TWI260457B - Aligning agent varnish for liquid crystal and liquid-crystal display element - Google Patents

Abstract

An aligning agent varnish for liquid crystals, which considerably influences especially the display characteristics of a liquid-crystal display element. It has improved properties so as to have an excellent total balance among liquid-crystal alignment properties, electrical properties, etc. It is characterized by containing a polyamic acid obtained from tetracarboxylic acids comprising as essential ingredients at least one tetracarboxylic acid having a tetracarboxylic acid residue represented by the formula (1) and cyclohexanetetracarboxylic dianhydride. A liquid-crystal display element produced with the aligning agent varnish, which contains the compound, eliminates the problems.

Description

1260457 Α7 Β7 Ministry of Economic Affairs Intellectual Property Office Employees' Consumption Cooperatives Printing V. INSTRUCTIONS (1) BACKGROUND OF THE INVENTION The present invention relates to a liquid crystal aligning agent lacquer containing poly-amphibious acid used in the field of electronic materials.本 In the present invention, the "tetracarboxylic acid" is defined as a tetracarboxylic dianhydride, and the two carboxyl groups of the tetracarboxylic acid are derivatives of a halogenated group and a tetracarboxylic acid of a non-anhydrous state. The general term for the compound of the residue. The liquid crystal display element is currently dominated by a display element using nematic liquid crystal, and the liquid crystal is a TN type liquid crystal display element using a 90° twist, and is generally a STN type liquid crystal display element having a twist of 180° or more, a thin film transistor, etc. A TFT type liquid crystal display element, and a transverse electric field type IPS type liquid crystal display element having improved viewing angle characteristics, a VA type liquid crystal display element in a vertically oriented state, or a CB type liquid crystal display element in a bent alignment state. Display elements of various modes have been put into practical use or have been reviewed. The progress of the liquid crystal display element has not only progressed in such a manner, but has frequently improved the peripheral material toward the characteristics of the liquid crystal display element. Further, the liquid crystal aligning agent is one of the important elements relating to the display quality of the liquid crystal display element. However, the demand for the liquid crystal aligning agent is further increased as the quality of the display element is required to be improved. The liquid crystal aligning agent which is mainly used at present is a polyimine-based orienting agent such as polyamido acid which is amidated by polyaminic acid and soluble polyimine. In addition to the polyimine-based orienting agent, a polymer compound such as polyamine which is substituted with a hydrogen atom of a polyamide bond of a polyamide and a polyamine, and a polyamine of the polyamine is also used. There are problems with the electrical characteristics of the liquid crystal element and the like. In addition, there are also a mixture of a plurality of polymer compounds, and the use of the block paper size is applicable to the Chinese National Standard (CNS) Α4 specification (2i〇: xT297 mm) ^ —-4- (please read the notes on the back first) I> HI emv 11 ►fill this page) Book 1260457 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 5, Inventions (2) Liquid crystal directional agent for polymer compounds, but consumes current, residual Charges, voltage retention, baking, etc. are still difficult at present. Thus, as the liquid crystal display element is used in various fields, the characteristics required for the liquid crystal display element become higher performance. Among these properties, the requirements for the alignment characteristics of the liquid crystal represented by the elevation angle of the liquid crystal, the requirements for the electrical characteristics of the liquid crystal display element such as current consumption, residual charge, voltage holding ratio, baking, etc., or for such characteristics are listed. Requirements for reliability for long-term use, and for image display of liquid crystal display elements, display quality requirements such as display unevenness, and the like. The front elevation angle of the liquid crystal among these characteristics varies depending on the driving mode of the liquid crystal display element. For example, a TN liquid crystal display device or a TFT liquid crystal display device in which the liquid crystal is 90° torsion must have a front elevation angle of about 1 to 6 degrees, and the STN liquid crystal display element having a large twist angle must be about 3 to 8 degrees ago. Elevation angle. However, the number of elevation angles before the request is required to vary depending on the application. Recently, the front elevation angle of 2 to 3 degrees or more is also required in the S T N type liquid crystal display element. On the other hand, in the I P S type liquid crystal display device, since the liquid crystal operates in the horizontal direction with respect to the substrate, it is not necessary to increase the front elevation angle, and the front elevation angle is about 1 to 3 degrees. On the other hand, in the V A type liquid crystal display element, it is necessary to have a large front elevation angle near 90 degrees, and in the 〇C B type liquid crystal display element, in order to stabilize the bending orientation state, a front elevation angle of 5 to 20 degrees is required. Further, it is important that not only the front elevation angle, but also the alignment property of the alignment uniformity, the orientation stability or the bonding energy of the liquid crystal alignment film interface, and the performance of the liquid crystal display element. Moreover, the Chinese National Standard (C'NS) a4 specification (210X297 mm) is applicable to the liquid crystal display meta-paper scale (please read the note on the back of the IP address to fill in this page) - Install -, 11-line 1260457 Ministry of Economics Intellectual Property Bureau employee consumption cooperatives print A7 _____ B7 V. Inventions (3) In the manufacturing process, the process limits of these characteristics are also important, the drying conditions of the solvent after coating by the directing agent, the rubbing treatment conditions or the liquid crystal injection The subsequent annealing treatment conditions and the like cause a change in the front elevation angle and the liquid crystal orientation change. The S T N type liquid crystal display element is particularly a low voltage type element used in the field of portable devices. Since the driving voltage of the liquid crystal display element is low, it is important for the current consumption 値. In other words, if the current consumption of the liquid crystal display element is increased, the voltage of the liquid crystal is lowered, so that the liquid crystal is not sufficiently activated and the contrast is lowered. Further, in the low-voltage type liquid crystal display device, the current consumption 値 change (reliability) in the long-term use of the liquid crystal display element is also important. Since the S T N type display element is caused by a slight potential difference due to the display of 〇N - 〇 F F , if the current consumption 値 of the element changes, the voltage applied to the liquid crystal also changes and cannot be normally driven. In the extreme case, the image of the liquid crystal display element is not displayed at all due to long-time driving. On the other hand, regarding the S T N type liquid crystal display element, it is particularly important to have a residual charge requirement for the voltage holding ratio. If the voltage holding ratio is low, the voltage applied to the liquid crystal during the frame period is lowered, and the contrast is lowered. Further, in the case where the residual electric charge is large, even if the voltage 〇 F F is applied after the voltage is applied, the electric charge remains in a state in which the electric charge remains, and the image to be erased remains in the afterimage type. This afterimage phenomenon is an important problem in the T F T type liquid crystal display element. In addition, in recent years, with the low voltage of the liquid crystal driving voltage, liquid crystals having a large dielectric anisotropy have been used, and thus the display of the paper size in the front side of the display is applicable to the Chinese National Standard (CNS) A4 specification (2) 0X 297. () Please read the note on the back of the Qin] gt; install -- π fill this page. Order -6 - 1260457 ΑΊ B7 V. Invention description (4) Spot (brightness spot) problem. In particular, if the water is washed in order to remove the debris generated when the alignment film is rubbed, the phenomenon of the water-washing phenomenon may become a phenomenon in which the spot type remains, which is a big problem. Disclosure of the Invention The present invention provides a liquid crystal display element which is excellent in liquid crystal display element and which has a moderate front elevation angle and which is excellent in liquid crystal orientation and electrical characteristics (voltage holding ratio, residual charge, baking). A liquid crystal aligning agent is a subject. The inventors of the present invention have made a review of the structure of the polyamic acid used for the liquid crystal directional paint, although the polyamic acid which uses cycloalkane as the skeleton of the tetracarboxylic dianhydride has been reviewed so far, but An example of a tetracarboxylic acid hydride having no cyclohexane tetracarboxylic dianhydride and a tetracarboxylic acid residue represented by the following formula (1) is found to be an accident which cannot be achieved by using it alone. The above problems are achieved and the present invention has been completed based on these findings. That is, the present invention has the following constitution.

Ji;装·—(Read the first note on the back of the page to fill out this page) Customize the Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperatives, printing, lacquer residue, four doses, to the specific acid with a crystal containing liquid Amine, enamel enamel agent can be used to determine the crystallized back-liquid species, a compound of the group Rj amine 1 C and the like acid carboxylic acid tetrabasic residual acid carboxylic acid four originals as the class of > acid 1 Carboxylic V3/C four-form alkyls have been used in the lower ring

The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1260457 A7 B7 V. Inventive Note (5) (However, in the formula (1), the bonding position of R is any position of the cyclobutane ring 'R is an alkyl group having 1 to 12 carbon atoms, a benzene ring or a cyclohexane ring, and Q is a number of 〇~4. When q is 2 to 4, each R is the same or different from each other. The hydrogen bonded to the benzene ring or the cyclohexane ring may be substituted by a lower alkyl group. [2] The liquid crystal aligning agent lacquer according to the above [1], wherein the liquid crystal directional varnish is contained in the enamel The diamine compound which is one of the amino acid raw materials is a diamine compound represented by the following formula (2). ---------Install -- (Please read the note on the back first to write this page)

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing system (2) 5, / and m are independently 〇 ~ 2, the methyl group for the benzene ring bonding position is arbitrary position) [3] as the above [1] Or the liquid crystal directional varnish of [2], wherein the diamine compound which is one of the polylysine raw materials contained in the liquid crystal aligning enamel paint is a diamine compound having a carbon number of 3 or more side chain groups. . [4] The liquid crystal aligning agent enamel according to the above [3], wherein the diamine compound having a carbon number of 3 or more side chain groups is selected from the group consisting of compounds represented by the following formulas (3) and (4). Diamine based compound.

(3) Line paper size applies to China National Standard (CNS) A4 specification (2] 0: < 297 mm) 1260457 A7 B7 V. Invention description (6 (However, in the above formula (3), R! Hydrogen or carbon number 丄~丄Y is a single bond or methylene group, ring A is 1,4 phenyl or cyclohexyl, Z is a single bond, methylene, ethyl or oxygen, rs is 〇~5. t is a number of 0 to 3, but t is 2 to 3 Z is the same or different from each other. Also, 'the hydrogen bonded to 1, 4 1,4 a cyclohexyl group can also be substituted by a lower alkyl group. Alkyl, 1,4 a stretched horse 0~3, the case, each ~ stretch phenyl or (please read the back of the note before Qin

XfB rX2—巳2-Latch 2) Chinese (4) I loaded -- ίτ fill this page) Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative (however, in the above formula (4), X i~X 2 are independent _一〇一,一C〇〇一,一〇C〇一,一NH—, a CONH—, or a C1-C12 alkyl group, B is independently represented as a single bond, or contains an aromatic ring Family and alicyclic soils φ ^ i ~ 3 rings of divalent groups, R 2 represents a Η, a F, - cn, a 〇Η, or a carbon number of 1 to 12 alkyl, fluoroalkyl or alkoxy Further, the bonding position of the substituent to the benzene ring is an arbitrary position) [5] The liquid crystal aligning agent enamel according to the above [4], wherein the diamine compound having a carbon number of 3 or more side chain groups is A diamine compound selected from the group consisting of compounds represented by formula (3). [6] The liquid crystal aligning agent enamel according to the above [4], wherein the diamine compound having 3 or more carbon atoms in the side chain group is a diamine compound selected from the group of compounds represented by the formula (4). And B 2 points Ding • Line·

