl, 2-pentenyl, 2-pentanyl-4-yl, 2-nonyl-2-butanyl, amidyl, cyclobutyl, cyclopentyl , Cyclohexyl, bicyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl Bicyclohexylmethyl, 2-cyclopentene-1 1-yl, 2,4-cyclopentadiene-1 1-yl, etc. unsaturated bond or organic ring having ring, having phenyl, 2,6-dimethyl Phenyl, (Please read the notes on the back before filling this page)-I! Order ---- Line · »-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -41 -Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 498090 A7 B7 V. Description of the invention (39) 2,6-Diisopropylphenyl, biphenyl, triphenyl, bitriphenyl, benzyl, biphenyl Methyl, triphenylmethyl, bitriphenylmethyl, 4-methylbenzyl, 4- (third butyl) benzyl, α-methylbenzyl, 1-naphthyl, 2-naphthalene Organic groups of aromatic rings such as methyl, 9-anthrylmethyl, 5-phenyl-2,4-pentanediyl, have cholesterol group, androsteryl group, θ-cholesteryl group, epiandrostyl group, wheat Kerosterol group, estradiol group, 1 1 α-hydroxymethyl sterol group, 1 1 α-progesterone group, lanosterol group, piperidyl alcohol group, fluorenyl sterol group, contraceptive sterol group, pregnancy Alkanolone Organic groups of steroid backbones, such as stilbene, sterol or cholesterol acetate, have methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, methoxymethyl , Methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxy Butylbutyl, ethoxypentyl, ethoxyhexyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl, hexyloxypentyl, hexyloxyhexyl, Phenoxy, benzyloxy, 4-methoxy; phenyl, biphenyloxy, tsaioxy, phenoxymethyl, unoxymethyl, biphenyloxymethyl, tsaioxymethyl Methyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, furanyl, yS-furanyl, methyl, oxylaniermethyl, 2-methyloxylanier Methyl, 3-oxetanylmethyl, fluoranil methyl, fluoranil methyl, methylfluorenyl, ethylfluorenyl, benzamidine, methoxycarbonyl, phenylmethyl Oxygen-containing organic groups such as oxycarbonyl, Fluoromethyl, perfluoroethyl, n-perfluoropropyl, n-perfluorobutyl, n-perfluoropentyl, n-perfluorohexyl, n-perfluoroheptyl, n-perfluorooctyl, n-perfluorononyl, Ortho-perfluorodecyl, ortho-perfluorodecyl, or per-perfluoro This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first? Please fill in this page again for matters) _Package ----- Order ---- -42- 498090 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (40) 12 bases, 13 perfluoro Base, n-perfluoro14-based, n-perfluoro15-based, n-perfluoro16-based, n-perfluoro17-based, n-perfluoro18-based, n-perfluoro19-based, n-perfluoro20-based , 4-trifluoromethylbenzyl and other halogen-containing organic groups, aminomethyl, aminopropyl, aminobutyl, aminopentyl, aminohexyl, aminoheptyl, aminooctyl, Amino nonyl, amino decyl, undecyl, amino dodecyl, amino tridecyl, amino tetradecyl, amino pentayl, amino hexadecyl, amino 17 Amino, octadecyl, amine nonadecyl, amino icosyl, 2-aminoisopropyl, 3-aminoisobutyl, 2-pyridylmethyl, 3-pyridylmethyl, 4-pyridylmethyl, 2'2'6,6-tetramethyl-4-piperidinyl, 2,2,6,6-tetramethyl-1- (2-propenyl) -4, 1-methyl-2,5-dipyridyl-3-pyrrolidinyl, (1,2,3,6-tetrahydro-1 3-Dimethyl-2,6-Dimethyl-7H-purine-7-yl) methyl, cyano, cyanomethyl, cyanoethyl, cyanopropyl, cyanophenyl, cyano Phenyl, cyanobiphenyl, cyanobenzyl, cyanophenylmethyl, cyanobiphenylmethyl, cyanobitriphenylmethyl, trimethylmethanyl, diethyl Organic groups containing nitrogen, silicon, or phosphorus, such as silyl, triphenylsilyl, 4-trimethylsilylbenzyl, dimethoxyphosphinomethyl, diethoxyphosphinomethyl, etc. . Among these, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl Group, third pentyl, vinyl, ethynyl, 1-propenyl, 2-propynyl, isopropynyl, 2-butynyl, 1,3-butadienyl, 2-pentynyl, 2 -pentene-4 monoyl, cyclopropyl, cyclobutyl, cyclopentene (please read the note on the back? Matters before filling out this page). Equipment ---- l · --- Order ---- Meaning 丨 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -43- 498090 A7

V. Description of the invention (41) Printed base, cyclopropylmethyl, cyclobutylmethyl, 2-cyclopentene-1 1-yl, 2 '4-cyclopentadiene 1- 1 , Trifluoromethyl, perfluoroethyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, methoxyfluorenyl, methoxyethyl, methoxypropyl, methyl Oxybutyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, furanyl, (3-furan Methyl), methyloxylanilylmethyl, 2-methyloxylanilylmethyl, 2-oxetanylmethyl, 3-oxetanylmethyl, fluorene A monovalent organic group having a carbon number of 5 or less, such as a lanierylmethyl group, a monolanylmethyl group, a methylamino group, and an ethylmethyl group. The monovalent organic groups of R 3 and R 4 which are related to the present invention are not limited thereto, and they may exist in various other forms within the scope of the object of the present invention. These monovalent organic groups can be used alone or in combination of two or more kinds. The N-substituted polyamidoamine of the present invention can be obtained by any of the two methods shown below. One of them is a method of polymerizing a dicarboxylic acid with a diamine compound in which a hydrogen atom of an amine group (N Η 2) is substituted with R 3 and / or R 4 (hereinafter referred to as a pre-substitution method), and the other is A method for polymerizing a diamine compound with a dicarboxylic acid, and replacing the hydrogen atom of the fluorene bond (CON) of the polyfluorene with R 3 and / or R 4 (hereinafter, referred to as post-substitution) Method). The above method is applicable to any method, but the latter is superior in reactivity and can increase the molecular weight of the polymer produced. Therefore, the film itself has good mechanical properties when used as a liquid crystal alignment film. It can avoid the shortcomings of the film, such as being removed, and disordered orientation, so it is more suitable. And this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back? Matters before filling out this page). Loading ---- l · --- Order ---- • Sen — -44- A7

V. Description of the invention (42) The substitution rate of the organic group of the N-substituted polyamine is more than 50%, preferably 70% or more, and more preferably 90% or more. The substitution ratio of less than 50% 'is difficult to produce an effect in the electrical characteristics of a liquid crystal display element. The substituted diamine compound related to the former substitution method is obtained by dehydrating and condensing a diamine, an aldehyde such as propionaldehyde or benzaldehyde, or a ketone such as methyl ethyl ketone or cyclohexanone by referring to a known organic synthesis method. A method for reduction by combining a double bond of an imine, a method for reducing a carbonyl group of an amidine obtained by reacting a diamine with an acid halide such as acetamido chloride or benzoic acid chloride with lithium aluminum hydride, and N-methylaniline, N, N-diphenylamine or N-methyl-3-aminotoluene and other N-substituted anilines and formaldehyde are reacted in the presence of an acid catalyst to obtain N, N /-substitution Diaminodiphenylmethanes can be easily prepared. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs on the other hand, the post-replacement method is to dissolve in dimethyl ether in the presence of bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide or triethylamine Polyamines in solvents such as N-methylpyrrolidone, N, N-dimethylformamide, or N, N-dimethylacetamide, and R3-X or R4-X, etc. The halide reaction is carried out, but when the reactivity is low, the interaction between the hydrazone bond and the sodium hydride or butyl lithium can be removed in advance, and then the reaction with the above-mentioned halide is more suitable. In the production of N-substituted polyamines, in any case, it is necessary to react N-substituted diamine compounds (for the former substitution method) or diamine compounds (for the later substitution method) with dicarboxylic acids, but this reaction is Condensing agents such as (Ph〇) 3P, (Ph 0) PC 1 2. P h P〇C 12 or (C 3 Η 7) 3 P (〇) 〇 should be used when necessary. China National Standard (CNS) A4 Specification (210 X 297 Public Love) -45- 498090 A7 ---__ B7 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (43) , N-methylpyrrolidone, N, N-dimethylformamide or N, N-dimethylacetamide in the presence of a solvent such that the reaction can be performed at a temperature ranging from 20 to 300 ° C. To proceed. In this case of low reactivity, a dicarboxylic acid dihalide is used instead of a dicarboxylic acid, and N, N / -diethylfluorenyldiamine or N 'N > is used instead of a diamine. Dimethylsilyl) diamine is also possible. Although the liquid crystal aligning agent of the present invention contains the aforementioned substituted polyamine as an essential component, there is no problem even if it is used in combination with other polymer components that do not impair the effect of the present invention. In particular, it can be used in combination with other polymer components