.IVT This paper scale is applicable to China National Standard (CNS) Α4 specification (210Χ 297 mm) -9 - 1260457 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (7) [7] as mentioned above [1] The liquid crystal aligning agent of any one of [6], wherein the ratio of the polyamic acid occupied by the liquid crystal aligning agent is 0.1 to 4% by weight. [8] A liquid crystal display element characterized by using the liquid crystal aligning agent lacquer according to any one of the above [1] to [7]. [9] A poly-proline or polyimine characterized by a tetracarboxylic acid having a tetracarboxylic acid residue represented by the formula (1) and a tetracarboxylic acid containing a cyclohexanetetracarboxylic acid, and a formula The compound represented by (2), (3) and (4) is obtained by reacting one or more kinds of diamine-based compounds. [10] A liquid crystal display device comprising a fluorine-based liquid crystal composition in the liquid crystal display device described in the above [8]. BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a tetracarboxylic acid having a cyclohexanetetracarboxylic acid and a tetracarboxylic acid residue represented by the formula (1) [hereinafter, a tetracarboxylic acid represented by the formula (1) Performance] Poly-amic acid obtained as a raw material, or liquid crystal directional paint containing them. The cyclohexanetetracarboxylic acid and the tetracarboxylic acid represented by the formula (1) are particularly used for the purpose of improving the liquid crystal directionality and electrical properties of the liquid crystal display device, and the effects are not obtained when they are used alone. Namely, the polyglycolic acid used in the present invention has an effect by the specificity of its structure, i.e., the tetracarboxylic acid residue. Therefore, if the raw material is provided with the same residue, the type of the raw material is not limited. When it is called "tetracarboxylic acid" as defined above, it means tetracarboxylic dianhydride, and the two carboxyl groups of the tetracarboxylic acid are warp. A group of a halogenated derivative and a tetracarboxylic acid in a non-anhydrous state. However, the following is applicable to the Chinese National Standard (CNS) A4 specification (2; OX 297 mm) in order to avoid the paper scale (please read the note on the back first^^^^|||:fill this page} J--装·线· -10- 1260457 Ministry of Economic Affairs Zhici Property Bureau employee consumption cooperative printing ΑΊ 五 五 五 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明Specific examples of the cyclohexanetetracarboxylic anhydride and the tetracarboxylic dianhydride represented by the formula (1) include 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 1, 2, 4, 5-ring. Hexanetetracarboxylic dianhydride, methyl-1' 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl- 1,2,3,4-cyclobutane tetracarboxylic dianhydride 1,1,3-dimethyl- 1 '2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3-trimethyl- 1,2,3,4-cyclobutanetetracarboxylic acid Anhydride and 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutane tetracarboxylic dianhydride. Use of cyclohexane tetradecanoic acid and tetracarboxylic acid of formula (1) Although the ratio varies according to the required characteristics, it is usually ( The molar ratio of hexane tetracarboxylic dianhydride/tetracarboxylic dianhydride represented by formula (1) is (97/3) to (3/97), preferably (90/10) to (10/). 90), more preferably (70/30) ~ (30/70). In order to maintain the voltage retention rate as much as possible, the ratio of tetracarboxylic dianhydride represented by formula (1) is not as good as 5, in order to be good. Maintaining the front elevation angle and orientation, it is preferable to make the ratio of the cyclohexane tetraresic acid dianhydride as small as possible. Therefore, it is desirable to use cyclohexanetetracarboxylic dianhydride and the tetracarboxylic acid represented by the formula (1). In particular, depending on the type of the diamine to be used, cyclohexanetetracarboxylic dianhydride is not used alone, and it is preferable to maintain the solubility and printability when it is used as a liquid crystal aligning agent. In the present invention, the tetracarboxylic dianhydride component of the raw material for producing a polyproline may be a tetracarboxylic dianhydride represented by the formula (1) or a tetracarboxylic dianhydride other than the cyclohexanetetracarboxylic dianhydride. Other tetracarboxylic dianhydrides which can be used in the invention may also be aromatic (including heterocyclic), and alicyclic (including heterocyclic-based paper standards applicable to China National Standard (CNS) a4 (2) 0 X 297厘) (Please read the note on the back to fill out this page) - Packing and Booking 1260457 A7 B7 Ministry of Economic Affairs, Intellectual Property Office, Consumers' Cooperatives, Printing 5, Inventions (9)) or Alien (Acyclic) Any one of the groups, which also has a ring structure, is preferred because it maintains the orientation of the liquid crystal. Therefore, when an aliphatic (non-cyclic) substance is used, it is combined with an alicyclic system and/or The aromatic-based substance is preferably used in an amount which does not adversely affect the directivity, and is less likely to cause a decrease in the gas-phase property of the liquid crystal display element. It is preferred to use a base which does not contain an ether, an ester or a thioether, but there is no problem in using such a tetra-residual acid dianhydride as long as the effect of the present invention is not impaired. The tetracarboxylic dianhydride which can be used together with the cyclohexanetetracarboxylic dianhydride and the dicarboxylic acid diterpene of the formula (1) can be arbitrarily selected from a plurality of compounds known in the prior art, and a specific example thereof can be enumerated. Cyclopentane tetracarboxylic dianhydride, biscycloheptane tetracarboxylic dianhydride, bicyclo(2,2,2 )-octyl(7)-ene-2,3,5,6-tetracarboxylic dianhydride, cyclohexyl Alkane-1,2,5,6-tetraki-one-dry>3,4-one residue-1,2,3,4-tetrachloro-ca- 1 succinic dianhydride, 3,3 / - double ring Hexyl-1,1/,2,2/tetrahydro acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5 (2'5-dioxytetrahydrofuranyl)-3 3-3-cyclohexene-1,2-dicarboxylic dianhydride; [,3,3 a,4,5,9 b-hexahydro-5-tetrahydro-2,5-dioxy-3 Monofuryl)~naphthalene [1,2-c]furan, 3-dione, 3,5,6-3 carboxyl-norbornane-2-acetylacetate, 2,3,4,5-tetrahydrofuran Residual acid dianhydride, tetracycline [6 · 2 . 1 1 , 3 · ◦ 2 , 7] ten ~ hospital - 4 ' 5 , 9 ' 1 〇 - tetracarboxylate Acid dianhydride, pyromellitic dianhydride, 3 ' 3 ' 4,4 / benzophenone tetracarboxylic dianhydride, oxalic acid dianhydride (2 scale applicable to China (2 〇 x 297 mm -) ^ ( Please read the following note on the back of the page. Loading-binding -12 - 1260457 Α7 Β7 V. Invention description (1〇), 3,6,7-naphthalic anhydride, etc.), 3,3^,4,4^ - diphenylmethanetetracarboxylic dianhydride, 3,4,4/diphenylethanetetracarboxylic dianhydride, 3,3 / ,4,4/diphenylpropane tetracarboxylic dianhydride, 3,3,,4,4/ diphenyl benzene tetracarboxylic dianhydride, 3,3,4,4 - diphenyl ether tetracarboxylic dianhydride, 3,3 -, 4,4, one Dimethyldiphenylnonanetetracarboxylic dianhydride, 4,4 / -bis(3,4-dicarboxyphenoxy)diphenyl sulphate, 4,4 / bis (3,4-dicarboxybenzene) Oxy)diphenyl dianhydride, 4,4 / -bis(3,4-dicarboxyphenylmethyl)diphenylmethane dianhydride, 4,4 / a pair (3, 4 - dicarboxyphenyl) Methyl)diphenylethanedione, 4,4 / bis( 3 ,4 -didecylphenylmethyl)diphenylpropane dianhydride, 4,4 / — double 3,6-Dicarboxyphenoxy)diphenylmethane dianhydride, 4,4 / bis(3,4-dicarboxyphenoxy)diphenylethane dianhydride, 4, 4 / one pair (3 , 4 - dicarboxyphenoxy)diphenylpropane dianhydride, 3 , 3 / , 4, 4 / - perfluoropropylene dicarboxylic acid dianhydride, 3,3 -, 4, monobiphenyl tetracarboxylate Acid dianhydride, bis(capric acid) phenyl hydroxide trihydrocarbyl sulphur dianhydride, p-phenyl-bis(triphenylphosphonic acid) dianhydride, m-phenylene bis(triphenyl decanoic acid) Anhydride, bis(triphenylphosphonic acid)-4,4' diphenyl ether dianhydride and bis(triphenylphosphonic acid)-4,4' diphenyl phthalic anhydride and these compounds A compound in which a lower alkyl group such as a methyl group and/or an ethyl group is partially substituted. Other examples include a compound having a different bonding position of a carboxyl group relative to the compounds, and a carbon number of the alkyl group and/or an alkylene group having a different structure, and an alkyl group and/or an alkyl group in the structure. Any C Η 2 is replaced by 〇 ,, any η is replaced by f, the aromatic ring paper size applies to Chinese national standards. (CNS ) Ad specifications (2 〇χ 297 mm) (please read first Note on the back of the page. - Installation · Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumer Cooperatives Printed - 13- 1260457 A7 B7 V. Description of Invention (11) For the replacement of a different number of alkyl groups, etc. Feel free to use. The diamine-based compound which is the other raw material of the poly-proline is also an aromatic (including a heterocyclic), an alicyclic (including a heterocyclic) or an aliphatic (the heterocyclic). Any one of the groups of non-rings, in which the ring structure is good, maintains the orientation of the liquid crystal, so that it is preferable. In the present invention, the diamine-based compound represented by the above formula (2) is preferably used, and specific examples thereof include 4,4/diaminodiphenylmethane, and di-(4-amino-2-carboxylate). Phenyl)methane, bis(4-monoamino-3-methylphenyl)methane, di-(4-amino-3,5-dimethylphenyl)methane, 4,4/diamino Diphenylethane, 1,2-bis(4-monoamino-3-methylphenyl)ethane, 1,2-di-(4-amino-3,5-dimethylphenyl) Alkane, 4,4/monodiaminodiphenylpropane, 1,3 bis-(4-monoamino-2-methylphenyl)propane, 1,3-bis-(4-amino- 3) Methylphenyl)propane, 1,3 -bis-(4-amino-3,5-dimethylphenyl)propane, 4,4/~diaminodiphenylbutane, 1 ,4 pair Mono(4-monoamino-3-methylphenyl)butane, 1,4-bis(4-amino-3,5-dimethylphenyl)butane, 4,4>-diamine Diphenylpentane, 1,5-bis(4-monoamino-2-methylphenyl)pentane, 1,5-bis-(4-aminol- 3 monomethylphenyl)pentane, 1,5-bis-(4-monoamino~3,5-dimethylphenyl)pentane, and the like. These diamine-based compounds are preferred compounds which are more effective in improving electro-oxidation characteristics than diamine-based compounds having one 〇_, -C〇-, one C(CF3) 2 - , and one C-polarity. This paper scale applies to the Chinese National Standard (CMS) A4 specification (210X 297 mm) (please read the note on the back to write this page) Loading and Customs Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed -14- 1260457 Α7 Β7 V. Inventive Note (12) The proportion of the diamine compound in the raw material diamine varies depending on the required electrical characteristics, but the larger the ratio, the more the residual charge, the voltage holding ratio, and the baking resistance are improved. Further, in the present invention, a compound represented by the formula (2) is used instead, or a compound represented by the formula (2) is used, and at least one compound having a carbon number of 3 or more side chain groups is used as a raw material diamine. The necessary raw materials are preferred for having a high front elevation angle. Examples of the diamine-based compound having a carbon number of 3 or more side chain groups include aliphatic hydrocarbons having a side chain group, hydrocarbons having an alicyclic structure, aromatic hydrocarbons, and a decyloxy group. A diamine-based compound having a steroid skeleton or a plurality of side chain groups thereof. Some of such hydrocarbons may be substituted with other atoms such as oxygen, and may have a substituent of an alkyl group, an alkoxy group, a halogen or the like in the alicyclic hydrocarbon group and the aryl group hydrocarbon group. As the diamine, a compound which does not contain a base such as an ether, an ester or a thioether 'thioester which is liable to cause deterioration in electrical properties of the liquid crystal display element is generally used, but it is used as long as it does not affect the effect of the present invention. There are no problems with this type of diamine. In the present invention, at least one compound selected from the group consisting of the compound represented by the above formula (3) and the compound represented by the formula (4) is used as a diamine compound having a carbon number of 3 or more side chain groups. It is better because it can express a high front elevation angle. In other words, only one or more compounds represented by the formula (3) may be selected, and only one or more compounds represented by the formula (4) may be selected, and one or more compounds represented by the formula (3) and one may be used. A compound represented by the above formula (4).