to further improve the properties. In this case, polymer components that can be used in combination with the N-substituted polyamines of the present invention include the liquid crystal alignment generally used. Polyacrylic acid, soluble polyimide, polyamine and other materials. Since the liquid crystal aligning agent of the present invention can form a liquid crystal aligning film on a substrate, the above-mentioned lacquer composition in a state where the above-mentioned N-substituted polyamine is dissolved in a solvent is usually obtained. In this varnish composition, the concentration of the polymer component is preferably from 0.1 to 40% by weight. When coating the lacquer composition on the substrate, in order to adjust the film thickness, the operation of diluting the polymer-containing composition with the solvent in advance is necessary, but if the concentration of the polymer component exceeds 40% by weight, The viscosity of the composition becomes too high, and even if a solvent is added, the mixing with the composition becomes unfavorable, and there is a disadvantage that the desired dilution cannot be obtained, and it is not suitable. In the case of spin coating method or printing method, in order to maintain the film thickness well, usually (please read the note on the back? Matters before filling out this page) ---- Order ---- Line · »_ This paper size applies to China National Standard (CNS) A4 Specification (210 X 297 mm) -46- Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 498090 A7 — B7 V. Description of Invention (44) It is set to be below 10% by weight. Other coating methods, such as the dipping method, are also available at lower concentrations than 10% by weight. On the other hand, when the concentration of the polymer component is less than 0.1% by weight, the problem of excessively thin film thickness of the obtained liquid crystal alignment film tends to occur. Therefore, the concentration of the polymer component is preferably 0.1 to 1% by weight or more, preferably 0.5 to 10% by weight, in a usual spin coating method or printing method. However, it can also be used at a thinner concentration by applying a lacquer. In the above-mentioned lacquer composition, a solvent that can be used simultaneously with the polymer component is applicable to a solvent having the ability to dissolve a polymer, without any particular limitation. The related solvents are widely used in the production steps or uses of N-substituted polyamines, polyamic acids, and soluble polyimides, and they can be appropriately selected according to the purpose of use. As examples of these solvents, non-protonic polar organic solvents, such as N-substituted polyamines and polyamic acids, and soluble polyfluorene imide as a solvent, such as N-methyl- 2-pyrrolidone, Methyltetrahydroimidazolidone, N-methylcaprolactam, N-methylpropanamide, N, N-dimethylacetamide, dimethylasicon, N, N-dimethylformamidine Amine, N, N-diethylformamide, diethylacetamide or > monobutyrolactone, etc., and other solvents for the purpose of improving coating properties, such as alkyl lactate, 3-methyl- 3 Glycol monoalkyl ethers such as monomethoxybutanol, decalin, isophorone, ethylene glycol monobutyl ether, and diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether Ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monobutyl ether, propylene glycol monoalkyl ether, diethyl malonate, ether, dipropylene glycol monomethyl ether, etc. Dipropylene glycol monoalkyl ether, or ester compounds such as acetates, etc. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm ^ ~ (Please read the precautions on the back first) Complete this page)

-47- 498090 A7 B7 V. Description of the invention (45) System. The lacquer composition obtained in this way is mainly suitable for the formation of liquid crystal alignment films for TFTs, but because it can give a moderate forward tilt angle, it is used to form ordinary TN elements, STN elements, and strong dielectrics. It is also useful when using liquid crystal alignment films for liquid crystals or anti-ferroelectric liquid crystal elements. Furthermore, because it has excellent electrical characteristics as a liquid crystal display device, it can also be used as a protective film or insulating film. aspect. In the case where a liquid crystal alignment film is to be formed, a step of applying a varnish composition on a substrate, a subsequent drying step, and necessary heat treatment for dehydration and ring-closing reactions are performed. As for the method of the coating step, a spin coating method, a printing method, a dipping method, or a dropping method is generally known, but these methods are also applicable to the present invention. In addition, as for the method of applying the necessary heat treatment step to the drying step and the dehydration and closed-loop reaction, the method of heat treatment in an oven or an infrared oven or the method of heat treatment on a hot plate is generally known, but These methods are equally applicable in the present invention. The drying step is preferably performed at a relatively low temperature in a range in which the solvent may evaporate, and the heat treatment step is generally performed at a temperature of 150 to 300 ° C. This varnish composition may contain various additives as needed. For example, in the case where an improvement in coating properties is expected, a surfactant suitable for the relevant purpose will be required, and an antistatic agent is necessary to improve the antistatic property. An antistatic agent will be used in the case of improving the adhesion to the substrate, and a silane coupling agent will be used. Mixtures or titanium-based coupling agents may also be used. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) (Please read Note 3 on the back before filling this page) Printed by Employee Consumption Cooperatives-48- 498090 Printed by Employee Consumption Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (46) Although the following examples cannot be hidden, the present invention is not limited by these% examples . Also in this embodiment, an example can be given in which N is used in combination with polyamine and polyamic acid for the purpose of further improving the characteristics, but even if it is used alone, as long as it does not harm this The effect of the present invention is not a problem for N-substituted polyamines. In each of the examples, the raw material ingredients used are represented by the abbreviations of item 1 below, and unless otherwise specified, the weight ratios or concentrations of the ingredients are based on weight. In addition, the synthesis of the polymer component was carried out by the method referred to in the second item, and the preparation of the lacquer for the formation of 疋 0 was formed by the method described in the third item. With reference to the method, the evaluation of the crystallization chamber was performed by the method of the fifth reference. 1 Use of raw materials

Terephthalic acid: T P E 1,4-Cyclohexanedicarboxylic acid: DCCh Diamine compound without side chains

44 / Monodiaminodiphenylmethane: DPM 4,4 / —Diaminodiphenylethane: DPEt Diamine compound having a side chain group with a carbon number of 3 or more 1,1—bis {4 1 [(4 monoaminophenyl)

Methyl] phenyl} cyclohexane: ChBlB 1,1 bis {4-mono [(4-aminophenyl) methyl] phenyl} -4 monobutyl hexahydrate: 4 C h Β 1 Β This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------------------ r --- Order ---- (Please read first Note on the back? Matters need to be filled out on this page) Thread " S · -49- 498090 A7 B7 V. Description of the invention (47) 1,1 Double {4 Mono (4 aminoaminophenoxy) phenyl} — 4 — (4-pentylcyclohexyl) cyclohexane: 5ChChB〇B 1 — (4-pentylcyclohexyl) — 4 — (4 —

: 5ChChDPM PMDACBDAN Μ PBC Amine group-2-aminophenyl) Cyclohexane tetracarboxylic dianhydride component pyromellitic dianhydride cyclobutane tetracarboxylic dianhydride solvent component N —methyl one 2 — Wake up slightly 2-Butoxyethanol 2. Polymer synthesis 1) Polyamine synthesis In a 500ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen inlet, TPA 3. 2156g, DPM 1.9185g 4ChBlB 4.8 6 5 5 Printed g by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, added dehydrated NM P 8 · 6 3 g and pyridine 9 · 3 3 g to make a homogeneous solution. To this, 12 · Ol of triphenyl phosphite, 4 g of lithium chloride, and 12 g of I5 chloride were sequentially added, and the reaction was performed at 100 to 140 ° C for 2 hours. The obtained reaction solution was reprecipitated with methanol and pure water, and then dried under reduced pressure to obtain polyamine (P A 1) 10 g. Other polyamides were also synthesized in the same manner. The composition of the synthesized polyamide is shown in Table 1. This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) -50- 498090 A7