First, a specific example of the diamine-based compound represented by the formula (3) is applied to the Chinese National Standard (CNS) A4 specification (210X 297 mm) in the R paper size. - I (Please read the back of the note first) i fill out this page) Customs Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Print -15-1260457 A7 B7 V. Invention Description (13), Υ, A ring, Z, r, s and t combination are shown below Table 1 to Table 14.尙, in the table, "B" means 1,4 - phenyl, and "ch" means 1, 4 and Cyclohexyl. Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Table 1 No. Ri Α Υ ζ 1* S t 1 Hydrogen - - - 0 - 0 2 CH3 - - - 0 - 0 3 C2H5 - - - 0 - 0 4 11- C3H7 - - - 0 - 0 5 η -C 4H 9 - - - 0 - 0 6 η - C 5 Η11 - - - 0 - 0 7 η - C 6 Η13 - - - 0 - 0 8 η - C 7 Η15 - - - 0 - 0 9 η - C 8 Η17 - - - 0 - 0 10 η - C9Η19 - - - 0 - 0 11 n-Ci〇H2i - - - 0 - 0 12 11-C11H23 - - - 0 - 0 13 η - C12Η 25 - - - 0 - 0 一--PI----衣衣-- (Please read the note on the back first to write this page) Line paper scale applies to China National Standard (CNS) Α 4 specifications (210 X 297 mm) -16- 1260457

7 7 AB V. INSTRUCTIONS (14) TABLE 2 No. Ri Α ring YZ rst 14 Hydrogen Ch - - 1 0 0 15 CHs Ch - - 1 0 0 16 C2H5 Ch - - 1 0 0 17 11-C3H7 Ch - - 1 0 0 18 11-C4H9 Ch - - 1 0 0 19 η - C 5 Η11 Ch - - 1 0 0 20 η - C eH ] 3 Ch - - 1 0 0 21 η -C 7Η15 Ch - - 1 0 0 22 η -C δΗ17 Ch - - 1 0 0 23 η -C 9Η19 Ch - - 1 0 0 24 η - C ι 〇Η 21 Ch - - 1 0 0 25 Π-Cl ΐΗ23 Ch - - 1 〇0 26 11 - C 1 2 Η 2 5 Ch - - 1 0 0 (Please read the note on the back to write this page) • Install · - Ministry of Economic Affairs, Intellectual Property Office, Employees, Consumer Cooperatives, Printed Paper Size Applicable to China National Standard (CNS) A4 Specifications (2) 297 297 mm) -17- 1260457 7 Β V. Description of invention (15) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Table 3 No. Ri Α Υ S r S t 27 Hydrogen Β - - 1 0 0 28 CHa Β - - 1 0 0 29 C2H5 Β - - 1 〇0 30 n-CsHv Β - - 1 0 0 31 η - C 4 Η 9 Β - - 1 0 0 32 η - C 5 Η11 Β - - 1 0 0 33 η-C βΗ13 Β - - 1 0 0 34 η - C 7Η15 Β - - 1 0 0 35 η - C 8 Η17 Β - - 1 0 0 36 η-C 9Η19 Β - - 1 0 0 37 η - C ι 〇Η 21 Β - - 1 0 0 38 n-CnH23 Β - - 1 0 0 39 η - C 】2 Η 2 5 Β - - 1 0 0 ( Please read the note on the back: write this page) The standard of the paper is applicable to the Chinese National Standard (CNS) Λ4 specification (2) 297 297 mm) -18 - 1260457 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative System 5, invention description (16) Table 4 No. Ri ring YZ rst 40 hydrogen Ch CH2 - 1 1 0 41 CH3 Ch CH2 - 1 1 0 42 C2H5 Ch CH2 - i 1 0 43 n-C3H7 Ch CH2 - 1 1 0 44 η-〇4Η9 Ch CH2 - 1 1 0 45 η - C 5 Η11 Ch CH2 - 1 1 0 46 n-CeHis Ch CH2 - 1 1 0 47 η -C 7Η15 Ch CH2 - 1 1 0 48 η -C βΗ17 Ch CH2 - 1 1 0 49 η -C 9Η19 Ch CH2 - 1 1 0 50 η - C ι 〇Η 2 ] Ch CH2 - 1 1 0 51 η - C11Η 2 3 Ch CH2 - 1 1 0 52 Π - C 1 2 Η 2 5 Ch CH2 - 1 1 0 :---7---^-- (Please read the note on the back first to write this page) Customize the paper size for the Chinese National Standard (CNS) A4 specification (2) OX 297 mm) -19- 1260457

B V. INSTRUCTIONS (17) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed Table 5 No. Ri Α Υ Ζ r S t 53 Hydrogen Β CH2 - 1 1 0 54 CH3 Β CH2 - 1 1 0 55 C2H5 Β CH2 - 1 1 0 56 n-C3H7 Β CH2 - 1 1 0 57 η - C 4 Η 9 Β CH2 - 1 1 0 58 η - C 5 Η11 Β CH2 - 1 1 0 59 η - C βΗ 13 Β CH2 - 1 1 0 60 11-C7H15 Β CH2 - 1 1 0 61 η -C δΗ 17 Β CH2 - 1 1 0 62 η ** C 9Η ] 9 Β CH2 - 1 1 0 63 11-C10H21 Β CH2 - 1 1 0 64 η - C11Η 2 3 Β CH2 - 1 1 0 6 5 Π - C 1 2 Η 2 5 Β CH2 - 1 1 0 (Please read the note on the back first - install - for writing this page) China National Standard (CNS) A4 Specification (2!〇X 297 mm) -20- 1260457 A7 B7 V. Invention Description (18) Table 6

No. Ri Α Υ S r S t 66 Hydrogen - - Oxygen 0 - 1 67 CHs - - Oxygen 0 - 1 68 C2H5 - - Oxygen 0 - 1 69 n-C3H? - - Oxygen 0 - 1 70 π - C 4 Η 9 - - Oxygen 0 - 1 71 η - C 5 Η]] - - Oxygen 0 - 1 72 η-C όΗ 13 - - Oxygen 0 - 1 73 η - C 7 Η 15 - - Oxygen 0 - 1 74 η - C 8 Η17 - - Oxygen 0 - 1 75 ll-C9Hl 9 - - Oxygen 0 - 1 76 η - C ι 〇Η 21 - - Oxygen 0 - 1 77 η - C11Η 2 3 - - Oxygen 0 - 1 78 11 - C 1 2 Η 2 5 - - Oxygen 0 - 1 Pack --- * kY (Please read the note on the back first ^ Write this page) Customize the Ministry of Economic Affairs Zhizhi Property Bureau Staff Consumer Cooperative Print this paper scale for China National Standard (CNS ) A4 size (21 OX 297 mm) -21 - 1260457

7 B V. INSTRUCTIONS (19) Table 7 No. Ri Α Ring YZ r S ΐ 79 Hydrogen Ch - Oxygen 1 〇1 80 CHs Ch - Oxygen 1 0 1 81 C2H5 Ch - Oxygen 1 0 1 82 n-CsHv Ch - Oxygen 1 0 1 83 η - C 4 Η 9 Ch - Oxygen 1 0 1 84 η - C 5 Η11 Ch • Oxygen 1 0 1 85 η-C eH13 Ch - Oxygen 1 0 1 86 η -C 7Η15 Ch - Oxygen 1 0 1 87 n-CsHiv Ch - oxygen 1 0 1 88 η - C 9 Η19 Ch - oxygen 1 0 1 89 η - C ι 〇Η 21 Ch - oxygen 1 0 1 90 η - C11Η 2 3 Ch - oxygen 1 0 1 91 η - C12 Η 2 5 Ch - Oxygen 1 0 1 (Please read the note on the back of this page first) - Install 'Customize the Ministry of Commerce, Intellectual Property Bureau, Staff and Consumer Cooperatives Print this paper scale for China National Standard (CNS) A4 size (2] OX 297 mm) - 22- 1260457 A7 B7 V. Description of invention (20) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Table 8 No. Ri Y Ring YZ Γ S t 92 Hydrogen Ch CH2 Oxygen 1 2 1 93 CH3 Ch CH2 Oxygen 1 2 1 94 C2H5 Ch CH2 Oxygen 1 2 1 95 n-C3H7 Ch CH2 Oxygen 1 2 1 96 η - C 4 Η 9 Ch CH2 Oxygen 1 2 1 97 η - C 5 Η11 Ch CH2 Oxygen 1 2 1 98 η-C βΗ13 Ch CH2 Oxygen 1 2 1 99 η - C 7 Η15 Ch CH 2 oxygen 1 2 1 100 n-CsHi7 Ch CH2 oxygen 1 2 1 101 11-C9H19 Ch CH2 oxygen 1 2 1 102 η - C1 〇Η 21 Ch CH2 oxygen 1 2 1 103 n-CnH23 Ch CH2 oxygen 1 2 1 104 η - C12 Η 2 5 Ch CH2 Oxygen 1 2 1 (Please read the note on the back first - install - 3⁄4马) This line of paper is applicable to China National Standard (CNS) A4 size (210X 297 mm) -23 - 1260457 A7 B7 V. INSTRUCTIONS (21) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed Table 9 No. Ri Α Υ ζ Γ S t 105 Hydroquinone - Oxygen 1 0 1 106 CHs Β - Oxygen 1 0 1 107 C2H5 Β - oxygen 1 0 1 108 n-C3H7 Β - oxygen 1 0 1 109 11-C4H9 Β - oxygen 1 0 1 110 η - C 5 Η11 Β - oxygen 1 0 1 111 η - C 6 Η13 Β - oxygen 1 0 1 112 η - C 7Η15 Β - Oxygen 1 0 1 113 n-CsH]7 Β - Oxygen 1 0 1 1 14 η - C 9 Η19 Β - Oxygen 1 0 1 115 η - C ι 〇Η 21 Β - Oxygen 1 0 1 1 16 Π - C 1 1 Η 2 3 Β - Oxygen 1 0 1 117 η - C12Η 25 Β - Oxygen 1 0 1 (Please read the note on the back first) - Gutter This paper size applies to Chinese national standards (CNS) A4 size (21 OX 297 mm) -24- 1260457 A7 B7 V. INSTRUCTIONS (22) Table 10 No. Ri Α Υ ζ 1· S t 118 Hydrogen - - CH2 0 - 1 119 CHs - - CH2 0 - 1 120 C2H5 - - CH2 0 - 1 121 n-CsHv - - CH2 0 - 1 122 η - C 4 Η 9 - - CH2 0 - 1 123 η - C 5 Η11 - - CH2 0 - 1 124 η - C 6 Η13 - - CH2 0 > 1 125 η - C 7 Η15 - - CH2 0 - 1 126 η - C 8 Η17 - - CH2 0. - 1 127 η-〇9Ηΐ9 - - CH2 0 - 1 128 η - C ι 〇Η 21 - - CH2 0 - 1 129 η - C11Η 2 3 - - CH2 0 1 130 Γ1 - C 1 2Η 25 - - CH2 0 - 1 ^ ^----Lianyi -- (Please read the note on the back first | Write this page) Customize the Ministry of Economic Affairs Intellectual Property Office Cooperatives printed this paper scale applicable to China National Standard (CNS) A4 specification (2] 0: < 297 mm) -25- 1260457 A7 B7 V. Invention description (23) Table 1 1

No. Ri Α ring YZ Γ S t 131 Hydrogen Ch - Oxygen 1 0 1 132 CH3 Ch - Oxygen 1 0 1 133 C2H5 Ch - Oxygen 1 0 1 134 11-C3H7 Ch - Oxygen 1 0 1 135 11-C4H9 Ch - Oxygen 1 0 1 136 η -C 5H η Ch - oxygen 1 0 1 137 η -C βΗ13 Ch - oxygen 1 0 1 138 η - C 7 Η15 Ch - oxygen 1 0 1 139 n-CsHi? Ch - oxygen 1 0 1 140 η - C 9 Η19 Ch - Oxygen 1 0 1 141 η - C ] 〇Η 21 Ch - Oxygen 1 0 1 142 η - C 11Η 2 3 Ch - Oxygen 1 0 1 143 Π - C 1 2 Η 2 5 Ch - Oxygen 1 0 1 ---:---;----Chair---(Please read the note on the back first to write this page) Line Economy Department Zhi Your Property Bureau Staff Consumer Cooperative Printed This paper scale applies to Chinese national standards (CNS) Λ4 size (210X 297 mm) -26- 1260457 A7 B7 V. Description of invention (24) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed Table 12 No. Ri Y Ring YZ rst 144 Hydrogen Ch CH2 CH2 1 2 1 145 CHs Ch CH2 CH2 1 2 1 146 C2H5 Ch CH2 CH2 1 2 1 147 n-CsH7 Ch CH2 CH2 1 2 1 148 11-C4H9 Ch CH2 CH2 1 2 1 149 η - C 5 Η11 Ch CH2 CH2 1 2 1 150 η -C βΗ13 Ch CH2 CH2 1 2 1 151 η - C 7 Η15 Ch CH2 CH2 1 2 1 1 52 η - C 8 Η17 Ch CH2 CH2 1 2 1 153 η - C 9 Η ] 9 Ch CH2 CH2 1 2 1 154 Π - C 1 〇Η 2 1 Ch CH2 CH2 1 2 1 155 η - C ] 1Η 2 3 Ch CH2 CH2 1 2 1 156 11 - C 1 2 Η 2 5 Ch CH2 CH2 1 2 1 (Please read the note on the back page first) - Install 'Line paper size for Chinese National Standard (CNS) A4 size (2) 0X29? mm) -27- 1260457 A7 B7 V. Description of invention (25) Table 1 3

No. Ri Α S r S t 157 Hydrogen hydrazine - CH2 1 0 1 158 CHs Β - CH2 1 0 1 159 C2H5 Β - CH2 1 〇1 160 n-CsH7 Β - CH2 1 〇1 161 η - C 4 Η 9 Β - CH2 1 0 1 162 η - C 5 Η11 Β - CH2 1 0 1 173 η -C βΗ13 Β - CH2 1 0 i 164 η -C 7Η15 Β - CH2 1 0 1 165 η -C δΗ17 Β - CH2 1 0 1 166 η - C 9 Η19 Β - CH2 1 0 1 167 η - C 〇Η 〇Η 2 ] Β - CH2 1 0 1 168 η - C11Η 2 3 Β - CH2 1 0 1 169 Π - C 1 2 Η 2 5 Β - CH2 1 0 1 (Please read the note on the back to write this page) • Install · Customize the Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Print this paper scale Applicable to China National Standard (CNS) A4 specification (210X 297 mm) -28- 1260457 Α7 Β7 V. Description of invention (26 ) Table 14 No. Ri Α Υ Ζ r S t 170 Hydrogen hydrazine CH2 CH2 1 1 1 171 CHs Β CH2 CH2 1 1 1 172 C2H5 Β CH2 CH2 1 1 1 173 n-C3H7 Β CH2 CH2 1 1 1 丄174 η -C4H9 Β CH2 CH2CH2 1 1 1 175 η - C 5 Η11 Β CH2 CH2 1 1 1 176 n-CeHi3 Β CH2 CH2 1 1 1 177 η - C 7 Η15 Β CH2 CH2 1 1 1 178 η-C δΗ17 Β CH2 CH2 1 1 1 179 η - C 9 Η19 Β CH2 CH2 1 1 1 180 η - C ι 〇Η 21 Β CH2 CH2 1 1 1 181 η - C 11Η 2 3 Β CH2 CH2 1 1 1 182 η - C) 2 Η 2 5 Β CH2 1 1 · 1 (Please read the note on the back to write this page) - Binding Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 尙 'i: a part of the diamine-based compound shown in the formula (3) does not mean The diamine compound represented by the formula (3) is limited to these examples. Further, the diamine-based compound represented by the formula (3) may be used in combination of two or more. In these diamine-based compounds, when r is 0, R i is Η or a short-chain courtyard base, the original polyamine can be used in the orientation film to make the front elevation angle smaller when the r is 1 to 3 Even if R 1 is Η, the front elevation angle can be made larger. Next, a specific example of the diamine-based compound represented by the formula (4) is shown by the combination of X 1 'X 2 ' Β !, Β 2 and R 2 in the following Table 1 5 to Table 2 7 China National Standard (CNS) A4 Specification (2) 0X 297 mm) -29- 1260457 A7 B7 V. Description of Invention (27).尙, the "B" in the table indicates 1,4 - phenyl, "Ch" indicates that 1, 4 is a cyclohexyl group, and the bond positions of the two amine groups are the first and third positions of benzene, X ^ The bonding position is the 5th position of the diaminobenzene. Further, for example, when "B - C h" and "C h - B" are described in B i and B 2 , the combination is described in the order of description. (Please read the note on the back first - install - for writing this page) Customize the Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives Print this paper scale applicable to China National Standard (CNS) A4 specifications (210X 297 mm) - 30-1260457 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printing V. Inventions (28) Table 1 5 No. Xl Bi χ2 Β2 r2 183 One-touch single-button single-key early key η -C^Hn 184 One-touch single-button single Key single key η - • C 1 2 Η 2 5 185 One-touch single-touch One-touch single-button η -C^Hn 186 One-touch one-touch One-touch single-button η- C 1 2 Η 2 5 187 〇 One-touch single-button single Key η -C.Hm 188 〇One-touch single-button single-button η- Cl2H25 189 〇One-touch single-button single-button η -CsHn 190 〇One-touch single-button single-button η- • C i 2 Η 2 5 191 COO One-touch single Key single key η -C5Hll 192 c〇〇 single key single key single key η- • C ] 2 H 2 5 193 coo single key single key α early key η -CsHn 194 coo single key single key single key η- 'C 1 2 H 2 5 195 〇c〇 single bond single bond α early key η -CsHn 196 〇c〇 single bond single bond single bond η- C 1 2 H 2 5 197 〇c〇 single bond single bond σ mouth early key η -CsHm 198 〇c〇 single button single button single button η- C 1 2 H 2 5 199 NH single button single button single button η -CsHn 200 NH single button D口早键单键η - C 1 2 H 2 5 201 NH Single button single button mouth early key η -CsHn 202 NH One button single button single button η > C ] 2 H 2 5 203 CONH One button single button single Key η· -C5Hu 204 CONH Single button Single button Single button η - C 1 2 H 2 5 205 CONH One button One button Single button η -C.Hn 206 CONH One button One button single button η - C ] 2 H 2 ? (Please read the note on the back to write this page) - Loading - Setting the paper size for the Chinese National Standard (CNS) A4 specification (2) 0X 297 mm) -31 - 1260457 A7 B7 V. Description of invention (29) Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed Table 1 6 No. Χι Βι X2 B2 R2 207 One-button B One-touch single button η -CsHn 208 One-button B One-touch single button η - C ] 2 Η 2 5 209 One-touch Ch One-touch single button η -CsHn 210 One-touch Ch One-touch single button η · • C12H25 211 One-touch BB One-touch single button η -CsHn 212 One-button BB port CJ early key single key η · • C 1 2Η 25 213 single key B-Ch single key single key η -CsHll 214 single key B-Ch single key single key η- C 1 2Η 2 5 215 single key Ch-B single key Single bond η -C 5 Η 1 1 216 Single bond Ch-B Single button Single button η- C 1 2 Η 2 5 217 Single button Ch-Ch One-touch single button η -C 5 Η 1 1 218 One-button Ch-Ch Single button single button η _ C 1 2 Η 2 5 219 Single button BBB One button single button η -CsHn 220 One button BBB One button single button η- C 1 2 H 2 5 221 One button BB-Ch One button single button η -C5Hll 222 single bond BB-Ch single button single button η - C 12H25 223 single button B-Ch-Ch single button single button η -C5H11 224 single button B-Ch-Ch single button single button η - C 1 2 H 2 5 225 single bond Ch-Ch-Ch mouth early key single key η -CsHll 226 single key Ch-Ch-Ch mouth early key single key η- Cl2H25 ---τ---1----0-- (Please read the note on the back first\^^write this page)

, one W This paper scale applies to China National Standard (CNS) A4 specification (2) 〇X 297 mm) -32- 1260457 A7 B7 V. Description of invention (30) Ministry of Economic Affairs Intellectual Property Bureau S (Working Consumer Cooperative Printed Form 1 7 No. X) Βι X2 B2 r2 227 〇B One-touch single button η - C 5 Η11 228 〇B One-touch single button 11 - C 1 2Η 2 5 229 〇Ch One-touch single button η - C 5 Η1 ] 230 〇Ch single button single button Π - C 1 2 Η 2 5 231 〇BB single button single button η - C 5 Η11 232 〇BB single button single button η - C 12Η25 23 3 〇B-Ch single button single button η-C5H11 234 〇B-Ch One-touch single button η - C 1 2 Η 2 5 235 〇Ch-B One-touch single button η -C 5Η11 236 〇Ch-B One-touch single button Π - C 1 2Η 25 237 〇Ch-Ch Single button single button η - C 5 Η11 238 〇Ch-Ch One-touch single button Π - C 1 2 Η 2 5 239 〇B winter B single button single button π - C 5 Η 1 1 240 〇BBB single button single button η - C 1 2 Η 2 5 241 〇BB-Ch One-touch single button η-〇5Ηι ι 242 〇BB-Ch One-touch single button Π - C 1 2 Η 2 5 243 〇B>Ch-Ch One-touch single button π - C 5 Η11 244 〇B-Ch-Ch One-touch single button Π - C 1 2 Η 2 5 245 〇 Ch-Ch-Ch One-touch single button n-CsHn 246 〇 Ch-Ch-Ch One-touch single button η - C12 Η 2 5 (Please read the note on the back first - install - write this page)

, 1T line paper size applicable to China National Standard (CNS) A4 specification (210X 297 mm) -33 ' 1260457 A7 B7 Table 18 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (31) No. Xl B ) X2 B2 r2 247 COO B One-touch single button η - C 5 Η η 248 COO B One-touch single button 11 - C 1 2 Η 2 5 249 COO Ch One-touch single button n-CsHn 250 COO Ch One-touch single button η ' C 1 2 Η 2 5 251 COO BB One-touch single button η - C 5 Η11 252 COO BB One-touch single button ΙΊ - C 1 2Η 2 5 253 COO B-Ch One-touch single button n-CsHn 254 COO B-Ch One-touch single button η - C ] 2Η25 25 5 COO Ch-B One-touch single button η - C 5 Η 11 256 coo Ch-B One-touch single button Π - C 1 2 Η 2 5 257 coo Ch-Ch One-touch single button η - C 5 Η ι) 258 coo Ch-Ch One-touch single-button η - C 1 2Η 25 259 coo BBB Single-button single-button π - C 5 Η11 260 coo BBB One-touch single button η - C 1 2 Η 2 5 261 Coo B winter Ch single-button single-button η - C 5 Η]] 262 coo BB-Ch single-button single-button η - C 1 2 Η 2 5 263 coo B-Ch-Ch single-button single-button η - C 5 Η 11 264 coo B-Ch-Ch One-touch single button 11 - C 1 2 Η 2 5 2 65 coo Ch-Ch-Ch One-touch single button n-CfHn 266 coo Ch-Ch-Ch One-touch single button 11-C12H25 (Please read the note on the back first - install - write this page) The scale applies to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) -34 - 1260457

7 7 A B V. INSTRUCTIONS (32) TABLE 1 9 Printed by the Consumers' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs

No. Biι Bi X2 B2 R2 267 ch2 B Single button single button π - C 5 Η ] 1 268 ch2 B Single button single button η - C 1 2 Η 2 5 269 CH2 Ch One-touch single button η - C 5 Η 11 270 CH2 Ch One-touch single button η - C 1 2 Η 2 5 271 CH2 BB One-touch single button η - C 5 Η 11 272 ch2 BB One-touch single button 11 - C 1 2 Η 2 5 273 CH2 B-Ch One-touch single button η -C 5Ηι ] 274 CH2 B-Ch One-touch single button 11 - C 1 2 Η 2 5 275 ch2 Ch-B One-touch single button n-CsHn 276 CH2 Ch-B One-touch single button η - C 】 2 Η 2 5 277 CH2 Ch-Ch One-touch single button η - C 5 Η11 278 CH2 Ch-Ch One-touch single button 11 - C 1 2 Η 2 5 279 CH2 B - B - B One-touch single button η -C sH11 280 CH2 BBB Single Key single key η - C12 Η 2 5 281 CH2 BB-Ch One-touch single button η - C 5 Η η 282 CH2 BB-Ch One-touch single button 11 - C 1 2 Η 2 5 283 CH2 B-Ch-Ch One-touch Single bond η - C 5 Η11 284 CH2 B-Ch-Ch One-touch single button η - C 1 2 Η 2 5 285 CH2 Ch-Ch-Ch One-touch single button η - C 5 Η11 286 CH2 Ch-Ch-Ch Single Key single key η - C 1 2 Η 2 5 (Please read the note on the back to write this page) - Install. Line paper size applies to Chinese national standards CNS) A4 size (210X 297 mm) -35- 1260457 Μ Β7 V. invention is described in (33) Table 20

No. X〗 Βι X2 B2 r2 287 〇 single bond CH2CH2 B n - C 5 H ]] 288 〇 single bond CH2CH2 B n - C12 H 2 5 289 〇 single bond CH2CH2 Ch n-CsHn 290 〇 single bond CH2CH2 Ch n - C12 H 2 5 291 〇 single bond CH2CH2 BB n - C 5 H11 292 〇 single bond CH2CH2 BB n - C12 H 2 5 293 〇 single bond CH2CH2 B-Ch π - C 5 H ] 1 294 〇 single bond CH2CH2 B-Ch n - C12 H 2 5 295 〇 single bond CH2CH2 Ch-B n - C 5 H 】1 296 〇 single bond CH2CH2 Ch-B n - C12 H 2 5 207 〇 single bond CH2CH2 Ch-Ch π - C 5 H11 208 〇 Single bond CH2CH2 Ch-Ch n - C12 H 2 5 299 〇 Single bond CH2CH2 BBB n - C 5 Η n 300 〇 Single bond CH2CH2 BBB n - C ] 2 H 2 5 301 〇 Single bond CH2CH2 BB-Ch nC 5H11 302 〇 Single bond CH2CH2 BB-Ch n - C 12 H 2 5 . 303 〇 single bond CH2CH2 B^Ch-Ch n - C 5 H11 304 〇 single bond CH2CH2 B-Ch-Ch n - C 12 H 2 5 305 〇 single bond CH2CH2 Ch-Ch-Ch π - C 5 H ] 1 306 〇 Single bond CH2CH2 Ch-Ch-Ch n - C 12 H 2 5 (Please read the note on the back to fill out this page) Ministry of Economic Affairs Intellectual Property Office Staff Cooperatives Printed paper scale applies to Chinese national standards (CNS) A4 specification (21C/X 297 mm) -36- 1260457 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (34) I 1 Table 21 1 1 No. Xl Bi X2 B2 R2 I 1 1 307 COO Single button CH2CH2 B n - C 5 Η n 1 Please first 1 308 coo Single button CH2CH2 B n - C12 H 2 5 Read 1 Back 1 309 coo Single button CH2CH2 Ch n - C 5 H11 Face I ^ 1 Note 310 coo single bond CH2CH2 Ch n - C 12 H 2 5 meaning 1 31 1 coo single bond CH2CH2 BB π - C 5 H11 Φ I 312 coo single bond CH2CH2 BB n - C12 H 2 5 1 loading 1 313 coo single key CH2CH2 B-Ch n - C 5 H j 1 V^^ 1 1 314 coo single bond CH2CH2 B-Ch n - C12H 2 5 1 1 315 coo single bond CH2CH2 Ch-B n - C 5 H11 1 1 316 coo single bond CH2CH2 Ch-B n - C12H 2 5 I 317 coo single bond CH2CH2 Ch-Ch n - C 5 H11 1 1 I 318 coo single bond CH2CH2 Ch-Ch n - C 12 H 2 5 1 1 319 coo single bond CH2CH2 BBB π - C 5 H n 1 101 320 coo single bond CH2CH2 BBB n - C12 H 2 5 line 1 321 coo single bond CH2CH2 BB-Ch n - C 5 H11 1 I 322 coo single CH2CH2 BB-Ch n-Ci2H25 1 1 I 323 coo single bond CH2CH2 B-Ch-Ch n - C 5 H11 1 1 324 coo single bond CH2CH2 B-Ch-Ch n - C 12H 2 5 1 325 coo single bond CH2CH2 Ch -Ch-Ch π ~ C 5 H n 326 coo Single bond CH2CH2 Ch-Ch-Ch n - C j 2 H 2 5 1 1 1 1 ! 1 This paper scale applies to Chinese National Standard (CNS) A4 specification (210Χ 297 公) PCT) -37 - 1260457 A7 B7 V. Description of invention (35) Table 22 Printed by the Consumer Cooperative of the Zhici Property Bureau of the Ministry of Economic Affairs