V. Description of the invention (48) Table 1 Molar fraction of raw materials for synthesis examples (%) Dixiang acid-free side chain di-use decane compound Diamine compound with side chain group TPA ChDC DPM DPEt ChBIB 4ChBIB 5ChChBOB 5ChChDPM PA1 50.0 32.5 17.5 PA2 50.0 32.5 17.5 PA3 50.0 25.0 25.0 PA4 50.0 32.5 17.5 PA5 50.0 32.5 17.5 PA6 50.0 32.5 17.5 PA7 50.0 32.5 17.5 2) N is replaced by polyamines with a thermometer, mixer, raw material inlet and nitrogen The entrance of the Ministry of Economic Affairs ’Intellectual Property Bureau employee printing cooperative printed a 200ml four-necked flask and added polyamine (pAl) 5 · 026 g and dehydrated NM P 2 · 6 · 9 g. After stirring at room temperature for a while, add The sodium hydride was 0.94 g, and stirring was continued for another 40 minutes. To this solution was added methyl iodide 3.07 g, and the reaction was allowed to proceed for 1 hour. The obtained reaction solution was reprecipitated in the same manner as the above-mentioned polyamine (P A 1), and then dried under reduced pressure to obtain N-substituted polyamine (N P A 1). Other N-substituted polyamides can also be synthesized by the same synthetic method. The composition of the synthesized polyamide is shown in Table 2. In addition, NPAs 8 to 11 in Table 2 were each synthesized by using ethyl bromide, n-heptyl bromide, benzyl bromide, and anthracene methyl bromide instead of bromide methyl. The weight average molecular weight of the obtained polymer also shows that this paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -51-498090 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 49) In Table 2. Table 2 Molar fraction (%) of the raw materials of the synthesis examples Substituent molecular weight Dicarboxylic acid diamine compound No side chain diamine compound Carbon number 3 or more β diamine) I compound having side chain group (a) (b) ( c) (d) (e) (f) (g) (h) NPA1 50.0 32.5 17.5 methyl 52000 NPA2 50.0 32.5 17.5 methyl 65000 NPA3 50.0 25.0 25.0 methyl 78000 NPA4 50.0 32.5 17.5 methyl 63000 NPA5 50.0 32.5 17.5 forma 51000 NPA6 50.0 32.5 17.5 Methyl 99,000 NPA7 50.0 32.5 17.5 Methyl 36000 NPA8 50.0 32.5 17.5 Ethyl 50000 NPA9 50.0 32.5 17.5 N-pentyl 48000 NPA10 50.0 32.5 17.5 Benzyl 49000 NPA11 50.0 32.5 17.5 Anthracene 51000 Base Note: In the table (A), (b), (c), (d), (e), (f), (g), and (h) each refer to TPA, C h DC, DP Μ, D PE t, C h B IB, 4 C h B IB, 5 C h C h BOB and 5 C h C h DPM. (Please read the phonetic on the back? Matters before filling out this page) f Line f This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -52- Printed by the Employees ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 498090 A7 B7 V. Description of the invention (50) 3) Synthesis of polyamic acid In a 5001111 four-necked flask equipped with a thermometer, a stirrer, a raw material input port and a nitrogen introduction port, add 0 to 14.8908, dehydrated NM P 9 0 · 0 g, dissolved by stirring under a stream of dry nitrogen. While maintaining the temperature of the reaction system at 5 to 70 ° C, PMDA2 · 6902g and CBDA2 · 4190g were added sequentially, and after 5 to 30 hours of reaction, BCl was added to synthesize a polymer concentration of 5%. Polyamic acid (PA acid). During the reaction, the temperature of the starting materials increases during the reaction, and the reaction temperature is suppressed to about 70 ° C and the reaction is allowed to proceed. The weight-average molecular weight of the obtained polymer was 7500. • The lacquer for orientation film formation was prepared from fluorinated polyamic acid having a polymer concentration of 5% obtained from a synthetic example of polyamic acid. Lacquer 18 · 0 g was added with N-substituted polyamines in a synthesis example of 0.10 g and dissolved, and then diluted with a diluting solvent to a polymer concentration of 3%, and used as an orientation film. Lacquer. 4 · Fabrication of chamber for evaluation of orientation film 1) Fabrication of chamber for evaluation of residual charge and voltage retention rate On glass substrates with transparent electrode IT 0, each coating varnish was coated with a spin coater at 80 ° C After preliminary firing for about 5 minutes, heat treatment was performed at 250 ° C for 30 minutes to form an alignment film. The surface of the substrate after the formation of the orientation film is polished by a polishing device for orientation treatment. Secondly, the paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 male-53-I equipment ----- r-- -Order --------- (Please read the notes on the back to write this page) | 498090 A7 ------- B7 V. Description of the invention (51) Spread 7 on it // Use it A gap material is used to form the orientation film as an inner side, and the periphery of the liquid crystal injection hole is sealed and removed with an epoxy hardener, and an antiparallel cell with a gap of 7 // m is produced. A liquid crystal composition (NI point: 8 1.3 ° C, complex refractive index: 0 · 0 9 2) is injected into this chamber, the injection port is sealed with a light hardener, and UV light is irradiated to harden the liquid crystal injection hole, followed by 1 1 Heated at 0 ° C for 30 minutes and used as a chamber for the evaluation of residual charge and voltage retention rate. (Please read the note on the back? Matters before filling this page) _____ Order ----

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -54- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 498090 A7 B7 V. Description of the invention (52) 2) In addition to using a 2 0 // spacer instead of a 7 μ spacer, the remaining charge and voltage retention rate were evaluated in the same manner as in the case of the ancient chamber. The inverse of the chamber thickness with 2 0 // The production of a parallel cell, the injection of the liquid crystal composition, and subsequent processing are used as a cell for forward tilt measurement. 5. The s-level estimation of the liquid crystal cell 1) The method of measuring the residual charge The measurement of the residual charge is, for example, the conventional method described in "Miyake et al., Shinichi Gakuin EID 9 1-1 1 1 page 19" , By measuring the hysteresis voltage. In addition, an alternating current of 50 m V and lkHZ and a direct current triangular wave having a frequency of 0.0Q36HZ were superimposed on the liquid crystal cell and measured. 2) Measurement method of voltage retention ratio The measurement of the voltage retention ratio is, for example, an existing method described in "Minzu et al., Proceedings of the 14th LCD Symposium, page 78". The measurement conditions are gate width 6 9 // s, frequency number 6 Ο Η Z, wave height ± 4 · 5 V, and measurement temperature is 60 ° C. 3) Measuring method of forward tilt angle The measurement of the forward tilt angle of the liquid crystal is performed by the crystal rotation method. 4) Evaluation method of orientation This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back? Matters before filling this page) l · —Order—

A -55- 498090 A7 B7 V. Explanation of the invention (53) The evaluation of the orientation is the presence or absence of a domain used to determine the domain when observing and measuring the lean angle under a polarizing microscope. Examples 1 to 1 1 In addition, 0.1 g of N-substituted polyhydric polyimide, which was added to 1.8 g of lacquer made of polyamino acid (p A acid 1) with a polymer concentration of 5%, was dissolved in 1.8 g. The amidines are each NPA 1 to 1 1 shown in the column of the synthesis example in Table 2. The rest is the same as the method described in item 3 above to prepare a lacquer for alignment film formation (liquid crystal aligning agent). Residual charge, voltage retention, rake angle and directivity. The results are shown in Table 3. -装 _ --- r I--Order- ί !! — · (Please read the note on the back? Matters to write on this page) Printed on paper standards of the Ministry of Economic Affairs, Intellectual Property Bureau, Employees' Cooperatives, Chinese paper standards ( CNS) A4 size (210 X 297 mm) -56- 498090 A7

V. Description of the invention (54) Table 3 Example N Residual Load of Substituted Amines / mV Voltage Retention Rate /% Leaning Angle / degree Directionality Example 1 NPAP1 6 98.4 2.5 Good Example 2 NPAP2 12 98.6 2.6 Good Example 3 NPAP3 8 98.2 3.5 Good example 4 NPAP4 3 98.2 2.9 Good example 5 NPAP5 15 98.4 2.0 Good example 6 NPAP6 26 98.0 5.6 Good example 7 NPAP7 12 98.8 7.7 Good example 8 NPAP8 18 98.2 2.2 Good example 9 NPAP9 14 98.5 1.2 Good example 10 NPAP10 8 98.6 1.5 Good example 11 NPAP11 10 98.5 1.5 Good I ϋ In I — ϋ One-port, · I ϋ ϋ. (Please read the note on the back? Matters before filling this page} Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 3 shows that the liquid crystal aligning agents of Examples 1 to 11 using the N-substituted polyamide of the present invention include electrical characteristics such as residual charge, voltage retention, or forward tilt, orientation Various characteristics including orientation characteristics