No. Xl B; X2 B2 R2 327 Single bond B CH2CH2 B n - C 5 H11 328 Single bond B CH2CH2 Ch n - C 5 H11 329 Single bond B CH2CH2 BB n - C 5 Η π 330 Single bond B CH2CH2 B-Ch n - C 5 Η π 331 single bond B CH2CH2 Ch-B n * C 5 H11 332 single bond B CH2CH2 Ch-Ch n - C 5 H1 ] 333 single bond Ch CH2CH2 B nC 5H11 334 single bond Ch CH2CH2 Ch n - C 5 Η n 335 Single bond Ch CH2CH2 BB n - C 5 Η π 336 Single bond Ch CH2CH2 B-Ch n - C 5 H11 337 Single bond Ch CH2CH2 Ch-B n - C 5 Η n 338 Single key Ch CH2CH2 Ch-Ch n - C 5 H11 339 Single bond BB CH2CH2 B n - C 5 H11 340 Single bond BB CH2CH2 Ch n - C 5 H11 341 Single bond B-Ch CH2CH2 B π - C 5 H1 ] 342 Single bond B-Ch CH2CH2 Ch n - C 5 H11 343 Single bond Ch-B CH2CH2 B n - C 5 H11 344 Single bond Ch-B CH2CH2 Ch π - C 5 H11 345 Single bond Ch-Ch CH2CH2 B n - C 5 H11 346 Single bond Ch-Ch CH2CH2 Ch π ~ C 5 H1 ] (Please read the note on the back first\^^Write this page) - Loading · Setting the paper size for the Chinese National Standard (CHS) A4 specification (2) 297 297 mm) > 38- 1260457 A7 B7 V. INSTRUCTIONS (36) Table 23 Ministry of Economics Property Office employees consumer cooperatives printed

No. Xl Βι X2 B2 r2 347 〇B CH2CH2 B n - C 5 H11 348 〇B CH2CH2 Ch n - C 5 H11 349 〇B CH2CH2 BB n - C 5 H11 350 〇B CH2CH2 B-Ch n - C 5 H i 1 351 〇B CH2CH2 Ch-B n - C 5 H11 352 〇B CH2CH2 Ch-Ch π - C 5 H1 ] 353 〇Ch CH2CH2 B 11-C5H11 354 〇Ch CH2CH2 Ch n - C 5 H ] 1 355 〇Ch CH2CH2 BB n - C 5 H11 35 6 〇Ch CH2CH2 B-Ch n - C 5 H1) 357 〇Ch CH2CH2 Ch-B n - C 5 H11 358 〇Ch CH2CH2 Ch-Ch n - C 5 H11 359 〇BB CH2CH2 B n -C5Hn 360 〇BB CH2CH2 Ch n - C 5 H11 261 〇B-Ch CH2CH2 B n ·* C 5 H11 262 〇B-Ch CH2CH2 Ch n - C 5 H11 363 〇Ch-B CH2CH2 B n - C 5 H11 3 64 〇Ch-B CH2CH2 Ch n - C 5 H11 365 〇Ch-Ch CH2CH2 B n - C 5 Η n 366 〇Ch-Ch CH2CH2 Ch n - C 5 H ] i (Please read the note on the back π * -- 3⁄43⁄4this page) The paper size is applicable to the Chinese National Standard (CNS) Α4 specification (2〗 0Χ 297 mm) - 39- 1260457 Ministry of Economic Affairs Zhici Property Bureau employee consumption cooperative printing 5, invention description (37) Table 24

No. X! B] X2 B2 R2 367 COO B CH2CH2 B n- CsH1i 368 coo B CH2CH2 Ch n - C 5 H11 369 coo B CH2CH2 BB n - C 5 H11 370 coo B CH2CH2 B-Ch n - C 5 H11 371 Coo B CH2CH2 Ch-B n-CsHn 372 coo B CH2CH2 Ch-Ch n - C 5 H11 373 coo Ch CH2CH2 B π - C 5 H11 374 coo Ch CH2CH2 Ch π - C 5 H11 375 coo Ch CH2CH2 BB n - C 5 H ] 1 37 6 coo Ch CH2CH2 B-Ch n-CsHi 1 377 coo Ch CH2CH2 Ch-B n-CsHu 378 coo Ch CH2CH2 Ch-Ch n - C 5 H11 379 coo BB CH2CH2 B n-CsHi 1 380 coo BB CH2CH2 Ch π - C 5 H11 381 coo B-Ch CH2CH2 B n-CsHi 1 382 coo B-Ch CH2CH2 Ch n · C 5 H ]] 383 coo Ch-B CH2CH2 B n - C 5 H 11 384 coo Ch - B CH2CH2 Ch n-CsHi ] 385 coo Ch-Ch CH2CH2 B n - C 5 H11 386 coo Ch^Ch CH2CH2 Ch n-CsHn (Please read the note on the back first - install - π write this page) Chinese National Standard (CNS) Λ4 Specifications (210Χ 297 mm) -40 - 1260457

A

7 B V. INSTRUCTIONS (38) TABLE 25 Printed by the Consumers’ Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs

No. Xl B] X2 B2 r2 387 CH2 B CH2CH2 B n - C 5 H1 ] 388 CH2 B CH2CH2 Ch n - C 5 H11 389 ch2 B CH2CH2 BB n - C 5 H11 390 ch2 B CH2CH2 B-Ch n - C 5 H11 391 CH2 B CH2CH2 Ch-B n - C 5 H11 392 CH2 B CH2CH2 Ch-Ch nC 5H11 393 CH2 Ch CH2CH2 B n - C 5 H11 394 CH2 Ch CH2CH2 Ch n - C 5 H11 395 CH2 Ch CH2CH2 BB n - C 5 H11 396 CH2 Ch CH2CH2 B-Ch n - C 5 H11 397 CH2 Ch CH2CH2 Ch-B n - C 5 H11 398 CH2 Ch CH2CH2 Ch-Ch n - C 5 H ] 1 399 ch2 BB CH2CH2 B n - C 5 H11 400 CH2 BB CH2CH2 Ch n - C 5 H11 401 CH2 B-Ch CH2CH2 B n - C 5 H i ] 402 CH2 E-Ch CH2CH2 Ch n - C 5 H 11 403 CH2 Ch-B CH2CH2 B n - C 5 H ] 1 404 CH2 Ch-B CH2CH2 Ch n - C 5 H11 405 CH2 Ch-Ch CH2CH2 B π - C 5 H ] 1 406 CH2 Ch-Ch CH2CH2 Ch n - C ? H 1 ] , ^ Batch! (Please read the note on the back to fill out this page) Line paper size applies to China National Standard (CNS) A4 size (210X 297 mm) -41 - 1260457 A7 B7 V. Invention description (39) Table 26 Ministry of Economics intellectual property Bureau employee consumption cooperative printing

No. Xl Bi X2 Β2 R2 407 〇 One-touch single button Β-Β Hydrogen 408 〇 Single button CJCJ Early button Β-Β Hydrogen 409 〇 One-touch single button Β-Β F 410 〇 One-touch single button Β-Β F 411 〇 One-touch single button Β-Β CN 412 〇 One-touch single button Β-Β CN 413 〇 One-touch single button Β-Β 0Η 414 〇 One-touch single button Β-Β 0Η 415 〇 One-touch single button Β-Β O-C2H5 416 〇One-touch single button Β-Β O-C2H5 417 COO One-touch single button Β-Β Hydrogen 418 COO One-touch single button Β-Β Hydrogen 419 COO One-touch single button Β-Β F 420 COO One-touch single button Β- Β F 421 COO One-touch single button Β-Β CN 422 COO One-touch single button Β-Β CN 423 COO One-touch 早 early button Β-Β 424 424 COO One-touch single button Β-Β 0Η 425 COO One-touch early button Β-Β O-C2H5 426 coo One-touch single button Β-Β O-C2H5 (Please read the note on the back page) Page 2 • Installed, 11-line paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) -42 - 1260457 A7 B7 V. Description of invention (40) Table 27 Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative

No. Xl Bi X2 B2 R2 427 〇 Single bond CH2CH2 BB Hydrogen 428 〇 Single bond CH2CH2 BB Hydrogen 429 〇 Single bond CH2CH2 BB F 430 〇 Single bond CH2CH2 BB F 431 〇 Single bond CH2CH2 BB CN 432 〇 Single button CH2CH2 BB CN 433 〇 single bond CH2CH2 BB OH 434 〇 single bond CH2CH2 BB 0H 435 〇 single bond CH2CH2 BB O-C2H5 436 〇 single bond CH2CH2 BB O-C2H5 437 COO single bond CH2CH2 BB hydrogen 438 coo single bond CH2CH2 BB hydrogen 43 9 coo single bond CH2CH2 BB F 440 coo single bond CH2CH2 BB F 441 coo single bond CH2CH2 BB CN 442 coo single bond CH2CH2 BB CN 443 coo single bond CH2CH2 BB OH 444 coo single bond CH2CH2 BB 0H 445 coo single bond CH2CH2 BB O-C2H5 446 coo single Key CH2CH2 BB OC crystal (please read the note on the back first - install - I write this page) Set the paper size for the Chinese National Standard (CNS) Λ 4 specifications (2) 0Χ 297 mm) -43- 1260457 A7 B7 V. INSTRUCTION DESCRIPTION (41) The above example is a part of the diamine compound represented by the formula (4), and does not mean that the diamine compound represented by the formula (4) is limited to these examples. In these diamine-based compounds, B^[jb2 has a larger number of rings, X: and 2 is a long-chain alkyl group, and R 2 is a long-chain alkyl group, a fluoroalkyl group or an alkoxy group. The situation is that the front angle is large. That is, in the present invention, the front elevation angle can be widely controlled by changing the ratio of the diamine group compound having three or more side chain groups having a carbon number to the total diamine group compound. For example, in the case of the STN type liquid crystal display element 'VA type liquid crystal display element, 〇c B type liquid crystal display element, 'in the case where a large front elevation angle is required, if two or more side chain groups having a carbon number are added, The ratio of the amine compound can be used. Alternatively, the front elevation angle may be increased by using a component of the side chain base length. In addition, in addition to the above examples, the diamine compound having three or more side chain groups preferably used in the present invention can be used in the present invention, for example, by using a diamine compound in which a benzene diamine is provided with a steroid side chain. Used within the scope of the purpose. Further, in the present invention, in order to adjust the front elevation angle to a desired enthalpy, the diamine compound represented by the above formula (2) and/or the diamine compound having a carbon number of 3 or more side chain groups may be used. In addition, diamine compounds other than those used are used. Specific examples of such a diamine-based compound can be referred to the compounds described in many well-known documents, and examples thereof include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, and 4,4/diamino group. Benzene, 4,4 / -diamine-linked '3' 3 -monomethylhydrazine, 1,3~bis(4-aminophenyl)propane, 2,2/-bis(4-aminophenyl)propane垸, bis(4-monoamino-3-methylphenyl)methane, bis(4-amino-2-methylphenyl)methanoin, 1, 2 -bis (4-amino-3) Base phenyl) The standard of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A ' ' -44- (Please read the note on the back first to write this page) • Install · Line Economics Zhici Property Bureau employee consumption cooperative printing 1260457 A7 B7 Ministry of Economic Affairs Zhici Property Bureau employee consumption cooperative printing 5, invention description (42), 1, 3 - bis (4-amino 3-methyl-phenyl) propane, 1, 2 a pair of (4-amino-2-methylphenyl)ethane, 1,3 -bis(4-monoamino-2-methylphenyl)propane, 1,4-bis(4-aminophenyl) Benzene 5 1 , 4 —bis[(4-aminophenyl)methyl]benzene, 1,4 —bis[(3-aminophenyl)methyl]benzene, 1,4-bis[(4-aminophenyl)ethyl]benzene , 1, 4 - bis[(3-aminophenyl)ethyl]benzene, 1,4-bis[(4-amino-3-methylphenyl)methyl]benzene, 1, 4 a pair [( 4-amino-3-methylphenyl)ethyl]benzene, 4,4/mono(4-aminophenyl)biphenyl, bis-[4-(4-aminophenylmethyl)phenyl]methane , bis-[4-(4-aminophenylmethyl)phenyl]ethane, bis-[4-(3-aminophenylmethyl)phenyl]methane, bis-[4-(3-aminobenzene) Methyl)phenyl]ethane, 2,2 / -bis-[4-(4-aminophenylmethyl)phenyl]propane, 2,2 / -bis-[4-(3-aminophenyl) Methyl)phenyl]propane, 2,6-diaminopyridine, bis(4-aminophenyl)diethyldecane, bis(4-aminophenyl)diethyldecane, bis-(4 Amine phenyl)-N-butylamine, N, N> - bis(4-aminophenyl)-N-methylamine, N-(3-aminophenyl)-4 Benzimidamide, 3,3 /-diaminodiphenylmethane, 3,3 / -diaminodiphenyl ether, 3,3 / -diaminodiphenyl milling, 2,2 / - double 3-aminophenyl)propane, 1,3 -bis(3-aminophenyl)propane, 3,3 >-diaminodiphenylsulfide, 2,3,5,6-tetramethyl-p-benzene Diamine, 2,5-dimethyl-p-phenylenediamine, p-xylylenediamine, m-xylylenediamine, p-xylylenediamine, m-xylenediamine, 2,4-12 Aminotoluene, 2,6-diamine (please read the note on the back of this page). Packing. The paper size applies to the Chinese National Standard (CNS) A4 specification (210: < 297 mm) - 45 - 1260457 A7 B7 V. INSTRUCTIONS (43) Toluene, 1, 2 -bis(3-diaminophenyl)ethane, 1,1>-bis(3-diaminophenyl)ethane, 4,4 /monoaminodiphenylhexafluoropropane, 2,2 / - bis(4-aminophenyl)hexafluoropropane, 4,4 / diamino benzophenone, 4,4 / dimethylamino Phenyl sulfide, 4,4 / diaminobiphenyl, 4,4-diaminomonophenyl ether ^ 3 , 4 - diamine Diphenyl ether, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene-bis[4-(4-aminophenoxy)phenyl]methane, 1, 1 / a pair [4 - ( 4-aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]phenyl, 1,1-bis[4-(4-aminophenoxy) Phenyl]propane, 2,2/-bis[4-(4-aminophenoxy)phenyl]propane, 2,2<-bis[4-(4-aminophenoxy)phenyl]butane , 4,4/a bis(4-aminophenoxy)benzophenone, bis[4-(4-aminophenoxy)phenyl] ruthenium, bis[4-(4-aminophenoxy)phenyl Sulfur, 1,3 -bis[4-(4-aminophenoxy)phenyl]benzene, 1,4-bis[4-(4-aminophenoxy)phenyl]benzene, 4,4 / [4-(4-Aminophenoxy)phenyl]biphenyl, 1,2-bis[4-(4-aminophenoxy)phenyl]cyclohexane, 1,3-bis[4(4) Monoaminophenoxy)phenyl]cyclohexane, 1,4-bis[4-(4-aminophenoxy)phenyl]cyclohexyl, bis[4-(4-aminophenoxy)phenyl 〕six Fluoride, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane , 2,2 / - bis [4 -(3 -aminocarbamimido-4-aminophenoxy)phenyl]hexafluoropropane, 2,2/-bis(3-aminocarbazyl-4-amine benzene Base) hexafluoropropane, 2, 2 / - double (3 paper scales applicable to Chinese National Standard (CNS) Α 4 specifications (2) 0X29? mm) (Please read the note on the back π write this page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing -46 - 1260457 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (44) monocarboxy- 4-aminophenyl) hexafluoropropane, 2, 2 / - double [4-(3-Amine acid- 4-aminophenoxy)phenyl]hexa-propylidene, 2' 2 / - bis[4-(3-carboxy-4-aminophenoxy)phenyl]hexafluoro Propane, 1,3 -bis[2,2>-丨4-(4-aminophenoxy)phenyl}hexafluoroisopropyl]benzene, 2,4-double (/3-amino-third Base) toluene, double [p-one (/5-methyl- 7-) Pentyl)benzene, a pair of (1,1-dimethyl-5-amine-pentyl)benzene, bis[p-one (stone-amino-t-butyl)phenyl]ether, double (4 Amine benzyloxy)propane, bis(4-aminobenzyloxy)cyclohexane, 1,4-diaminodicyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1, 4 Bis(aminomethyl)cyclohexane, 4,4/diaminodicyclohexylmethane, bis(2-methyl-4-amine-cyclohexyl)methane, isophoronediamine, 2,5-double (Aminomethyl)-bicyclo[2 · 2 · 1]heptane, 2,6-bis(aminomethyl)-bicyclo[2 . 2 · 1]heptane, 2,3-diaminobicyclo[2. 2 · 1] heptane, 2,6-diaminobicyclo[2 · 2 . 1]heptane, 2,7-diaminobicyclo[2 · 2 · 1]heptane, 2,3-diamino —7 —吖 Bicyclo[2 · 2 · 1]heptane, 2,5-diamino-7-indolebicyclo[2 · 2 · 1]heptane, 2,6-diamino-7-indole bicyclo[ 2 · 2 · 1] heptane, 2,3-diamino-7-thiabicyclo[2 · 2 · 1]heptane, 2,5-diamino-7-thiobicyclo [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]octane, 2,5-diaminobicyclo[This paper scale applies to Chinese national standards (CNS) A4 specification (2丨0; < 297 mm) A 47 - (Please read the note on the back first ¥ π write this page) - Packing · Line 1260457 Α7 Β7 Ministry of Economic Affairs Zhici Property Bureau employee consumption cooperative 5, invention description (45) 2 · 2 · 2] octane-7-ene, 2,5-diamino-7-indolebicyclo[2 · 2 · 2] octane, 2,5-diamino —7 —吖 Bicyclo [ 2 · 2 . 2 ] octane, 2,5-diamino-7-thiabicyclo[2 · 2 · 2]octane, 2,6-diaminobicyclo[3 · 2 . 1] octane, 2,6-diaminoindole ring [3 · 2 · 1] octane, 2,6-diaminoindole bicyclo [3 . 2 · 1] octane, 2,6-diamino group Thiocyclo[3 · 2 · 1 ]octane, 2,6-diaminobicyclo[3 · 2 · 1 ]nonane-8-ene, 2,6 — Amino-8-indole bicyclo[3 · 2 • 2]decane, 2,6-diamino-8-indole bicyclo[3 · 2 · 2 ]decane, 2,6-diamino-8-thio Bicyclo[3 · 2 · 2] decane, etc. In addition, as for the diamine, the binding position of the amine group may be different, and the carbon number of the alkyl group and/or the alkylene group in the structure is different, and any one is replaced by a F. The aromatic ring is substituted by a different number of alkyl groups. Other than the above diamine, a diamine having an oxygen atom structure in an alkylene group can also be mentioned. Further, these diamine-based compounds may be used alone or in combination of two or more. The aliphatic diamine among these diamine compounds is preferably used within a range in which the liquid crystal orientation can be favorably maintained. Further, it is preferable that the diamine-based compound is a diamine-based compound which does not contain a base such as an acid 'vinegar, a thioether' thioester which is liable to cause deterioration in electrical properties of the liquid crystal display element, but is only suitable for the present invention. There is no problem with the use of such compounds. The polyaminic acid used in the present invention can be obtained by subjecting the above tetracarboxylic dianhydride to a diamine compound in an equimolar reaction. This reaction is to apply the above-mentioned cost of paper to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (please read the note on the back first - install π - write this page)

, tT line ~ 48 - 1260457 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau S Industrial Consumer Cooperatives Printing 5, invention description (46) sub-in the reaction vessel with inert gas introduction pipe, raw material input port, thermometer, mixer, as needed In the presence of a solvent such as dimethyl hydrazine, N-methylpyrrolidone, N'N/-dimethylformamide or N,N/-dimethylacetamide, at a concentration of 3 to 5 Ow t%, The range of 〇~2 0 0 °C is carried out for 1 to 50 hours. Further, in addition to the tetracarboxylic dianhydride and the diamine based compound, a monoamine compound which forms a terminal reaction of the polyaminic acid, and/or a monocarboxylic anhydride may be used in combination. Further, in order to improve the adhesion to the substrate, a monoamine compound such as an amine polysiloxane compound may be introduced. The amine polyoxymethane compound may be exemplified by p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxydecane, m-aminophenyltriethoxydecane, and amine C. Trimethoxy decane and the like. The polylysine used in the present invention is preferably a gelled-penetration chromatography (GPC) in which the weight average molecular weight (Mw) of the polyphenylene bromide is about 100,000 to 500,000, and The range is 2〇, 000~2〇0,000 is better. There is no problem in using other polymer compounds as long as the effects of the present invention are not impaired. In particular, the use of polyamines, soluble polyamines, and polyamidimines can further improve electrical properties. Further, the polyglycolic acid of the present invention can also be used in the form of a soluble polyimine or a polyphthalate as long as the effects of the present invention are not impaired. The liquid crystal aligning agent usable in the present invention is applied to the substrate and then melamined by heat treatment. Therefore, when all or a part of the constituent components of the liquid crystal aligning agent of the present invention are polyacrylic acid, a solvent such as acetic anhydride/pyridine is used as a soluble polyamine, or an alcohol is reacted with the proline in advance to form a polypeptone. Amino acid (please read the note on the back of this page) Install 'Take the paper size for the Chinese National Standard (CNS) A4 specification (2) OX29"7 mm) -49- 1260457 A7 B7 V. Description of invention ( 47), both of them can be heat-treated in the process of producing a liquid crystal display element to form a liquid crystal alignment film containing a polyacid imide as a main component, and thus it is possible to observe the effects of the present invention. The liquid crystal aligning agent enamel of the present invention is a solution composition in which the polymer compound in which the poly-amic acid is used as a main component is dissolved in a solvent. The liquid crystal aligning agent has a polymer compound concentration of preferably from 1 to 40% by weight. When the liquid crystal directional paint is applied to the substrate, in order to adjust the film thickness, the enamel paint must be diluted with a solvent in advance, and in order to allow the solvent to be uniformly mixed for the enamel paint and to be well diluted, the polymer must be polymerized. The concentration of the compound is kept in the range of not more than 40% by weight. In the case of the spin coating method and the printing method, in order to make the film thickness uniform, it is usually more than 10% by weight. Other coating methods, for example, may be made to a concentration lower than 10% by weight by the dipping method. On the other hand, when the concentration of the polymer compound is less than 0.1% by weight, the film thickness of the liquid crystal alignment film tends to be too small. Therefore, the concentration of the polymer compound is suitably 0.1% by weight or more, preferably 〇 5 to 10 or so, by a usual spin coating method or printing method. However, depending on the coating method of the enamel paint, a thinner concentration can also be used. The solvent used in the liquid crystal aligning agent enamel of the present invention is not particularly limited as long as it has a solvent capable of dissolving a polymer compound. Therefore, the solvent which is usually used in the production steps and the method of use of polyamine, polyamic acid, soluble polyimine, etc. may be appropriately selected depending on the purpose of use. For such solvents, aprotic polar organic solvents which are polyglycine, soluble polyimine, and polyamine as a solvophilic solvent can be used. For example, the N-type paper size is applicable to the Chinese National Standard (CNS) Α4 specification (2) 】 297 297 mm) (Please read the note on the back first ¥装-- π write this page) Customs Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed -50-1260457 Ministry of Economic Affairs Zhici Property Bureau 8 workers consumer cooperatives printed A7 ___________ B7_____ V. Description of the invention (48) bis- 2-pyrrolidone, dimethylimidazolidinone, N-methyl caprolactam, N-methylpropionamide, N,N/-dimethyl Indamine, dimethyl hydrazine, N, N / dimethyl carbamide, N, N, monoethylformamide, diethyl acetamide or r-butanone, etc. Other solvents for the purpose of improving coatability and the like, such as alkyl lactate, 3-methyl-3-methoxybutanol, tetrahydronaphthalene, isophorone, ethylene glycol monobutyl ether, etc. Alcohol monoalkyl ether, diethylene glycol monoethyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether a propylene glycol monoalkyl ether such as propylene glycol monobutyl ether, a dialkyl malonate such as diethyl malonate, a dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether, or an ester compound such as an acetate thereof. system. The liquid crystal aligning agent enamel of the present invention may contain various additives as needed. For example, in the case where it is desired to improve the coatability, a surfactant which can be used in accordance with such a purpose can be blended with an antistatic agent in the case where it is necessary to improve the antistatic property, and it can be blended with a decane couple in the case where it is desired to improve the adhesion to the substrate. Mixture and titanium coupling agent. The liquid crystal aligning agent lacquer obtained in this manner is suitable for forming a liquid crystal alignment film for a TFT, and is suitable for forming a normal TN type liquid crystal display element because it can provide an appropriate front elevation angle, and is used for an STN liquid crystal display element. For IPS type liquid crystal display elements, VA type liquid crystal display elements, 〇CB type liquid crystal display elements, and liquid crystal alignment films for ferroelectric liquid crystals or anti-strong dielectric liquid crystal display elements are also useful, and Since it is excellent in electrical characteristics as a liquid crystal display element, it can also be used for a protective film, an insulating film, etc. Using the liquid crystal aligning agent of the present invention to form a liquid crystal alignment film, the substrate tensor scale is applicable to the Chinese National Standard Cold (CNS) Λ4 specification (2] 0X297 public f) (please read the note on the back first to write the π π page) Line-51 - 1260457 A7 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed 5, Inventions (49) 'And form a substrate with the same or different liquid crystal alignment film in opposite direction, and sandwich the liquid crystal between them to form a liquid crystal clip The substrate is held, and a liquid crystal display element can be produced according to a known method. When the liquid crystal alignment film is formed, the step of applying a liquid crystal aligning agent to the substrate is carried out, followed by a drying step and a step of heat treatment necessary for the ring closure reaction by dehydration. The method of coating the step is generally known by spin coating, printing, dipping or dropping, and the like is also applicable to the present invention. Further, the method of the drying step and the heat treatment step necessary for the dehydration of the closed-loop reaction are generally known as a method of heat treatment in an oven or an infrared furnace, and a method of heat treatment on a hot plate, etc. The same applies to the present invention. The drying step is preferably carried out at a lower temperature in the range of the evaporable solvent, and further, the heat treatment process is preferably carried out at a temperature of about 150 to 300 °C. The liquid crystal composition preferably used in the liquid crystal display device of the present invention is used, for example, in an s Τ N type liquid crystal display device, and it can be exemplified by the special opening 8 - i 5 7 ^ 8 Pain Gazette 'Special Kaiping 8 - 2 3 1 9 6 0 Japanese Laid-Open Patent Publication No. Hei 9-241644, and Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 0 8 6 2 2 No. 8, Patent 2 6 3 5 4 3 No. 5, Special Table Flat 5 - 5 0 1 7 3 No. 5 'Special Kaiping 8~1 9 9 1 6 No. 8 'Special Kaiping 9~2 3 5 5 5 2 5 Hu Kung Pao, Special Kaiping 9 1 2 4 1 6 4 No. 3 Gazette, Special Kaiping 9 2 5 5 9 5 6 Bulletin, Special Kaiping 1 〇 - 2 0 4 〇 1 6 1 1 inch Kaiping 1〇1〇2 4 3 3 6 bulletin, special Kaiping 1〇一~^^^^^5?7^757^^(210>( 297 mm) "----- (please read first Note on the back of this page) - loaded.