such as orientation are comprehensively observed, and the balance is good and superior. The industrial applicability is as described above. According to the present invention, it can be used for liquid crystals. The improvement of various properties such as the forward rake angle or directivity expected by the centrifugal agent, and the electrical characteristics such as residual charge, voltage retention, and baking can be comprehensively and well-balanced. The paper size applicable to this national standard (CNS) A4 specification (210 X 297 mm) -57- 498090 A7-one-_B7_ V. Description of the invention (55) Polyamide compound for liquid crystal aligning agent. In addition, the liquid crystal aligning agent containing the polyamine compound is especially expensive. @ TFT element (TN-type TFT element, IPS element) For its excellent electrical characteristics, the forward tilt angle can be adjusted arbitrarily, so it can be used even for STN element, ferroelectric liquid crystal, and anti-ferroelectric liquid crystal element. It can also be used as a protective film or insulation film. Please read the note above

Page Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm) 58

Claims (1)

498090 〇〇ω Amendments to the scope of the Chinese patent application in February of the Republic of China • Amended a polyamine compound characterized by the formula (1) R3 R4 -R1—CO—N—R2—N— (In the formula, R 1 represents A divalent organic residue derived from a dicarboxylic acid, R 2 represents a divalent organic residue derived from a diamine, but at least one of these is a divalent organic residue having a side chain group having a carbon number of 3 or more R 3 and R 4 represent independent hydrogen or a monovalent organic group, but the content of the monovalent organic group is based on the total amount of R 3 and R 4 being 30 mol% or more, and n is a natural number) At least one of the polyamine compounds represented by R2 is the formula (2 — 1) to (2 — 4) (Please read the precautions on the back before filling this page) i # Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (2-1) This paper size applies to China National Standard (CNS) A4 (210X297 mm) ^ 16v_y ^ l7 (2-4) f 498090 A8 B8 C8 D8 VI. Application scope of patent (Various alkyl rings, z 0 ~ 3 t is 2, R 5, R], Y represents a single bond represents a single bond, s When the table is 0 to 3, (2-2) on each Z benzene ring or cyclohexane ring, the formula (2 is reduced. Those that are enlarged or cracked increase or decrease, and the organic residues can be replaced by monovalent organic groups. The base group is selected from the group of 2. 6, R17 represents hydrogen or carbon number 1 ~ 1 2 junction or CH2, ring A represents benzene ring or cyclohexane CH2, CH2CH2 or or oxygen, r represents 5, and t represents 0 ~ 3. Respective positive integers, but may be the same as each other or may be different; and arbitrary hydrogen may also be substituted by lower alkyl; but any ring of the steroid backbone such as formula-3) may be a bicyclic ring, any position The unsaturated bond may be a hydrogen atom at any position or an alkyl group is any one of the polyamine compounds having a side chain group of 3 or more carbon atoms, which is characterized by the formula (1) (please read first Note on the back, please fill out this page) T, f 2 f R1——CO—N——R2—N——OC- (1) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (form , R 1 represents a divalent organic residue derived from a dicarboxylic acid, and R 2 represents a divalent organic residue derived from a diamine, but at least one of them is a side chain group having a carbon number of 3 or more Divalent organic residues, R 3 and R 4 represent independent hydrogen or monovalent organic groups, but the content of the monovalent organic group is based on the total amount of R3 and R4 being 30 mol% or more, n is natural Polyamine compound represented by at least one of the formulas, at least one of R 2 is the formula (3) The paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 2- 498090 Α8 Β8 C8 D8, scope of patent application (In the formula, X1 represents a single bond, CH2 or CH2CH2, R6 and R7 represent each independently hydrogen or an alkyl or perfluoroalkyl group having 1 to 12 carbon atoms, but at least one of them represents a carbon number of 3 or more. Alkyl group or perfluoroalkyl group 'u is 0.3, but when u is 2-3, each X1 may be the same or different from each other; and the hydrogen on any benzene ring may be substituted by alkyl group) An organic residue of a side chain group having 3 or more carbon atoms. 