, 1T line -52- 1260457 ΑΊ Β7_ 5, invention description (51)

Pyromellitic dianhydride: P M D A

1 , 2, 3, 4 - butane tetracarboxylic dianhydride: BDA Μ Ρ D alkyl benzene benzene II > base amine amide 2 amide ' amine 4 II, < 4 4

I-I group amine {: r double courtyard I Ν Ν ' ring 4 1 base 4 Ε Ρ D alkyl ethyl benzene 4 Β I Β h C 4 carbamoyl / aniline benzene 4 (please read the note on the back first) ¥ 5 4

4 /IV base 1 3 phenyl - amine 4 diylhexyl pentyl benzene / - \ hexyl ring A D P n Β h c h c 5 A K舄 page) Printed by the Intellectual Property Office of the Ministry of Economic Affairs

Ν Μ Ρ BCGBL Ύ <solvent component> Ν-methyl-2-pyrrolidone-based cellosolve-butyrolactone synthesis (synthesis of poly-proline) with thermometer, stirrer, raw material input and inlet and nitrogen introduction A 100 ml four-necked flask was charged with DPM2·4273 g, dehydrated ΝP 3 5 .0 g' and stirred and dissolved under a dry nitrogen stream. - while maintaining the temperature of the reaction system at 2 〇t: below - adding c β da 1 · 2 〇 05 g and CHDA1 gram sequentially, and while maintaining the reaction temperature below - while reacting for 30 hours, add Bc scale is suitable;] China national i (CNS) -54-1260457 A7 B7 V, invention description (52) 20 · 0 g, GBL40 · 0 g, the production of polymer concentration of 5% poly-proline solution. The polylysine in this solution is represented by P A 1 . The weight average molecular weight of PA 1 is 5 600. Further, except that the raw materials were replaced as shown in Table 28, the respective 5% by weight solutions of the polyamic acid PA2 to PA17 were produced in the same manner. Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Table 2 8: Composition of Polyamide Acid__ Raw Material Molar Rate (%) Weight Average Tetracarboxylic Acid dianhydride Diamine Molecular Weight CB MCB DMCB CH ΡΜ BD DP DP 4ChB 5ChChB (GPC) DA DA DA DA DA A Μ Et IB 1PDA PA1 25 25 50 56,000 PA2 25 25 50 52,000 PA3 25 25 50 50,000 PA4 13 12 25 50 51,000 PA5 13 12 25 50 70,000 PA6 45 5 50 66,000 PA7 35 15 50 51,000 PA8 15 35 50 45,000 PA9 5 45 50 67,000 PA10 20 20 10 50 57,000 ΡΑ11 20 20 10 50 55,000 ΡΑ12 25 25 50 88,000 ΡΑ13 25 25 20 30 65,000 ΡΑ14 25 25 20 30 74,000 ΡΑ15 50 50 43,000 ΡΑ16 50 50 99,000 ΡΑ17 50 50 107,000 ΡΑ18 50 20 30 74,000 ΡΑ19 50 1 20 30 123,000 (Please read the note on the back to write this page) Pack - Order----Line paper size applies to China National Standard (CNS) A4 size (210X 297 mm) -55- 1260457 A7 B7 V. INSTRUCTIONS (53) EXAMPLES 1 (1) Blending of liquid crystal directional paint (please read the note on the back first) Write this page. The 5% by weight solution of polylysine p A 1 manufactured by the synthesis example is (Ν Μ P / BC ) The dilution solvent (1 / 1) was diluted to prepare a liquid crystal aligning agent lacquer having a polymer concentration of 3% by weight. (2) Production of components for voltage holding rate evaluation, Ministry of Economic Affairs, Zhici Property Bureau, Staff Consumer Cooperative, printed on a glass substrate with a transparent electrode I ,, and a liquid crystal directional paint containing the above polyacrylic acid PA 1 It was coated with a spin coater, pre-calcined at 80 ° C for about 5 minutes, and then subjected to heat treatment at 250 ° C for 30 minutes. Next, the surface of the substrate on which the alignment film is formed is subjected to rubbing treatment by a rubbing device to perform orientation treatment. Prepare an identical substrate for the same operation. The substrate of one of them is spread 7 / / with the spacer material, and the other substrate is formed as the inner side of the oriented film surface, the liquid crystal injection hole is left in the periphery, and sealed with an epoxy hardener to make a gap 7 // m anti-parallel battery. A liquid crystal composition was injected into the battery, and the injection port was sealed with a light hardener, and the U V was irradiated to harden the liquid crystal injection hole. Next, heat treatment was carried out for 30 minutes at 1 10 ° C to prepare a battery for evaluation of voltage holding ratio. The composition of the liquid crystal composition used is shown below. The composition has a N I point of 1 0 0 · 0 t: and, in turn, a complex refractive index of 0 · 0 9 3 . 】7wu This paper scale applies Chinese National Standard (CNS) A4 specification (21GX 297 mm) -56 - 1260457 Α7 Β7 Invention description (54) 〇必7~〇~~ 17vt4 Mil—{D~~F l6wt·% lOvtj 〇3Η7~^3~ F 5^.χ l〇wtj 6wtj c^K>-<〇M^-F C5H11 6vtj I3wt· C Please read the note on the back first π write this page) -裴-订经济Ministry of Intellectual Property Bureau employee consumption cooperative printing (3) The battery for measuring the front elevation angle is used in addition to the use of 2 Ο // the spacer material used to anger 9 m - day ^ 1 1 fly for 7 # used spacer material, and In the same manner as in the production of the battery for measuring the voltage holding ratio described in (2), the anti-parallel battery for measuring the elevation of the cell was prepared. The liquid crystal material in the measurement of the front elevation angle also uses the same material as the liquid crystal material in the measurement of the voltage holding ratio. 4 Evaluation method of liquid crystal battery This paper scale applies to China National Standard (CNS) A4 specification (2] 〇X 297 mm) ---- Line 57 ~ 1260457 A7 B7 One ^ ~ One..... - - _______________ _5. Description of the Invention (55) With respect to the liquid crystal cell obtained above, the voltage holding ratio was measured by a known method (for example, it is contained in the first liquid crystal seminar pre-set p 7 8 ). The measurement conditions were a gate width of 6 9 // s , a cycle number of 60 Η z , and a wave height of 4 · 5 V ' measured temperature of 60 ° C. Further, the elevation angle before the liquid crystal was measured by the crystal rotation method. The battery at the time of the front elevation was measured under a bias microscope, and the orientation was evaluated by investigating whether or not the orientation was poor. The results are shown in Table 29. Examples 2 to 14 and Comparative Examples 1 to 5 Using the polyacrylic acid shown in Table 2, and in addition to firing at a temperature of 袠2, a liquid crystal display element was produced according to Example 1: i evaluated the voltage holding ratio, The results of the front elevation and orientation are shown in the same paragraph. (Please read the notes on the back first)

-JTI J7I for the purchase of the book) - Gutter Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed This paper scale applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -58- 1260457 A7 B7 Ministry of Economic Affairs Employees' Consumption Cooperatives Printing 5, Inventions (56) Table 2 9: Examples and Comparative Examples Examples Polyamide calcination temperature °C Voltage retention rate /% Forward elevation / degree orientation Example 1 ΡΑ1 210 98.4 1.2 Good Example 2 ΡΑ 2 230 98.2 L1 Good Example 3 ΡΑ 3 250 98.3 1.1 Good Example 4 ΡΑ 4 250 98.1 1.1 Good Example 5 ΡΑ 5 250 98.0 1.0 Good Example 6 ΡΑ 6 250 98.2 1.1 Good Example 7 ΡΑ 7 230 98.6 1.2 Good Example 8 ΡΑ 8 210 98.7 1.2 Good example 9 ΡΑ 9 210 98.8 1.4 Good example 10 ΡΑ 10 180 98.3 L2 Good example 11 ΡΑ 11 230 98.2 1.5 Good example 12 ΡΑ 12 230 98.2 1.5 Good example 13 ΡΑ 13 250 98.5 5·2 Good example 14 ΡΑ14 250 98.0 9·5 Good Comparative Example 1 ΡΑ15 210 98.8 1.3 Bad Comparative Example 2 ΡΑ16 230 97.2 0.5 Good Comparative Example 3 ΡΑ17 180 97.4 1.5 Good Comparative Example 4 ΡΑ18 250 98.5 5.6 Poor Comparative Example 5 ΡΑ19 250 97.0 6.0 Good According to Examples 1 to 14 4, it is known that the liquid crystal directional paint of the polyglycolic acid of the present invention is used. The characteristic is that the voltage holding ratio is above 9 8 %. The paper scale is applicable to the Chinese national standard rate (CNS j A4 specification (2) 〇χ 29*7 mm) n^- ml · i in- sm n —i (please first Read the note on the back of this page.) Ordering line -59 - 1260457 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 __B7 V. Invention description (57), front elevation angle, good orientation. According to Comparative Example 1~5 In addition, it is known that CBDA is used alone, and PMDA is used as a tetracarboxylic dianhydride, and the orientation is good, but the voltage retention rate is deteriorated to 98% or less. Conversely, when CHDA is used alone, the voltage retention rate is good, but The front elevation angle is lowered and the orientation is deteriorated. From the above, the characteristics of the liquid crystal aligning agent enamel of the embodiment using the polyamic acid of the present invention are superior in balance to the comparative example. Industrial Applicability By using a liquid crystal aligning agent enamel containing the polyamic acid of the present invention, it is possible to obtain a liquid crystal display element which is excellent in coatability, can be arbitrarily adjusted in front elevation angle, and has a high voltage holding ratio. The liquid crystal aligning agent enamel of the present invention is particularly suitable for use in a TFT type liquid crystal display element (TN type, IPS type, VA type, OCB type), and has excellent electrical characteristics, and the front elevation angle can be arbitrarily adjusted, and thus It is used as an STN type liquid crystal display element, a ferroelectric liquid crystal, and an orientation agent for an anti-strong dielectric liquid crystal display element. Further, since the film of the liquid crystal aligning agent is excellent in electrical characteristics, it can be used as a protective film or an insulating film. (Please read the note on the back first. Pack - π write this page) Order ----^ Line This paper scale applies to China National Standard (CNS) Α4 specification (210Χ 297 mm) -60 -

Claims (1)

1260457 A8 B8 C8 D8 Type (1) Packing 6. Patent Application 1 1 · A liquid crystal aligning agent enamel which is obtained by reacting a tetracarboxylic acid with a diamine compound to contain 〇·]~40 weight a liquid crystal aligning agent lacquer having a ratio of %, which is characterized in that at least one of tetracarboxylic acids having a tetracarboxylic acid residue represented by the following formula (1) and cyclohexanetetracarboxylic acid are used as a raw material, In the above formula (1), the bonding position of R is an arbitrary position of the cyclobutane ring, R is a methyl group, and Q is a number of 〇~2), and the diamine compound of another raw material contains the following formula ( 2) The diamine-based compound shown; C Please read the note on the back first to write this page) Order (CH3), h2n-' (CH2)n (CH3)m (2) Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperatives, printing number, the base of the mixture is the side to the residue, 2 amines are fixed, and ~ two crystals are used. It is the same as the liquid tetragen 3 is I), and the carbon is the same as the ip acid; the carboxy group is different from the S0, the four%1 acid is divided into the quantity {carboxy has mJ, the 0® type four contains 40, the alkane is <li lacquer, the Isf 淸 0.1 has a ring 1 bond to form a mixture with the acid, η Cycloamine to make a benzene crystal II in a substrate, less Amines in the liquid to the second to the second species 2 of the species of S1 彳 一 得 特 类 类 胺 胺 胺 胺 所 所 所 所 所 , , , , , , , , , , , 2 2 2 2 羧 羧 羧 羧 羧 羧 羧? The other chain of the material is applicable to the Chinese National Standard (CNS) Α4 specification (2Ι0Χ297 mm) -61 - 1260457 A8 B8 C8 D8 VI. Patent application scope 2 Printed by the Consumers' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs (but in the above formula (1), the bonding position of R is any position of the cyclobutane ring, R is a methyl group, and q is a number of 〇~2). 3. The liquid crystal aligning agent enamel according to item 2 of the patent application, wherein the diamine compound having a carbon number of 3 or more side chain groups is selected from the group consisting of compounds represented by the following formulas (3) and (4) Diamine-based compound; z ""^nh2 formula (3) (but in the above formula (3), R: is hydrogen or an alkyl group having a carbon number of 1 to 12, γ is a single bond or a methylene group, and the ring A is 1 , 4 phenyl or 1 , 4 —cyclohexyl 'Z is a single bond 'methylene, ethyl or oxygen, r is 〇~3 , ^ S is 0~5 , t is 0~3 a number, but in the case where t is 2 to 3, each z may be the same or different from each other, and may be bonded to hydrazine, 4 phenyl or i, 4 to any of the cyclohexyl groups may be substituted by a lower alkyl group) H2Nn__/NH2 U Xi—Bi—X2—b2—R2 Formula (4) (But in the above formula (4), X 1 to X 2 are each independently a single bond, ~〇一,一c〇〇一,一〇c〇一,_NH —, (Please read the note on the back to write this page) • Install the paper size for the country of the country (CNS) A4 grid (21 OX 297 mm) 62- 1260457 A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Office staff Printed by the Consumer Cooperatives, the patent application scope is 3~C〇NH—, or the alkyl group with a carbon number of 1~1 2 , B! and B2 are respectively represented by a single bond, or contain an aromatic ring group and an alicyclic ring. The divalent group of 1 to 3 rings selected, R2 is a group representing -Η, - F, - CN, or a carbon number of 1 to 1 2, a fluorine-based or a hospitaloxy group, and, & The bonding position of the base to the benzene ring is an arbitrary position). 4. The liquid crystal aligning agent lacquer according to item 3 of the patent application, wherein the diamine compound having a carbon number of 3 or more side chain groups is a diamine compound selected from the group of compounds represented by the formula (3). 5. The liquid crystal aligning agent enamel according to item 3 of the patent application, wherein the diamine compound having a carbon number of 3 or more side chain groups is a diamine compound selected from the group of compounds represented by the formula (4). A liquid crystal display element characterized by using a liquid crystal aligning agent lacquer as disclosed in any one of claims 1 to 3 to 5. 7 - a poly-proline, characterized by having a tetracarboxylic acid having a tetracarboxylic acid residue represented by the formula (1) and a tetracarboxylic acid containing a cyclohexanetetracarboxylic acid, and the formula (2), ( 3) and (4) a compound obtained by reacting one or more kinds of diamine-based compounds, wherein (cyclohexane tetra-residual dianhydride/tetracarboxylic acid represented by the following formula (1) The molar ratio of the tetracarboxylic dianhydride of the acid residue is (97/3) to (3/97), Rigid formula (1) (But in the above formula (1), the bonding position of R is any position of the cyclobutane ring, R is a methyl group, (1 is a number of 0 to 2), and the paper size is applicable to the Chinese country.禚准 (CNS) A4 this grid (2!0X297 mm) (Please read the note on the back: write this page), tr -63- 1260457 Α8 Β8 C8 D8 Patent application scope 4 (CH3), (CH3)r (CH2)n However, in the above formula (2), n is 1, and < and m are each independently 〇, and the bonding position of the methyl group to the benzene ring is an arbitrary position) Equation (2) ~ 2 Ζ- ττ •ΝΗ 2 -νη2 (t (3) (Please read the note on the back ^^ write this page) -Install 'Island Department of Intellectual Property Bureau employee consumption cooperative printing (However, in the above formula (3), R! is hydrogen or an alkyl group having 1 to 12 carbon atoms, Y is a bond or a methylene group, and the ring is 1, 4 or phenyl or 1,4-cyclohexylene. , Z is a single bond, methylene, ethyl or oxygen, r is 〇~3, s is 0~5, t is 0~3, but t is 2~3, each Z can be each other The same or different, in addition, any hydrogen bonded to the 1, 4 -phenyl or 1, 4 -cyclohexyl group may be substituted by a lower alkyl group), ^2~H2 (4) (but in the above formula (4) , X i ~ X 2 are independently a single bond, one by one, one C 〇〇 one, one 〇 C 〇 one, one NH —, —CONH —, or a carbon number of 1 to 1 2 alkyl, B〗 &B2 is independently expressed as a single bond, or contains an aromatic ring group and an alicyclic ring selected 1~ This paper size is applicable to China National Standard (CNS) A4 specification (2]〇X 297 mm) -64 - 1260457 Α8 Β8 C8 D8 VI. Apply for a patent range of 5 3 rings of divalent groups, 1^2 for one Η, one F, — CN, one 〇Η, or an alkyl group having a carbon number of 1 to 12, fluoroalkyl or The alkoxy group, and the substituent is bonded to the benzene ring at an arbitrary position). A liquid crystal display element characterized by a liquid crystal display element according to claim 6 and containing a fluorine-based liquid crystal composition. 9. A polyimine acid characterized by having a tetracarboxylic acid having a tetracarboxylic acid residue represented by the formula (1) and a tetracarboxylic acid containing a cyclohexanetetracarboxylic acid, and the formula (2), ( The cyclohexanetetracarboxylic dianhydride obtained by reacting one or more kinds of diamine compounds in the compound group represented by 3) and (4) / the tetracarboxylic acid having the tetracarboxylic acid residue represented by the following formula (1) The molar ratio of anhydride is (97/3)~(3/97), (Read the first note on the back ^|^Write this page} - Install · Order (1) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing (R)q (However, in the above formula (1), the bonding position of R is any position of the cyclobutane ring, R is a methyl group, Q is a number of 0 to 2), (CH3), h2n-- (CH2)n (CH3) Formula (2) (However, in the above formula (2), n is 1, < and m are independently the number of 〇~2, and the position of the methyl group for the bonding position of the benzene ring is arbitrary), the paper size is applicable China National Standard (CNS) A4 Specification (23〇X 297 mm) ^65- 1260457 A8 B8 C8 D8 Patent Application Range 6 *2 nh2 t Formula (3) (However, in the above formula (3), Ri is hydrogen or an alkyl group having 1 to 12 carbon atoms, Y is a single bond or a methylene group, and an anthracene ring is a 1, 4-phenylene group. Or 1, 4 - extended cyclohexyl, Z is a single bond, methylene, ethyl or oxygen, r is 〇~3, s is 0~5, t is 〇~3, but t is 2~3 In the case where each Z may be the same or different from each other, and any hydrogen bonded to the 1,4-phenylene or 1,4-cyclohexyl group may be substituted by a lower alkyl group, 2 -J-B-, -X2~日2 - 卩2 Type (4) (Please read the note on the back first to write this page). Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative (but in the above formula (4) , X!~X2 are independently a single bond, one by one, one C〇〇~-, one C〇 one, one NH—, one CONH—, or an alkyl group having a carbon number of 1 to 12, Bi&B2 Respectively expressed as a single bond, or a divalent group containing 1 to 3 rings selected from the aromatic ring group and the alicyclic ring, and R2 represents -Η, -F, - CN, a 〇Η, or a carbon number of 1~ A hospital base of 12, a fluoroalkyl group or an alkoxy group, and, in addition, the bonding position of the substituent to the benzene ring is an arbitrary position). The paper size is applicable to the Chinese National Standard (CNS) A4C (2) 297 297 mm) -66 - Patent application No. 91914958 Republic of China 94 Chinese version of the revised manual (including the scope of application for patents) Preface / 7 Application period: July 5, 1991 Π Case No. 91914958 All categories above the column are filled by this Bureau) A4 C4 Set J Patent Specification Invention 々 / First, the name of the new Chinese liquid questioning agent enamel paint and liquid product display: η; for English Aligning agent varnish for ' 1iquid crystal and 1iquid-crysta play cloiiiont _: _ 1 Name (1) Ruo Tianbin bow (2 ) Gentamine (3) Murata Mirror male nationality (1) Π本网·下叶市市市市五弁海岸五岙戢之 · · The PiJ company's functional materials research institute in-house, residence invention / (2) Yu Jing _ Qianchao County Wuhe Coast Wuyi Deng One Songsong Company Functional Materials Research Institute (3) π本P千菜县市市市五井海岸五#一行行索心济化学有有隈公司Functional lining research institute name (name) Ministry of Economic Affairs intellectual property contract · employee consumption cooperative printing 3, applicant's nationality residence, residence (office) representative name (1)少^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Ding Wei Liu Fan San 2 Mirror 0 □ Ben Ρ 京 Jing Jing Central [塍 _ 2" Ί丨 · ·:! #馈··号(1) 藤藤舜吉 S) Yoshiro Shoji 1 This paper scale applies Chinese National Standard (CNS) A4 specification (2丨0X 297 mm) 1260453⁄4^3⁄43⁄4 Application A7 B7 Republic of China Buzhengwu, invention description ((Please read the precautions on the back and then write this page) 2 3 1 4 8 2nd bulletin, special opening 2〇Ο〇一〇8 7〇4 0 公幸 g, special opening 2 Ο〇1 1 4 8 The liquid crystal composition disclosed in the publication of the above-mentioned publication, the liquid crystal composition for a TFT liquid crystal display device described in the above publication, and the liquid crystal aligning agent of the present invention. The liquid crystal display element formed by the combination of the obtained liquid crystal alignment films is suitably used in the field of high voltage holding ratio, and has a large effect of improving baking. That is, the liquid crystal aligning agent of the present invention has and has the terminal described herein. - a compound of a CF 3 group and a fluorine-based liquid crystal composition having a high voltage holding ratio, such as a compound having 1 to 3 or more fluorine atoms, are used in combination as a property. Further, the liquid crystal composition is used in one or more kinds. Optically active compounds are also fine. Example The embodiments of the present invention are described in detail below, but the present invention is not limited by the embodiments. The compound names of the raw material components used in the respective examples and the abbreviations thereof are described below. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives <tetracarboxylic dianhydride> 1, 2, 3, 4 - cyclobutane tetracarboxylic dianhydride: CBDA 1,2,4,5 -cyclohexane tetracarboxylate Acid dianhydride: CHDA methyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride: MCBDA 1,3 - dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride: DMCBDA This paper scale applies to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) -53-