3. —A kind of polyamine compound, which is characterized by the formula (1)-(Please read the precautions on the back before filling this page), 1T (In the formula, R \ represents a divalent organic residue derived from a dicarboxylic acid, and R 2 · represents a divalent organic residue derived from a diamine, but at least one of these is a compound having a carbon number of 3 or more. A divalent organic residue of a side chain group, R 3 and R 4 represent independent hydrogen or a monovalent organic group, but the content of the monovalent organic group is based on the total amount of R 3 and R 4 is 30 moles % Or more, n is a natural number), at least one of R 2 is represented by formula (4) This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) # Γ Intellectual property of the Ministry of Economy Printed by the Bureau's Consumer Cooperatives 498090 A8 B8 C8 D8 Patent Application Scope -R8——X3—R9—RU (In the formula, 'X2, X1 represent independent single bonds, 〇, c〇〇, 〇C〇, NH, CONH (CH2) n, R8, R 9 Is a bivalent fluorene containing 1 to 3 rings, each containing a single bond or an aromatic ring and / or an alicyclic ring, R1. It represents hydrogen, F, a hydrocarbon group, a gasified hydrocarbon group, an alkoxy group, a cyano group, or 〇Η group, n is an integer from 1 to 5; but the group-XR-X 3-R 9-R is not a hydrogen atom, any of the alkyl alkoxy group or trifluoromethyl group of carbon ^ ~ 8) means An organic residue of a side chain group having 3 or more carbon atoms. 4 · A polyamine compound characterized by the formula (1) R3 R4 -R1——CO—N——R2——N——OC- ⑴ (Please read the notes on the back before filling this page} i ·, 1T. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (In the formula, R 1 represents a divalent organic residue derived from a dicarboxylic acid, and R 2 represents a divalent organic residue derived from a diamine. At least one of these is a divalent organic residue having a side chain group having a carbon number of 3 or more. R 3 and R 4 represent independent hydrogen or a monovalent organic group, but the content of the monovalent organic group. Based on the polyamine compound represented by the total amount of R 3 and R 4 being 30 mol% or more, η is a natural number, in which at least one of R 2 is represented by formula (5) This paper size applies Chinese national standards ( CNS) A4 specification (210 × 297 mm) -4 498090 A8 B8 C8 D8 々, patent application scope Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (In the formula, Ai represents a hydrogen atom., Or a linear or branched alkyl group having 1 to 12 carbon atoms. More than any arbitrary methylene group may be substituted by an oxygen atom, As represents a single bond or a radical group having a carbon number of 1 to 5, one of the radical groups or two or more adjacent arbitrary methylene groups It may be substituted by an oxygen atom, m is 0 to 3, and η is 1 to 5). An organic residue having a side chain group of 3 or more carbon atoms. 5. The polyamine compound according to any one of claims 1 to 4, wherein R3 and R4 in the polyamine compound represented by the aforementioned formula (1) represent mutually independent hydrogen or a carbon number of 5 or less The monovalent organic group has a content of 50 mol% or more based on the total amount of R 3 and R 4. 6. Polyamines according to any one of claims 1 to 4. The compound, wherein R3 and R4 in the polyamine compound represented by the aforementioned formula (1) represent mutually independent hydrogen or a carbon number of 5 or less A monovalent organic group selected from the respective alkyl group or oxygen-containing alkyl group, and the content of the monovalent organic group is 70 mol% or more based on the total amount of R 3 and R 4. 7. The polyamine compound according to any one of items 1 to 4 of the patent application No. Fe, which is contained in a liquid crystal aligning agent. '8 · If the polyamide compound of item 5 of the patent application scope, it is a package (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) 498 090 090 A8 B8 C8 D8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the patent application scope is included in the liquid crystal alignment agent. 9. The polyamide compound according to item 6 of the patent application scope, which is contained in a liquid crystal aligning agent. (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm)