TW591056B - Polyamide-imide, liquid crystal orientating ingredient varnish and liquid crystal display - Google Patents

Abstract

The present invention is about a new polyamide-imide that is used in an electron material domain. A liquid crystal orientating ingredient varnish which is provided by the present invention can provide moderate pre-tilt angle, bester liquid crystal orientation, and electricity characteristic which has better total balance to correspond the purpose in a liquid crystal display. The polyamide-imide show as below: The polyamide-imide only has the compositing unit of formula (1-1) between the compositing unit of the formula (1-1), the compositing unit of the formula (1-2), the compositing unit of the formula (1-3). Or the polyamide-imide has two or more compositing units between those compositing units. In the polyamide-imide, at least one between the organic missing residue group from the carboxylic acid type and the organic missing residue group from the diamine compounds is an organic missing residue group that has a side chain group which has three or more carbon. The symbols in the formula are defined as below. T1-T3 is the organic missing residue group from the carboxylic acid type. D1-D3 is the organic missing residue group from the diamine compounds. R1-R3 is the hydrogen or a monovalence organic group, respectively. The monovalence organic group chooses from alkyl, hydroxy alkyl, alkoxy alkyl, unsaturated fatty group, the group having alicyclic group, aryl group, heterocyclic ring group having oxygen, the group having steroid skeleton, the group having carbonyl group, organosilyl, and the group having organosilyl. The random hydrogen of the alkyl having the organic group and the alkylene having the organic group can be replaced by fluorine. In the aryl group, the random hydrogen of the aromatic ring also can be replaced by alkyl, alkoxy, and -CN. The random hydrogen of the alkyl and the alkoxy also can be replaced by fluorine. The aralkyl group is a kind of aryl group. The alkylene of the aralkyl also can be combined to aromatic ring with oxygen atom. And the 30 mole % of the total amount of R1-R3 of the polyamide-imide is monovalence organic group.

Description

591056 9825 pif 1 发明 Description of the invention: Inventive jaw field The present invention relates to a new type of polyamide-imide used in the field of electronic materials. By using this polyamidoamine-iminomine, a liquid crystal alignment film having better liquid crystal alignment can be obtained. The use of the liquid crystal alignment film can give the liquid crystal display element better electrical characteristics. BACKGROUND OF THE INVENTION Liquid crystal display elements are mainly display elements using nematic liquid crystals. In this regard, it is known to include TN type liquid crystal display elements with a liquid crystal having a 40 degree spiral, and STN types with a liquid crystal having a spiral of 180 degrees or more A liquid crystal display element and a so-called TFT-type liquid crystal display element using a thin film transistor. Recently, In-Plane Switching (IPS) type liquid crystal display elements with improved horizontal visual field characteristics, vertical alignment (Vertical Alignment (VA) type liquid crystal display elements using vertical alignment state), or Research on optically compensated birefringence (OCB) type liquid crystal display elements using curved alignment states, among which one of the aforementioned parts has even been put into practical use. The progress of liquid crystal display devices has not only progressed in the above-mentioned manner, but also has been actively moving toward the improvement of peripheral materials for the purpose of improving the characteristics of liquid crystal display devices. Since the liquid crystal alignment agent is an important factor for the display quality of the liquid crystal display element, and when the high quality of the liquid crystal display element is required, the ratio of the liquid crystal alignment agent becomes a more important factor. At present, the liquid crystal alignment agents that are mainly used are polyamidoamines that are used to aminate polyamidoamines, and polyamidoamines such as soluble polyamidoamines. 8 9825 pifl In addition to polyimide-based alignment agents, various liquid crystal alignment agents have also been explored. They are used for heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment properties, electrical properties, and display. Whether characteristics, etc. are inappropriate. Among the polyimide-based alignment agents, polyamic acid has a high solubility in a solvent, and thus has good substrate coating properties. However, when forming the alignment film, since heating is necessary for a sintering process called imidization, there is a problem that characteristics are deteriorated due to low-temperature sintering. On the other hand, the soluble polyamidoamine has a problem of poor solubility in solvents, and even when a limited solvent is not used, there is a disadvantage of poor printability. In addition to polyamidine-based alignment agents, polymer compounds such as polyamidamine and N-substituted polyamidine (polyamidine in which a hydrogen atom of (amidron-bonded (-CONH-)) is replaced with another group), etc. Be investigated. Polyamides have good liquid crystal alignment, but they have some disadvantages regarding solubility and printability, and they have problems with electrical characteristics. N-substituted polyamides have good solubility, printability, and electrical properties, but they have some shortcomings about the alignment of the liquid crystal. There are also liquid crystal alignment agents mixed with a plurality of polymer compounds, and liquid crystal alignment agents using block copolymerized polymer compounds. However, in the present situation, the foregoing still has some shortcomings about electrical characteristics such as current consumption, residual charge, voltage retention, sintering, and liquid crystal alignment. Among the required topics, only certain properties are better, so as The practical application of liquid crystal alignment agents is still difficult. The liquid crystal alignment agent must have a combined balance characteristic. When the field of use of liquid crystal display elements becomes wider, the requirements for the characteristics of liquid crystal display 591056 9825 pifl elements are also relatively increased. The requirements include requirements for liquid crystal alignment represented by the forward tilt of the liquid crystal, requirements for electrical characteristics of liquid crystal display elements such as current consumption, voltage retention, and residual charge, and long-term use of the aforementioned characteristics. Reliability requirements, afterimage phenomenon of liquid crystal display elements, and display quality requirements such as uneven display. Among the aforementioned characteristics, the front tilt angle of the liquid crystal can be changed by the driving method of the liquid crystal display element to the required number. For example, the TN-type liquid crystal display element and the TFT-type liquid crystal display element whose liquid crystal is 90-degree spiral are about 1 to 6 degrees. In the STN type liquid crystal display element with a large helix angle, it is necessary to have a front tilt angle of about 3 to 8 degrees. However, the angle of inclination before this requirement may vary depending on the application. Recently, STN type liquid crystal display elements have also been required to be 2 to 3 degrees or 8 degrees or more. On the other hand, in the IPS-type liquid crystal display element, in order to change the liquid crystal to the substrate in the horizontal direction, the tilt angle does not need to be large before, and the forward tilt angle is changed by about 1 to 3 degrees. On the other hand, in the VA type liquid crystal display element, a large forward tilt angle of about 90 degrees must be used, and in the OCB liquid crystal display element, in order to stabilize the bending alignment state, a large value of 5 to 20 degrees must be used. Lean forward. Furthermore, not only the forward tilt angle, but also the liquid crystal alignment characteristics such as alignment uniformity, alignment stability, or anchoring energy at the liquid crystal-alignment film interface have a more important influence on the performance of the liquid crystal display element. In the manufacturing process of a liquid crystal display device, the process margin of this characteristic is also important. The drying conditions after the alignment agent is applied, and the annealing treatment conditions after the liquid crystal is injected will inevitably change the rake angle or the alignment. 10 591056 9825 pifl STN liquid crystal display elements, especially low-voltage type display elements used in the field of portable devices, have low driving voltages, so the magnitude of current consumption is important. That is, when the current consumption of the liquid crystal display element becomes larger, the voltage applied to the liquid crystal is relatively reduced, so that the rise of the liquid crystal becomes unstable, thereby reducing the contrast. Furthermore, in a low-voltage type liquid crystal display element, a change in current consumption 可靠 (reliability) during long-term use of the liquid crystal display element becomes important. Since the display on-off of the STN type display element is performed only by the potential difference, when the element's current consumption 値 changes with the voltage applied to the liquid crystal, normal driving cannot be performed. In more extreme cases, as a result of driving for a long time, the image of the liquid crystal display element may not be completely displayed. On the other hand, in a TFT-type liquid crystal display element, the performance regarding voltage retention and residual charge is particularly important. When the voltage holding ratio is low and the voltage applied to the liquid crystal decreases during the patterning period, the problem of lowered contrast tends to occur. Furthermore, when the residual charge is large, after the voltage is applied, it will remain as an "off" charge, so the image after being erased will have an afterimage. In the TFT-type liquid crystal display element, this afterimage phenomenon (sintering) is a very important issue. In recent years, as the driving voltage has been lowered, liquid crystals having a large dielectric constant and a different dielectric constant have been used. However, in accordance with this tendency, a problem of uneven display (uneven brightness) occurs on the display surface. Since the sizing of the alignment film after honing may occur, the phenomenon is not removed and the water is washed. At this time, uneven display may occur due to residual washing marks, and this phenomenon is a major problem. 11 591056 9825 pif 1 The present invention provides a liquid crystal alignment agent, which is used to obtain among the various characteristics required by the aforementioned liquid crystal display elements, in particular, it has a better front tilt angle, liquid crystal alignment, and electrical characteristics (current consumption, voltage, voltage Liquid crystal display elements with better balance such as retention, residual charge, and sintering). Description of the Invention The present inventors have conducted research in order to solve the above problems, and as a result, the above-mentioned object can be achieved by using polyimide-imide in the following structure in a liquid crystal alignment agent varnish. . That is, the present invention has the following structure. < [1] Polyamidamine-imidoamine having a structural unit represented by formula (1-1) or a structural unit represented by formula (1-2) and formula (1-3), respectively.

Ο II C T2 " XN-E ^-(1-2)

(1-3) In the above formula, the symbols used are defined as follows. τ1, T2 and T3 refer to organic residues derived from carboxylic acids (missing 12 9825 pif 1 residue). D1, D2 and D3 refer to organic residues derived from diamine compounds. Among them, at least one of T1, T2, T3, D1, D2, and D3 is an organic residue having a side chain group having a carbon number of 3 or more. R1, R2 and R3 are each independently hydrogen or a monovalent organic group. This monovalent organic group is selected from alkyl groups having 1 to 20 carbon atoms, hydroxyalkyl groups having 1 to 8 carbon atoms, alkoxyalkyl groups having 2 to 20 carbon atoms, and Saturated aliphatic group, alicyclic group, aromatic hydrocarbon group, oxygen-containing heterocyclic group, group having nest skeleton, group having carbonyl group, organosilyl group, and organic Silyl groups. Any hydrogen contained in the alkyl group and alkylene group contained in such an organic group may be replaced with fluorine. In the aromatic hydrocarbon group, any hydrogen of the aromatic ring may be replaced with an alkyl group, an alkoxy group, or -CN. Any hydrogen of the aforementioned alkyl and alkoxy groups may be replaced with fluorine. Alkylene on an aralkyl group, which is an aromatic hydrocarbon group, can also be bonded to the aromatic ring through an oxygen atom. Moreover, 30 mol% or more of the total amount of R1 to R3 in the polyamidoamine-iminomine molecule is a monovalent organic group. [2] In the polyamidoamine-iminomine described in the item [1], at least one of the organic residues derived from the diamine compound is selected from the group consisting of groups represented by formulas (2) to (5) Group of people. 13 591056 9825 pif 1

The symbols used in the formula (2) are defined as follows. R4 means hydrogen or an alkyl group having 1 to 12 carbon atoms.

Ring A means 1,4 · phenylene (l, 4-phenylene) or 1,4-cyclohexylene. Arbitrary hydrogen in the ring may be substituted with an alkyl group having 1 to 4 carbon atoms. Z1 and Z2 are independent single bonds, -CH2-, -CH2CH2- or -0. r is an integer of 0 to 3, s is an integer of 0 to 5, tl is an integer of 0 to 3, and t2 is an integer of 0 to 3. However, when t1 is 2 or 3, a plurality of Z1 may be the same as each other, or may be different from each other. When t2 is 2 or 3, a plurality of Z2 may be the same as each other or may be different from each other.

(3) In the formula (3), the position of the radical in the benzene ring is arbitrary. The symbols in this formula are defined as follows. X1 and X2 are individually independent single bonds, -0-, -00-, -OCO-, -NH-, -C0NH- or alkylenes having 1 to 12 carbon atoms. G1 and G2 are individually independent single bonds or divalent groups containing 1 to 3 rings. The ring system is selected from the group consisting of an aromatic ring and an alicyclic ring. R5 means hydrogen, fluorine, -CN, -0H, an alkyl group having 1 to 12 carbon atoms, or 14 591056. 9825 pif 1 alkoxy group having 1 to 12 carbon atoms. Any hydrogen of this alkyl group may be replaced with fluorine. However, when G2 is a single bond and X2 is not a single bond or an alkylene group, R5 is hydrogen or an alkyl group. When G1 and G2 are both single bonds, the total carbon number of X1, X2 and R5 is 3 or more.

In formula (4), any hydrogen of 1,4-phenylene may be substituted with an alkyl group having 1 to 4 carbon atoms. The symbols in this formula are defined as follows. X3 and X4 are independent single bonds, -ch2-, ch2ch2-, or -0. R6 and R7 are each independently hydrogen, an alkyl group having 1 to 12 carbons, or a gas-substituted compound having 1 to 12 carbons. ul and u2 are independent integers of 0 to 3.

However, at least one of R6 and R7 is an alkyl group having 3 or more carbon atoms or a fluoroalkyl group having 3 or more carbon atoms. When ul is 2 or 3, multiple X3s may be the same as each other or different from each other. When u2 is 2 or 3, a plurality of X4 may be the same as each other or may be different from each other.

In formula (5), the bonding position of the substituent and the radical with respect to the benzene ring is arbitrary. The symbols in this formula are defined as follows. R8 is hydrogen or an alkyl group having 1 to 12 carbon atoms. Any -CH2- in this courtyard can also be replaced with -0-. X5 refers to a single bond or an alkylene group having 1 to 5 carbon atoms. Any -CH2_ 15 591056 9825 pif 1 in this alkylene can also be replaced with -〇-. m is an integer of 0 to 3, and η is an integer of 1 to 5. [3] In the polyamidoamine-iminomine described in the item [1] or [2], R1 in the formula (1-1) of the item [1] and the formula described in the item [1] In (I-2), r2 and R3 are individually independent hydrogen or monovalent organic groups having a carbon number of 5 or less, and more than 50 mol% of the total amount of R1 to R3 in the molecule are monovalent organic groups. . [4] In the polyfluorenimidine-methyleneimide described in the item [3], the carbon number is 5 or less. The monovalent organic group is selected from an alkyl group having a carbon number of 5 or less and a carbon number of 5 or less. A group consisting of a hydroxyalkyl group of 0 and an alkoxyalkyl group having a carbon number of 5 or less. Among them, 70 mol% or more of the total amount of R1 to R3 in the molecule is a carbon number of 5 or less. Organic. [5] Liquid crystal alignment agent lacquer containing polymer compound and solvent and the proportion of polymer compound is 0.1% to 40% by weight based on the total weight of lacquer, wherein the polymer compound is N A mixture of substituted polyamidoamine-iminomine or N-substituted polyamidoamine-amidoamine and other polymers. However, the N-substituted polyamidoamine-iminomine system is the polyamidoamine-iminomine described in item [1], and the other polymer systems are selected from polyamic acid, soluble polyimide, and polyamidamine. Choose at least one of the groups consisting of amines and other polyamidoamines. # [6] Contains high molecular compounds and solvents and the proportion of high molecular compounds * In the case of the total weight of the lacquer as the basis, it is 0.1% to 40% by weight of the liquid crystal alignment agent lacquer, which is high The molecular compound is a mixture of N-substituted polyamidoamine-iminomine or N-substituted polyamidoamine-iminomine and other polymers. However, the N-substituted polyamidamine-imidamine system is polyamidine-591056 9825 pifl imidazine described in item [2], and other polymer systems are selected from polyamic acid, soluble polyimide, Select at least one group of polyamidamine and other polyamidamine-amidamine groups. [7] Liquid crystal alignment agent lacquer containing polymer compound and solvent and the proportion of polymer compound is 0.1% to 40% by weight based on the total weight of lacquer, wherein the polymer compound is N Mixtures of polyamidoamine-iminomine or N-substituted polyamidoamine-iminomine and other polymers. However, the N-substituted polyamidamine-amidamine system is the polyamidamine-amidamine described in item [3], and the other polymer systems are selected from polyamic acid, soluble polyimide, and polyamidamine. And at least one of the polyamidamine-amidamine groups. [8] A liquid crystal alignment agent lacquer containing a polymer compound and a solvent and the proportion of the polymer compound based on the total weight of the lacquer is 0.1% to 40% by weight, in which the polymer compound is It is a mixture of N-substituted polyamidoamine-iminomine or N-substituted polyamidoamine-iminomine and other polymers. However, the N-substituted polyamidamine-amidamine system is the polyamidamine-amidamine described in item [4], and the other polymer systems are selected from polyamic acid, soluble polyimide, and polyamidamine. And at least one of the polyamidamine-amidamine groups. [9] A liquid crystal display element, a transparent electrode is provided on a pair of transparent substrates, a liquid crystal alignment film is formed on the transparent electrodes, and the substrate is combined face-to-face with a gap material, and then a liquid crystal material is sealed to obtain a liquid crystal display element . At least one liquid crystal alignment film formed on the substrate is a liquid crystal 17 591056 9825 pif 1 alignment film formed using the liquid crystal alignment agent paint described in any one of [5] to [8]. In the above-mentioned structure towel, the base is turned to form an alignment film and a shaft of a leg leaven. Dragon is a material suitable for lacquering as an alignment agent for liquid crystal display elements. In addition, "another amine_iminomine" refers to _amine_iminomine which is outside the axis of the present invention. Detailed description of the preferred embodiment In the present invention, the alkyl group, alkylene group, alkoxy group, hydroxyalkyl group, alkoxyalkyl group, and fluoroalkyl group may be a linear group or a branched group. In the description of construction, the structural unit represented by the formula (1_1) is described by the structural unit (M). The structural unit represented by the formula (I-2) is described in terms of the structural unit (1-2). The structural unit represented by the formula (1-3) is described in the structural unit (1_3). An organic residue having a side chain group having a carbon number of 3 or more will be described as a residue with a larger side chain. The first feature of the polyamidoamine-iminomine of the present invention is a structure having a structural unit U-1) or a structure having both structural units (1-2) and (1-3). The polyamidoamine-iminomine having the structural unit (1_1) may further include at least one of the structural units (1-2) and (1-3). The second feature is at least one large side chain residue. The residue of this larger side chain may also be at least one residue from a carboxylic acid. The residues of this larger side chain may also be at least one residue from a diamine. The residue of this larger side chain may also have at least one residue from a carboxylic acid and at least one residue from a diamine. Moreover, the third feature is that a part or all of the hydrogen atoms of the amine bond (-CONH-) may be replaced with a monovalent organic group. In the following description, the polyamidoamine-iminomine of the present invention is collectively referred to as N-substituted polyamidoamine-iminomine. 591056 ----------- 9825 pifl Ο

(1-1)

(1-2)

T1 in formula (1-1) refers to an organic residue derived from a tricarboxylic acid. T2 in formula (1-2) refers to an organic residue derived from a dicarboxylic acid. T3 in formula (1-3) means an organic residue derived from a tetracarboxylic acid. D1 to D3 refer to so-called diamine-derived organic groups. The term "dicarboxylic acids" used in the present invention is a general term including dicarboxylic acids, dicarboxylic anhydrides, and oxyhalo compounds of dicarboxylic acids. Tricarboxylic acids and tetracarboxylic acids have the same meaning. The polyvalent carboxylic acids are a general term for dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids. These polyvalent carboxylic acids may also belong to aromatic systems (containing heterocyclic rings), alicyclic systems (containing heterocyclic rings), and aliphatic systems (non-cyclic). In addition, the polyvalent carboxylic acids having a cyclic structure can maintain good liquid crystal alignment. Therefore, when using aliphatic (non-cyclic) materials, this ring or aromatic system can be used at the same time, and the amount used can be controlled within a range that will not adversely affect the liquid crystal alignment. In addition, τ1 to τ3 are preferably those having a structure that does not contain general groups such as ether, ester, thioether, and thioester. 19 591056 9825 pif 1 structure. The reason is that such groups are the cause of the decrease in the electrical characteristics of the liquid crystal display element. However, even with the aforementioned structure, there is no problem as long as it does not affect the electrical characteristics. Examples of the dicarboxylic acids used in the present invention can be divided into aliphatic dicarboxylic acids, alicyclic dicarboxylic acids and aromatic dicarboxylic acids. The details are shown below. 0 Aliphatic dicarboxylic acids are, for example, malonic dihalides. Product, oxalic acid dihalide, dimethylmalonic acid dihalide, succinic acid dihalide, trans-butenedioic acid dihalide, glutaric acid dihalide, adipic acid dihalide, adipate Diene dihalide, 2-methyladipate dihalide, trimethyladipate dihalide, pimelic acid dihalide, 2,2-dimethylglutarate dihalide, 3 , 3-diethylsuccinic acid dihalide, azelaic acid dihalide, sebacic acid dihalide, suberic acid dihalide, and the like. The alicyclic dicarboxylic acid is, for example, 1,1-cyclopropanedicarboxylic acid dihalide, 1,2-cyclopropanedicarboxylic acid dihalide, 1,1-cyclobutanedicarboxylic acid dihalide, 1, 2-cyclobutanedicarboxylic acid dihalide, 1,3-cyclobutanedicarboxylic acid dihalide, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid dihalide, 2, 4-diphenyl-1,3-cyclobutanedicarboxylic acid dihalide, 3,4-bis (hydroxyphenyl) -1,2-cyclobutanedicarboxylic acid dihalide, 2,4-bis (Hydroxyphenyl) -1,3-cyclobutanedicarboxylic acid dihalide, 1-cyclobutene-1,2-dicarboxylic acid dihalide, 1-cyclobutene-3,4-dicarboxylic acid Dihalide, 1,1-cyclopentanedicarboxylic acid dihalide, 1,2-cyclopentanedicarboxylic acid dihalide, 1,3-cyclopentanedicarboxylic acid dihalide, 1,1- Cyclohexanedicarboxylic acid dihalide, 1,2-cyclohexanedicarboxylic acid dihalide, 1,3-cyclohexanedicarboxylic acid dihalide, M-cyclohexanedicarboxylic acid dihalide, 1,4- (2-bicycloheptene) dicarboxylic acid 20 591056 9825 pif 1 acid dihalide, dicycloheptene-2,3-dicarboxylic acid dihalide, bicyclo [2.2.2] octane- M-dicarboxylic acid dihalide, bicyclo [2.2.2] octane-2,3-di Carboxylic acid dihalide, 2,5-dioxo-1,4-bicyclo [2.2.2] octane dicarboxylic acid dihalide, 1,3-adamantane dicarboxylic acid dihalide, 4,8 -Dioxo-1,3-adamantane dicarboxylic acid dihalide, 2,6-spiro [3.3] heptane dicarboxylic acid dihalide, 1,3-adamantane diacetic acid dihalide, camphoric acid dihalide Halides, etc. Aromatic dicarboxylic acids are, for example, phthalic acid dihalide, isophthalic acid dihalide, terephthalic acid dihalide, 5-methylisophthalic acid 0 dihalide, 5-tert-butyl Diisophthalic acid dihalide, 5-aminoisophthalic acid dihalide, 5-hydroxyisophthalic acid dihalide, 2,5-dimethylterephthalic acid dihalide, tetramethylparahalide Phthalic acid dihalide, 1,4-naphthalenedicarboxylic acid dihalide, 2,5-naphthalenedicarboxylic acid dihalide, 2,6-naphthalenedicarboxylic acid dihalide, 2,7-naphthalenedicarboxylic acid Acid dihalide, 1,4-anthracene dicarboxylic acid dihalide, 1,4-anthraquinone dicarboxylic acid dihalide, 2,5-biphenyldicarboxylic acid dihalide, 4,4'-biphenyl Dicarboxylic acid dihalides, 1,5-biphenylene dicarboxylic acid dihalides, 4,4 "-biphenyldicarboxylic acid dihalides, 4,4'-diphenylmethanedicarboxylic acid dihalides Compounds, 4,4'-diphenylethanedicarboxylic acid dihalides, 4,4-diphenylpropanedicarboxylic acid dihalides, 4,4'-diphenylhexafluoropropanedicarboxylic acid bis Halide, 4,4'-diphenyl ether dicarboxylic acid dihalide, 4,4'-bibenzyl dicarboxylic acid dihalide, 4,4'-stilbene Acid dihalide, 4,4'-diphenylacetylene dicarboxylic acid dihalide, 4,4'-carbonyldi'benzoic acid dihalide, 4,4'-thithiodibenzoic acid dihalide, 4, 4'-dithiodibenzoic acid dihalide, terephthalic acid dihalide, 3,3'-terephthalic acid dihalide, 4-carboxycinnamic acid dihalide, terephthalic acid dihalide Compounds, 3,3 '-(4,4'-(methylene diphenylene)) dipropionate dihalide, 4,4'- 21 591056 (WipMIU y ,, 9825 pifl (4,4 '· (hydroxyl Di-p-benzene)) dipropionate dihalide, 4,4, _ (4,4,-(hydroxydi-p-phenylene)) dibutyric acid dihalide, (isopropylidene diphenylene dihydroxy) dibutyric acid Dihalides, bis (p-carboxyl) dimethylsilane, 1,5- (9-oxofluorene) dihalide dihalides, 3,4-pyrano diresidue dihalides, 4,5-thiazoles Di-residual acid dihalide, 2-phenyl-4,5-thiazoledicarboxylic acid dihalide, thiadiazole-3,4-dicarboxylic acid dihalide, 1,2,5-oxadiazole_3 2,4-dicarboxylic acid dihalide, 2,3-pyrazine dicarboxylic acid dihalide, 2,4-pyrazine dicarboxylic acid dihalide, 2,5-pyrazine diresidic acid dihalide, 2 , 6-pyrazine dicarboxylate Acid dihalide, 3,4-pyrazinedicarboxylic acid dihalide, 3,5-pyrazinedicarboxylic acid dihalide, 3,6-pyridinedicarboxylic acid dihalide, etc. Used in the present invention Dicarboxylic acids are not limited to the dicarboxylic acid dihalides described above. When T2 is a substance that provides this organic residue, dicarboxylic acid derivatives other than dihalides can also be used. Here, dicarboxylic acid derivatives For example, the active fluorenyl derivative. For example, the dihalide of the dicarboxylic acid dihalide can be replaced by ethenyloxy, alkyloxy, phenyloxy or phenylthio. Dicarboxylic acid derivatives and the like. Furthermore, not only derivatives but also other dicarboxylic acids (compounds having 2 -COOH) can be used. In addition, in order to avoid affecting the alignment of the liquid crystal, the dicarboxylic acids used in the present invention are preferably a dicarboxylic acid having a linear structure of polyamidamine-imideneamine. The preferred dicarboxylic acids are, for example, 1,4-cyclohexanedicarboxylic acid dihalide, terephthalic acid dihalide, isophthalic acid dihalide, pyrazinedicarboxylic acid dihalide, naphthalenedicarboxylic acid. Acid dihalide, 1,4-anthracene dicarboxylic acid dihalide, 4,4'-biphenyldicarboxylic acid dihalide, 4,4 "-tert-benzenedicarboxylic acid dihalide, 4,4 ' -Diphenylmethanedicarboxylic acid dihalide, 4,4'-diphenylethane 22 591056 9825 pifl dicarboxylic acid dihalide, 4,4'-diphenylpropanedicarboxylic acid dihalide, 4,4 ' -Diphenylhexafluoropropane dicarboxylic acid dihalide, 4'-diphenyl ether dicarboxylic acid dihalide, etc. Compounds which can give the same residues as such compounds can also be used. Dicarboxylic acid derivatives other than substances. In addition, for the purpose of improving the adhesion between polyamidoamine and iminomine to the substrate, the polysiloxane of formula (6) may be used instead. A carboxylic acid dihalide or an active fluorenyl derivative other than an acid dihalide which can give the same residue. In this case, a compound in which X in formula (6) is replaced with hydrogen may also be used.

记 The symbols shown in formula (6) are defined as follows. R9 and R1Q refer to each independently methyl, ethyl, phenyl, or cyclohexyl. X refers to halogen. V, W, and X refer to independent integers of 1 to 5.

The N-substituted polyamidoamine-iminomine system of the present invention has at least one large side chain residue. Moreover, when using such $ N to replace polyhedral and iminoamine, it is possible to obtain a low-value __ compound_ in liquid crystal. The residue of the side bond of the thief can also be guided by the three miscellaneous double-painted objects shown by the formula. Can be given to Chi_ 的 残 _ 化合 _ can be used instead of acid _ ^ dents _ Yan_. Furthermore, a compound in which X in the foregoing formula is replaced with hydrogen may be used instead. 23 591056 9825 pifl X-^-\ x ^ Rn ⑺ x—οΛ == /

II ο In formula (7), the bonding position of -COX with respect to the benzene ring is arbitrary. The symbols in this formula are defined as follows. The symbols in the formula (7) are defined as follows. X6 means a single bond, -0_, -COO-, _OCO_, -NH-, -NHCO-, -CONH-, -S_ or an alkylene group having 1 to 6 carbon atoms. X means halogen, preferably chlorine or bromine. R11 means an alkyl group having 3 to 20 carbon atoms, a fluoroalkyl group having 3 to 20 carbon atoms, or a nested group having a substituent. Nesting skeletons are, for example, biliary, basal, β-biliary, epistasal, Ergosteryl, estrogen, 11α-mesomethyl, 11α luteal nest, wool nest, Methyltestostery.

Norethisteryl, gestational base, β-granular base, ugly nest base, Testosteryl, cholicol acetate

In formula (8), the bonding position of -C0X with respect to the benzene ring is arbitrary. The symbols in this formula are defined as follows. R12 and R13 refer to individual alkyl groups having 1 to 12 carbon atoms, and the total carbon number of R12 and R13 is 4 or more. X means halogen, preferably chlorine or bromine. The dibasic acids used in the present invention are not limited to the above compounds as 24 591056 9825 pif 1, and two or more of the foregoing compounds may be used in combination. Next, the tricarboxylic acids used in the present invention will be described.

In each of the above formulae, X means halogen, preferably chlorine or bromine. The tricarboxylic acid used to produce the N-substituted polyamidoamine-iminomine of the present invention need only be a compound that gives this organic residue in T1, so the above-mentioned tricarboxylic acid anhydride halide is not used as limit. In addition, active fluorenyl derivatives other than halides can also be used, examples of which are trivalent carboxylic acid anhydride halides. Halogen substitutes can be replaced with ethenyloxy, alkyloxy, phenyloxy 25 9825 pif 1 or a tricarboxylic acid derivative obtained by combining groups such as phenylthio. Furthermore, it is also possible to use a compound in which two carboxyl groups of the tricarboxylic acid are dehydration-polymerized anhydride structures and the remaining one is a carboxyl-only compound or a compound containing a tricarboxylic acid (a compound having 3 -COOH). Among them, trimellitic anhydride halide of the formula (9) is preferably used. The tricarboxylic acids may be used in combination of two or more of the aforementioned compounds. Some examples of the tetracarboxylic acids used in the present invention can be divided into alicyclic tetracarboxylic acids, aliphatic tetracarboxylic acids, and aromatic tetracarboxylic acids. The details are shown below. The alicyclic tetracarboxylic acids are, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5,6 -Cyclohexanetetracarboxylic diacid anhydride, bicyclo (2,2,2) -octyl olefin-2,3,5,6-tetracarboxylic diacid anhydride 3,3'-bibicyclohexane-1, 1 ', 2,2'-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydrofuranylidene) -3-form Methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, 1,3,3 &, 4,5,91) -hexahydro-5- (tetrahydro-2,5_ — ^ oxo-3 -Pyranyl) -naphthalene [l, 2, -c] -pyran-1,3-monofluorene, 3,5,6-tri-n-bicycloheptane-2-acetic anhydride, 2,3,4 , 5-tetrahydrofurantetracarboxylic dianhydride and the like. In addition, a compound substituted with a lower alkyl group such as a methyl group, an ethyl group, or the like which is partially bonded to the hydrogen of the ring of the compound may be used. The aliphatic tetracarboxylic acids are, for example, ethylene tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, pentane tetracarboxylic acid dianhydride, hexanetetracarboxylic acid dianhydride, heptane tetracarboxylic acid dianhydride, and the like. Aromatic tetracarboxylic acids are, for example, pyromellitic acid dianhydride, 26 591056 9825 pif 1 3,3 ', 4,4'-diphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-phenylhydrazone Pyromellitic acid dianhydride, 2,3,6,7-naphthoic acid dianhydride, 3,3 ', 4,4'-biphenylmethylenetetracarboxylic dianhydride, 3,3', 4,4'-bi Phenyl ether tetracarboxylic acid anhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic acid anhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl Sulfide diacid anhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylmaphenic anhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane Dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylsulfinic acid anhydride, terephthalic acid (triphenylterephthalic acid) Acid anhydride, m-benzenebis (triphenylterephthalic acid) diacid anhydride, bis (triphenylterephthalic acid) _4,4'_diphenyl ether diacid anhydride, bis (triphenylterephthalic acid) _4 , 4'_diphenylmethane dianhydride and so on. Among the above-mentioned preferred tetracarboxylic acids are cyclobutanetetracarboxylic acid anhydride, cyclopentanetetracarboxylic acid anhydride, tricarboxycyclopentylacetic acid anhydride, cyclohexanetetracarboxylic acid anhydride, butanetetracarboxylic acid. Dianhydride, and pyromellitic dianhydride. The tetracarboxylic acid used to produce the N-substituted polyamidoamine-iminomine of the present invention need only be a compound that gives this organic residue in T2, so it is not limited to the tetracarboxylic dianhydride described above. That is, tetracarboxylic acids other than dianhydride may be used. One example of this is the dehydration condensation of two carboxyl groups in a tetracarboxylic acid to an anhydride and the hydrogen of the remaining carboxyl group is halogen, ethoxyl, alkyloxy, phenyloxy, or phenylsulfide. Derivatives substituted with a base. A further example is a derivative in which all hydrogens of four carboxyl groups in a tetracarboxylic acid are replaced with a group such as' halogen, ethenyloxy, alkyloxy, phenyloxy, or phenylthio. What's more, not only derivatives but also substances containing tetracarboxylic acids (compounds having 4 -COOH). It is also possible to use a combination of two or more substances containing the aforementioned tetracarboxylic acids. 27 9825 pif 1 In the present invention, the N-substituted polyamidoamine-iminomine system has at least one large side chain residue. The residue of the larger side chain may be an organic residue derived from a carboxylic acid, or may be It is an organic residue derived from a diamine, or both. That is, the polyfluorene is replaced by N containing the structural unit (1-1) and not including the structural unit (1-2) and the structural unit (1-3). In the amine-iminomine, at least one of T1 and D1 has a residue having a large side chain. Further, it is preferably a residue with a large side chain of D1, and moreover, T1 and D1 may be at the same time. Residues with larger side chains. Among N-substituted polyamido-amidoamines containing the structural unit (1-1) and the structural unit (1-2), at least one of T1, T2, D1, and D2 must have Residues with larger side chains. Moreover, it is preferred that at least one of D1 and D2 has a residue with a larger side chain. Furthermore, when at least one of D1 and D2 is In the case of a residue having a larger side chain, T2 also has a residue of a larger side chain. In the N-substituted polyamidamine-sulfuronamine containing the structural unit (1-1) and the structural unit (1-3), At least one of T1, T3, D1, and D3 must have a residue with a large side chain. Further, it is preferably a residue with at least one of D1 and D3 having a large side chain. The structural unit (1-2) is included. In the N-substituted polyamido-iminomine of the structural unit (1-3), at least one of T2, T3, D2, and D3 must have a residue having a large side chain. Moreover, it is preferably D2 and D3. At least one residue with a larger side chain. Furthermore, when at least one of D2 and D3 has a residue with a larger side chain, T2 also has a residue with a larger side chain. 1) In the structural unit (1-2) and the N-substituted polyamidoamine-iminomine of the structural unit (1-3), at least one of T1, T2, T3, D1, D2, and D3 is required. 28 591056- 9825 pifl Residues having larger side chains. Furthermore, it is preferable that at least one of D1 to D3 has a residue having a large side chain. Furthermore, when at least one of D1 to D3 has a residue having a large side chain , T2 also has Residues with larger side chains. The diamine compounds used in the production of the N-substituted polyamidoamines and sulfoximines of the present invention are also the same as the aforementioned carboxylic acids, and can be classified as aromatic (including heterocyclic) and alicyclic (Including heterocyclic), aliphatic (non-cyclic), etc. In addition, in order to maintain good liquid crystal alignment, a diamine φ compound having a ring structure is preferred. This diamine compound is generally preferred It is a substance having a structure that does not contain general groups such as ether, ester, thioether, and thioester in the structure. The reason is that such groups are the cause of lowering the electrical characteristics of the liquid crystal display element. However, even with the aforementioned structure, there is no problem as long as it does not affect the electrical characteristics. When the N-substituted polyamidoamine-iminomine of the present invention is produced, in the case where the carboxylic acid used is a residue capable of providing a large side chain, a diamine compound having no side chain can be used. However, it is preferred to use both a carboxylic acid having a side chain group having a carbon number of 3 · or more and a diamine compound having a side chain group having a carbon number of 3 or more. Furthermore, when a carboxylic acid having a side chain with a carbon number of 3 or more is not used, it is necessary to use a diamine compound having a side chain with a carbon number of 3 or more. In this case, the side chain group having a carbon number of 3 or more is, for example, an aliphatic hydrocarbon group, a hydrocarbon group containing an alicyclic structure, an aromatic hydrocarbon group, a group having a siloxane group, A group having a nested skeleton or a side chain group mixed with the aforementioned structure. An alicyclic hydrocarbon group or an aromatic group 29 591056 9825 pifl A hydrocarbon group may have a substituent such as an alkyl group, an alkoxy group, a halogen, or 0H. Part of this type of hydrocarbon structure can also be replaced with other atoms such as oxygen. However, it is preferable not to contain groups such as -S-, -CO ·, -COO-, or -SOO-. When the carbon number of the side chain group includes a cyclic structure such as cyclohexane, it means the number of carbons constituting the ring. Preferred examples of the diamine compound having a side chain group having a carbon number of 3 or more are compounds capable of providing the organic residues represented by the formulas (2) to (5), respectively. Such compounds are preferably used in the production of the N-substituted polyamidoamines of the present invention. Furthermore, in the N-substituted polyamidoamine-iminomine of the present invention, it is preferable that the residue contains at least one residue selected from the group of organic residues.

The symbols used in the formula (2) are defined as follows. R4 means hydrogen or an alkyl group having 1 to 12 carbon atoms. Ring A refers to 1,4-phenylene or 1,4-cyclohexylene. Arbitrary hydrogen in the ring may be substituted with an alkyl group having 1 to 4 carbon atoms. Z1 and Z2 are independent single bonds, -CH2_, -CH2CH2- or -0. Γ is an integer of 0 to 3, s is an integer of 0 to 5, tl is an integer of 0 to 3, and t2 is an integer of 0 to 3. However, when tl is 2 or 3, a plurality of Z1 may be the same as each other, or may be different from each other. When t2 is 2 or 3, a plurality of Z2 may be the same as each other or different from each other. (3) 12 2 5

G-X-G-R In formula (3), for the bonding position of the substituent in the benzene ring and two positions

The position of the radical is arbitrary. The symbols in this formula are defined as follows. X1 and X2 are individually independent single bonds, -0-, -00-, -OCO-, _NH_, _CONH · or alkylenes having 1 to 12 carbon atoms. G1 and G2 are individually independent single bonds or divalent groups containing 1 to 3 rings. The ring system is selected from the group consisting of an aromatic ring and an alicyclic ring. R5 means hydrogen, fluorine, -CN, -OH, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbons. However, when G2 is a single bond and X2 is not a single bond or an alkylene group, R5 is hydrogen or an alkyl group. When G1 and G2 are both single bonds, the total carbon number of X1, X2 and R5 is 3 or more. 6

In formula (4), any hydrogen of 1,4-phenylene may be replaced with an alkyl group having 1 to 4 carbon atoms. The symbols in this formula are defined as follows. X3 and X4 are independent single bonds, -CH2-, -CH2CH2 ·, or -〇-. r6 and R7 are each independently hydrogen, an alkyl group having 1 to 12 carbons, or a fluoroalkyl group having 1 to 12 carbons. ul and u2 are independent integers of 0 to 3. 31 591056 However, at least one of R6 and R7 is an alkyl group having 3 or more carbon atoms or a fluoroalkyl group having 3 or more carbon atoms. When ul is 2 or 3, multiple X3s may be the same as each other or different from each other. When u2 is 2 or 3, a plurality of X4 may be the same as each other, or may be different from each other.

In formula (5), the spring position with respect to the bonding position of the substituent and the radical of the benzene ring is arbitrary. The symbols in this formula are defined as follows. R8 is hydrogen or an alkyl group having 1 to 12 carbon atoms. Any -CH2- in this alkyl group may be replaced with 0-. X5 refers to a single bond or an alkylene group having 1 to 5 carbon atoms. Any -CH2- in this alkylene can be replaced with -0_. m is an integer of 0 to 3, and η is an integer of 1 to 5. The diamine compound capable of giving an organic residue represented by the formula (2) is represented by the formula (17).

In Formula (17), R4, a, Z1, Z2, r, s, tl, and t2 are the same as the symbols shown in Formula (2), respectively. Part of the specific examples of the diamine compound shown in this formula (17) is obtained by a combination of R, ring A, Z, r, s, and t, as shown in Tables 1 to 5. 32 591056 9825 pifl and ‘Z1 = Z2 = Z’ tl = t2 = t. In addition, in the column of ring A in this table, B represents 1,4-phenylene, and Ch represents 1,4-cyclohexene. 33 591056 9825 pif 1 Table 1

No · R4 AZ rst 1 H 0 0 2 ch3 0 0 3 C2H5 0 0 4 11-C3H7 0 0 5 11-C4H9 0 0 6 n-CsHn 0 0 7 n-C6H13 0 0 8 11-C7H15 0 0 9 n- CgHis 0 0 10 11-C9H19 0 0 11 11-C10H21 0 0 12 11-C11H23 0 0 13 11-C12H25 0 0 14 H Ch 1 0 0 15 ch3 Ch 1 0 0 16 c2h5 Ch 1 0 0 17 n-C3H7 Ch 1 0 0 18 11-C4H9 Ch 1 0 0 19 11-C5H11 Ch 1 0 0 20 η-〇6Ηΐ3 Ch 1 0 0 21 11-C7H15 Ch 1 0 0 22 η-〇8Ηΐ8 Ch 1 0 0 23 11-C9H19 Ch 1 0 0 24 n-Ci〇H2i Ch 1 0 0 25 11-C11H23 Ch 1 0 0 26 n-Ci2H25 Ch 1 0 0 27 HB 1 0 0 28 ch3 B 1 0 0 29 C2H5 B 1 0 0 30 11-C3H7 B 1 0 0 31 11-C4H9 B 1 0 0 32 n-C5Hu B 1 0 0 33 n-C6Hi3 B 1 0 0 34 11-C7H15 B 1 0 0 35 η-〇δΗΐ8 B 1 0 0 36 11-C9H19 B 1 0 0 37 n-C10H21 B 1 0 0 38 11-C11H23 B 1 0 0 39 11-C12H25 B 1 0 0 34 591056 9825 pifl Table 2

No. R4 AZ rst 1 H Ch 1 1 0 2 ch3 Ch 1 1 0 3 C2H5 Ch 1 1 0 4 11-C3H7 Ch 1 1 0 5 n-C4H9 Ch 1 1 0 6 Π-〇5Ηι Ch 1 1 0 7 n -C6Hi3 Ch 1 1 0 8 I1-C7H15 Ch 1 1 0 9 n-CgHi8 Ch 1 1 0 10 11-C9H19 Ch 1 1 0 11 11-C10H21 Ch 1 1 0 12 11-C11H23 Ch 1 1 0 13 11-C12H25 Ch 1 1 0 14 HB 1 0 15 ch3 B 1 1 0 16 C2H5 B 1 1 0 17 11-C3H7 B 1 1 0 18 11-C4H9 B 1 1 0 19 11-C5H11 B 1 1 0 20 n-C6H13 B 1 1 0 21 11-C7H15 B 1 1 0 22 n-CgHis B 1 1 0 23 11-C9H19 B 1 1 0 24 11-C10H21 B 1 1 0 25 11-C11H23 B 1 1 0 26 11-C12H25 B 1 1 0 27 H 0 0 1 28 ch3 0 0 1 29 C2H5 0 0 1 30 11-C3H7 0 0 1 31 11-C4H9 0 0 1 32 n-CsHu 0 0 1 33 n-C6H13 0 0 1 34 11-C7H15 0 0 1 35 η-ΟδΗΐδ 0 0 1 36 11-C9H19 0 0 1 37 n-Ci〇H2i 0 0 1 38 11-C11H23 0 0 1 39 11-C12H25 0 0 1 35 591056 9825 pif 1 Table 3

No. R4 AZ Γ st 1 H Ch 0 1 0 1 2 ch3 Ch 0 1 0 1 3 C2H5 Ch 0 1 0 1 4 11-C3H7 Ch 0 1 0 1 5 n-C4H9 Ch 0 1 0 1 6 n-C5Hn Ch 0 1 0 1 7 n-C6H13 Ch 0 1 0 1 8 n-CyHis Ch 0 1 0 1 9 n-C8Hi8 Ch 0 1 0 1 10 11-C9H19 Ch 0 1 0 1 11 n-Ci〇H2i Ch 0 1 0 1 12 11-C11H23 Ch 0 1 0 1 13 11-C12H25 Ch 0 1 0 1 14 H Ch 0 1 2 1 15 ch3 Ch 0 1 2 1 16 C2H5 Ch 0 1 2 1 17 n-C3H7 Ch 0 1 2 1 18 11-C4H9 Ch 0 1 2 1 19 n-C5Hn Ch 0 1 2 1 20 n-CeHn Ch 0 1 2 1 21 11-C7H15 Ch 0 1 2 1 22 η-〇8Ηΐ8 Ch 0 1 2 1 23 11-C9H19 Ch 0 1 2 1 24 n-Ci〇H2i Ch 0 1 2 1 25 11-C11H23 Ch 0 1 2 1 26 11-C12H25 Ch 0 1 2 1 27 HB 0 1 0 1 28 ch3 B 0 1 0 1 29 C2H5 B 0 1 0 1 30 11-C3H7 B 0 1 0 1 31 n-C4H9 B 0 1 0 1 32 11-C5H11 B 0 1 0 1 33 n-C6H13 B 0 1 0 1 34 11-C7H15 B 0 1 0 1 35 η -〇δΗΐ8 B 0 1 0 1 36 11-C9H19 B 0 1 0 1 37 n-Ci〇H2i B 〇1 0 1 38 11-C11H23 B 0 1 0 1 39 n-Ci2H25 B 0 1 0 1 36 591056

9825 pif 1 Table 4

No. R4 AZ rst 1 H ch2 0 1 2 ch3 ch2 0 1 3 C2H5 ch2 0 1 4 11-C3H7 ch2 0 1 5 11-C4H9 ch2 0 1 6 11-C5H11 ch2 0 1 7 n-C6Hi3 ch2 0 1 8 11 -C7H15 ch2 0 1 9 η-ΟδΗΐδ ch2 0 1 10 11-C9H19 ch2 0 1 11 n-Ci〇H2i ch2 0 1 12 n-CuH23 ch2 0 1 13 11-C12H25 ch2 0 1 14 H Ch ch2 1 0 1 15 ch3 Ch ch2 1 0 1 16 C2H5 Ch ch2 1 0 1 17 n-C3H7 Ch ch2 1 0 1 18 11-C4H9 Ch ch2 1 0 1 19 11-C5H11 Ch ch2 1 0 1 20 n-CeHn Ch ch2 1 0 1 21 11-C7H15 Ch ch2 1 0 1 22 η-〇8Ηΐ8 Ch ch2 1 0 1 23 11-C9H19 Ch ch2 1 0 1 24 n-Ci〇H2i Ch ch2 1 0 1 25 n-CnH23 Ch ch2 1 0 1 26 tl- Ci2H25 Ch ch2 1 0 1 27 H Ch ch2 1 2 1 28 ch3 Ch ch2 1 2 1 29 C2H5 Ch ch2 1 2 1 30 11-C3H7 Ch ch2 1 2 1 31 11-C4H9 Ch ch2 1 2 1 32 n-C5Hn Ch ch2 1 2 1 33 n-C6H13 Ch ch2 1 2 1 34 n-C7H15 Ch ch2 1 2 1 35 n-CgHis Ch ch2 1 2 1 36 11-C9H19 Ch ch2 1 2 1 37 n-Ci〇H2i Ch ch2 1 2 1 38 11-C11H23 Ch ch2 1 2 1 39 11-C12H25 Ch ch2 1 2 1 37 591056 9825 pif 1 Table 5

No. R4 AZ Γ st 1 Η B ch2 1 0 1 2 ch3 B ch2 1 0 1 3 C2H5 B ch2 1 0 1 4 11-C3H7 B ch2 1 0 1 5 n-C4H9 B ch2 1 0 1 6 n-CsHn B ch2 1 0 1 7 n-C6Hi3 B ch2 1 0 1 8 11-C7H15 B ch2 1 0 1 9 n-C8Hi8 B ch2 1 0 1 10 11-C9H19 B ch2 1 0 1 11 n-Ci〇H2i B ch2 1 0 1 12 n-CnH23 B ch2 1 0 1 13 n-Ci2H25 B ch2 1 0 1 14 HB ch2 1 ^ 1 1 15 ch3 B ch2 1 1 1 16 C2H5 B ch2 1 1 1 17 11-C3H7 B ch2 1 1 1 18 11-C4H9 B ch2 1 1 1 19 n-CsHn B ch2 1 1 1 20 11-C6H13 B ch2 1 1 1 21 11-C7H15 B ch2 1 1 1 22 n-CgHis B ch2 1 1 1 23 11-C9H19 B ch2 1 1 1 24 11-C10H21 B ch2 1 1 1 25 11-C11H23 B ch2 1 1 1 26 11-C12H25 B ch2 1 1 1 The diamine compound represented by formula (Π) is not the compound shown in the above example as limit. Two or more of the above compounds may be used in combination. In such a diamine compound, when r is 0 and R4 is hydrogen or a short-chain alkyl group, a liquid crystal alignment film having a slightly smaller forward tilt angle on the liquid crystal can be imparted. When r is 1 to 3 and R4 is hydrogen, a liquid crystal alignment film having a large forward tilt angle on the liquid crystal can be given. A liquid crystal alignment film having a small front tilt angle is more suitable for an IPS type liquid crystal display element. A liquid crystal alignment film having an inclination angle of 3 to 8 degrees is more suitable for a TN type liquid crystal display element. Furthermore, in the case of STN-type liquid crystal display elements, VA-type liquid crystal display elements and 0CB-type liquid crystal 38 9825 pif 1 display elements, since a larger forward tilt angle is required, it is preferable to use a side chain group in this case. Longer diamine compound. Alternatively, a diamine compound having a side chain group having a carbon number of 3 or more represented by the formula (18), the formula (19), and the formula (20) may be used instead. 39 591056 9825 pif 1

(18)

(19) In this formula, z1, Z2, tl, and t2 are the same as the symbols shown in formula (2), respectively. R14 and R15 are each independently hydrogen or an alkyl group having 1 to 12 40 591056 9825 pifl. However, any ring in the nest skeleton of the formulas (18) and (19) may be a material that shrinks, expands, or opens the ring, or may be a bicyclic ring, or an unsaturated bond may be added at any position The reduced or reduced substance may be one in which hydrogen or an alkyl group at any position is replaced with another monovalent organic group. The diamine compound capable of giving an organic residue represented by the formula (3) is represented by the formula (21).

In the formula (21), X1, X2, G1, G2, and R5 are the same as the symbols shown in the formula (3), respectively. Part of the specific examples of the diamine compound represented by the formula (21) is obtained by a combination of χ1, Gi, G2, and R5, as shown in Tables 6 to 12. In this table, "-" means a single bond, "B" means 1,4-phenylene, and "Ch" means I, 4-cyclohexyl. In addition, "B-Ch", "Ch-B", "B-Ch_Ch", etc. represent the kind of ring and the order of bonding. For example, when G1 is B_Ch, it means that they are not bonded in the order of χ1, U4 · phenylene, 1,4-cyclohexane, and X2. When G2 is Ch-B, it means that they are bonded in the order of X2, 1,4-cyclohexene, i, phenylene, and R5. The compounds described in this table are 1,3-diaminebenzene derivatives, and X1 is a diamine compound bonded to the fifth position of diaminebenzene. 41 591056 9825 pif 1 Table 6

No. X1 Gl X " Gl R5 1----n-CsHn 2---n-Ci2H25 3---11-C5H11 4----11-C12H25 5 0---n-CsHn 6 0-- -Il-Ci2H25 7 0---n-CsHn 8 0---11-C12H25 9 co-o----11-C5H11 10 co-o---11-C12H25 11 co-o---n-CsHn 12 co-o---11-C12H25 13 o-co--n-C5Hn 14 o-co---11-C12H25 15 o-co---n-C5Hu 16 o-co---11-C12H25 17 NH---n-C5Hu 18 NH---11-C12H25 19 NH---n-C5Hu 20 NH---11-C12H25 21 CO-NH---11-C5H11 22 CO-NH---11- C12H25 23 CO-NH---n-C5Hn 24 CO-NH---n-Ci2H25 25-B--n-CsHn 26-B--11-C12H25 27-Ch--n-CsHn 28-Ch-- 11-C12H25 29-BB--n-CsHn 30-BB--11-C12H25 31-B-Ch--n-CsHn 32-B-Ch--11-C12H25 33-Ch-B--n-CsHn 34 -Ch-B--n-Ci2H25 35-Ch-Ch--n-C5Hn 36-Ch-Ch--11-C12H25 37-BBB--n-C5Hu 38-BBB--11-C12H25 42 591056 9825 pifl table 7

No. X1 G1 X2 G2 R, 1-BB-Ch--n-CsHn 2-BB-Ch--11-C12H25 3-B-Ch-Ch--n-CsHn 4-B-Ch-Ch--11 -C12H25 5-Ch-Ch-Ch--n-CsHn 6-Ch-Ch-Ch--11-C12H25 7 0 B--11-C5H11 8 0 B-11-C12H25 9 0 Ch-n-C5Hu 10 0 Ch--Il-Ci2H25 11 0 BB--11-C5H11 12 0 BB--11-C12H25 13 0 B-Ch-11-C5H11 14 0 B-Ch--11-C12H25 15 0 Ch-B--n- CsHn 16 0 Ch-B--n-Ci2H25 17 0 Ch-Ch--11-C5H11 18 0 Ch-Ch--I1-C12H25 19 0 BBB--n-CsHn 20 0 BBB--11-C12H25 21 0 BB -Ch--n-CsHn 22 0 BB-Ch--11-C12H25 23 0 B-Ch-Ch--n-CsHn 24 0 B-Ch-Ch--11-C12H25 25 0 Ch-Ch-Ch-- 11-C5H11 26 0 Ch-Ch-Ch--11-C12H25 27 co-o B--11-C5H11 28 co-o B--n-Ci2H25 29 co-o Ch--I1-C5H11 30 co-o Ch --11-C12H25 31 co-o BB--n-CsH ,, 32 co-o BB--11-C12H25 33 co-o B-Ch--n-CsHn 34 co-o B-Ch--11- C12H25 35 co-o Ch-B--n-C5Hu 36 co-o Ch-B--11-C12H25 37 co-o Ch-Ch--n-C5Hn 38 co-o Ch-Ch--n-Ci2H25 43 591056 9825 pif 1 Table 8

No. X1 G1 X " G2 R " 1 co-o BBB--n-CsHn 2 co-o BBB--Il-Ci2H25 3 co-o BB-Ch--11-C5H11 4 co-o BB-Ch-- n-Ci2H25 5 co-o B-Ch-Ch--n-CsHn 6 co-o B-Ch-Ch--11-C12H25 7 co-o Ch-Ch-Ch--n-C5Hu 8 co-o Ch -Ch-Ch--11-C12H25 9 ch2 B--n-CsHn 10 ch2 B--11-C12H25 11 ch2 Ch--n-C5Hn 12 ch2 Ch-〆11-C12H25 13 ch2 BB--n-C5Hu 14 ch2 BB--n-Ci2H25 15 ch2 B-Ch--n-C5Hu 16 ch2 B-Ch--11-C12H25 17 ch2 Ch-B--n-CsHn 18 ch2 Ch-B--11-C12H25 19 ch2 Ch -Ch--11-C5H11 20 ch2 Ch-Ch--11-C12H25 21 ch2 BBB--n-CsHn 22 ch2 BBB--II-C12H25 23 ch2 BB-Ch-n-CsHn 24 ch2 BB-Ch--n -Ci2H25 25 ch2 B-Ch-Ch--26 ch2 B-Ch-Ch--11-C12H25 27 ch2 Ch-Ch-Ch--n-C5Hn 28 ch2 Ch-Ch-Ch--11-C12H25 29 0- CH2CH2 B n-CsHn 30 0-CH2CH2 B 11-C12H25 31 0-CH2CH2 Ch n-C5Hu 32 0-CH2CH2 Ch 11-C12H25 33 0-CH2CH2 BB n-C5Hn 34 0-CH2CH2 BB 11-C12H25 35 0-CH2CH2 B -Ch n-C5Hn 36 0-CH2CH2 B-Ch 11-C12H25 37 0-CH2CH2 C h-B n-CsHn 38 0-CH2CH2 Ch-B 11-C12H25 44 591056 9825 pif 1 Table 9

No. X1 Gl G " R, 1 0-CH2CH2 Ch-Ch n-CsHn 2 0-CH2CH2 Ch-Ch 11-C12H25 3 0-CH2CH2 BBB n-CsHn 4 0-CH2CH2 BBB 11-C12H25 5 0-CH2CH2 BB- Ch n-C5Hn 6 0-CH2CH2 BB-Ch 11-C12H25 7 0-CH2CH2 B-Ch-Ch n-CsHn 8 0-CH2CH2 B-Ch-Ch 11-C12H25 9 0-CH2CH2 Ch-Ch-Ch n-CsHn 10 0-CH2CH2 Ch-Ch-Ch 11-C12H25 11 co-o-CH2CH2 B n-CsHn 12 co-o-CH2CH2 B 11-C12H25 13 co-o-CH2CH2 Ch n-CsHn 14 co-o-CH2CH2 Ch 11 -C12H25 15 co-o-CH2CH2 BB n-C5Hn 16 co-o-CH2CH2 BB 11-C12H25 17 co-o-CH2CH2 B-Ch n-C5Hn 18 co-o-CH2CH2 B-Ch 11-C12H25 19 co-o -CH2CH2 Ch-B n-C5Hu 20 co-o-CH2CH2 Ch-B 11-C12H25 21 co-o-CH2CH2 Ch-Ch 11-C5H11 22 co-o-CH2CH2 Ch-Ch n-Ci2H25 23 co-o-CH2CH2 BBB n-C5Hn 24 co-o-CH2CH2 BBB 11-C12H25 25 co-o-CH2CH2 BB-Ch 11-C5H11 26 co-o-CH2CH2 BB-Ch 11-C12H25 27 co-o-CH2CH2 B-Ch-Ch n -C5Hn 28 co-o-CH2CH2 B-Ch-Ch 11-C12H25 29 co-o-GH2CH2 Ch-Ch-Ch n-CsHn 30 co-o-CH2CH2 Ch-Ch-Ch 11-C12H25 31-B CH2CH2 B n -C5Hn 32-B CH2 CH2 Ch n-C5Hn 33-B CH2CH2 BB n-C5Hn 34-B CH2CH2 B-Ch n-CsHn 35-B CH2CH2 Ch-B 11-C5H11 36-B CH2CH2 Ch-Ch n-C5Hn 37-Ch CH2CH2 B n- CsHn 38-Ch CH2CH2 Ch n-C5Hu

45 591056 9825 pif 1 Table 10

No. X1 G1 X2 G2 R5 1-Ch ch2ch2 BB 11-C5H11 2-Ch CH2CH2 B-Ch 11-C5H11 3-Ch ch2ch2 Ch-B 11-C5H11 4-Ch CH2CH2 Ch-Ch n-C5Hu 5-BB CH2CH2 B n-C5Hn 6-BB CH2CH2 Ch n-C5Hn 7-B-Ch CH2CH2 B 11-C5H11 8-B-Ch CH2CH2 Ch n-C5Hn 9-Ch-B CH2CH2 B 11-C5H11 10-Ch-B ch2ch2 Ch n- C5Hn 11-Ch-Ch CH2CH2 B n-C5Hn 12-Ch-Ch CH2CH2, Ch 11-C5H11 13 0 B CH2CH2 B n-C5Hn 14 0 B ch2ch2 Ch n-C5Hn 15 0 B CH2CH2 BB n-C5Hu 16 0 B CH2CH2 B-Ch 11-C5H11 17 0 B CH2CH2 Ch-B n-C5Hn 18 0 B ch2ch2 Ch-Ch 11-C5H11 19 0 Ch ch2ch2 B 11-C5H11 20 0 Ch ch2ch2 Ch Ϊ1-〇5Ηιι 21 0 Ch ch2ch2 BB II- C5H11 22 0 Ch CH2CH2 B-Ch n-CsHn 23 0 Ch CH2CH2 Ch-B n-C5Hn 24 0 Ch ch2ch2 Ch-Ch n-CsHi, 25 0 BB CH2CH2 B n-C5Hu 26 0 BB CH2CH2 Ch n-C5Hu 27 0 B-Ch CH2CH2 B n-C5Hu 28 0 B-Ch ch2ch2 Ch n-C5Hii 29 0 Ch-B GH2CH2 B n-C5Hn 30 0 Ch-B CH2CH2 Ch n-CsHn 31 0 Ch-Ch CH2CH2 B n-C5Hu 32 0 Ch-Ch CH2CH2 Ch 11-C5H11 33 co-o B CH2CH2 B n-C5Hu 34 co-o B CH2CH2 Ch n-C5Hu 35 co-o B CH2CH2 BB n-C5Hu 36 co-o B CH2CH2 B-Ch 11-C5H11 37 co-o B CH2CH2 Ch-B 11-C5H11 38 co-o B CH2CH2 Ch-Ch n-C5Hu

46 591056 9825 pif 1 Table 11

No. ΧΑ 1 co-o 2 co-o 3 co-o 4 co-o 5 co-o 6 co-o 7 co-o 8 co-o 9 co-o 10 co-o 11 co-o 12 co- o 13 co-o 14 co-o 15 ch2 16 ch2 17 ch2 18 ch2 19 ch2 20 ch2 21 ch2 22 ch2 23 ch2 24 ch2 25 ch2 26 ch2 27 ch2 28 ch2 29 ch2 30 ch2 31 ch2 32 ch2 33 ch2 34 ch2 35 0 36 0 37 0 38 0 G1 X2 Ch CH2CH2 Ch CH2CH2 Ch CH2CH2 Ch CH2CH2 Ch CH2CH2 Ch CH2CH2 BB CH2CH2 BB CH2CH2 B-Ch CH2CH2 B-Ch CH2CH2 Ch-B CH2CH2 Ch-B CH2CH2 Ch-Ch CH2CH2 Ch-Ch CH2CH2 B CH2CH2 B CH2CH2 B CH2CH2 B CH2CH2 B CH2CH2 B CH2CH2 Ch CH2CH2 Ch CH2CH2 Ch CH2CH2 Ch CH2CH2 Ch CH2CH2 Ch ch2ch2 BB CH2CH2 BB CH2CH2 B-Ch GH2CH2 B-Ch CH2CH2 Ch-B CH2CH2 Ch-B CH2CH2--

G2 R " B 11-C5H11 Ch n-CsHn BB n-C5Hn B-Ch 11-C5H11 Ch-B n-CsHn Ch-Ch 11-C5H11 B n-CsHn Ch n-CsHu B n-CsHn Ch n-C5Hn B n-CsHn Ch 11-C5H11 B n-C5Hu Ch n-C5Hn B n-CsHn Ch 11-C5H11 BB n-C5Hn B-Ch n-CsHn Ch-B n-C5Hn Ch-Ch n-CsHn B n-CsHn Ch n-CsHn BB n-C5Hn B-Ch 11-C5H11 Ch-B n-CsHn Ch-Ch 11-C5H11 B n-CsHn Ch n-CsHn B n-CsHn Ch 11-C5H11 B n-C5H " Ch n-C5Hu B n-C5Hu Ch n-CsHn BB H BB H BB F BB F 47 591 056 9825 pifl Table 12

No. X1 G1 X2 G2 R5 1 0--BB CN 2 0--BB CN 3 0--BB OH 4 0-One BB OH 5 0-BB O-C2H5 6 0--BB O-C2H5 7 C0-0 --BB H 8 C0-0--BB H 9 C0-0--BB F 10 C0-0--BB F 11 C0-0--BB CN 12 C0-0--BB CN 13 C0-0-Leak BB OH 14 C0-0--BB OH 15 C0-0--BB O-C2H5 16 C0-0--BB O-C2H5 17 0-ch2ch2 BB H 18 0-CH2CH2 BB H 19 0-CH2CH2 BB F 20 0 -CH2CH2 BB F 21 0-CH2CH2 BB CN 22 0-CH2CH2 BB CN 23 0-CH2CH2 BB OH 24 0-CH2CH2 BB OH 25 0-CH2CH2 BB O-C2H5 26 0 CH2CH2 BB O-C2H5 27 C0-0-CH2CH2 BB H 28 C0-0-CH2CH2 BB H 29 C0-0-CH2CH2 BB F 30 C0-0-CH2CH2 BB F 31 C0-0-CH2CH2 BB CN 32 C0-0-CH2CH2 BB CN 33 C0-0 CH2CH2 BB OH 34 C0 -0-CH2CH2 BB OH 35 C0-0-CH2CH2 BB O-C2H5 36 C0-0-ch2ch2 BB O-C2H5 The diamine compound represented by the formula (21) is not limited to the compounds shown in the above examples. Two or more of the above compounds may be used in combination. In such a diamine compound, when G1 and / or G2 have multiple rings, and X1 and / or X2 48 591056 9825 pif 1 is a long-chain alkylene, when R5 is a group having a large carbon number At this time, a liquid crystal alignment film having a large previous tilt angle on the liquid crystal can be obtained. The diamine compound capable of providing an organic residue represented by the formula (4) is as represented by the formula (22). 6

In formula (22), X3, X4, R6, R7, ul, and u2 are respectively the same as the symbols shown in formula (4). Part i of the specific example of the diamine compound represented by formula (22) is obtained by a combination of X3, ul, R6, and R7, as shown in Tables 13 to 19. Then X4 = X3 and u2 = ul. In this table, "-" indicates a single bond. 49 5 殳 1056 9825 pifl Table 13

No. X3 ul R6 R7 1 0 H n-C3H7 2 0 H iso-C3H7 3 0 H 11-C4H9 4 0 H 1S0-C4H9 5 0 H SCC-C4H9 6 0 H tcrt-C4H9 7 0 H n_C5Hu 8 0 H η -〇6Ηΐ3 9 0 H 11-C7H15 10 0 H η-〇δΗΐ7 11 0 H 11-C9H19 12 0 H n-Ci〇H2i 13 0 H n-CnH23 14 0 H n-Ci2H25 15 0 CII3 n-C3H7 16 0 ch3 1S0-C3H7 17 0 ch3 11-C4H9 18 0 ch3 1SO-C4H9 19 0 ch3 sec-C4H9 20 0 ch3 tert-C4H9 21 0 ch3 n-C5Hu 22 0 ch3 n-C6H13 23 0 ch3 11-C7H15 24 0 ch3 n -CgHn 25 0 ch3 11-C9H19 26 0 ch3 11-C10H21 27 0 ch3 11-C11H23 28 0 ch3 11-C12H25 29 0 I1-C3H7 c2h5 30 0 11-C3H7 11-C3H7 31 0 I1-C3H7 11-C4H9 32 0 I1-C3H7 n-C5Hn 33 0 11-C3H7 n-QHu 34 0 I1-C3H7 n-C7H15 35 0 n-C3H7 n-CeHn 36 0 n-C3H7 11-C9H19 37 0 11-C3H7 n-CioH2i 38 0 n-C3H7 n-CnH23 39 0 11-C3H7 11-C12H25 40 0 n-C4H9 41 0 1SO-C4H9 1SO-C4H9 42 0 sec-C4H9 sec-C4H9 43 0 tert-C4H9 44 0 n- CeHn η-ΟόΗπ 45 0 11-C12H25 11-C12H25 50 591056 9825 pif 1 Table 14

No. X3 ill R6 R7 1-1 H 11-C3H7 2-1 H 1SO-C3H7 3-1 H 11-C4H9 4-1 H 1SO-C4H9 5-1 H sec-C4H9 6 1 H tert-C4H9 7-1 H n-C5Hn 8-1 H η-〇6Ηΐ3 9-1 H n-C7H15 10-1 H n-CgHn 11-1 H 11-C9H19 12-1 H 11-C10H21 13-1 H n-CnH23 14-1 H n-Ci2H25 15-1 ch3 n-C3H7 16-1 ch3 iso-C3H7 17-1 ch3 n-C4H9 18-1 ch3 ISO-C4H9 19-1 ch3 sec-C4H9 20-1 ch3 tdt-C4H9 21-1 ch3 n-C5Hn 22-1 ch3 η-ΟόΗπ 23-1 ch3 n-C7H15 24-1 ch3 n-C8H17 25 1 ch3 11-C9H19 26-1 ch3 11-C10H21 27-1 ch3 11-C11H23 28-1 ch3 11- C12H25 29-1 I1-C3H7 c2h5 30-1 n-C3H7 I1-C3H7 31-1 11-C3H7 11-C4H9 32-1 11-C3H7 11-C5H11 33-1 11-C3H7 n-CeH ^ 34-1 11- C3H7 n-C7H15 35-1 11-C3H7 n-CgHn 36 Zen 1 11-C3H7 11-C9H19 37-1 11-C3H7 11-C10H21 38-1 11-C3H7 n-CiiH23 39-1 11-C3H7 40 -1 11-C4H9 11-C4H9 41-1 1S0-C4H9 1SO-C4H9 42-1 sec-C4H9 sec-C4H9 43-1 tert-C4H9 tert-C4H9 44-1 nC ^ Hn n-CeHn 45-1 11-C12H25 11-C12H25 51 591056 9825 pif 1 Table 15

No. X3 ul R6 R7 1 ch2 1 H 11-C3H7 2 ch2 1 H ISO-C3H7 3 ch2 1 H η-〇4Η9 4 ch2 1 H 1S0-C4H9 5 ch2 1 H sec-C4H9 6 ch2 1 H 7 ch2 1 H n-CsHn 8 ch2 1 H η-〇Η13 9 ch2 1 H 11-C7H15 10 ch2 1 H n-CgHn 11 ch2 1 H 11-C9H19 12 ch2 1 H n-Ci〇H2i 13 ch2 1 H n-CnH23 14 ch2 1 H 11-C12H25 15 ch2 1 ch3 11-C3H7 16 ch2 1 ch3 1S0-C3H7 17 ch2 1 ch3 11-C4H9 18 ch2 1 ch3 1SO-C4H9 19 ch2 1 ch3 sec-C4H9 20 ch2 1 ch3 tert-C4H9 ch3 11-C5H11 22 ch2 1 ch3 n-C6H13 23 ch2 1 ch3 11-C7H15 24 ch2 1 ch3 n-C8H17 25 ch2 1 ch3 11-C9H19 26 ch2 1 ch3 11-C10H21 27 ch2 1 ch3 11-C11H23 28 ch2 11-C12H25 29 ch2 1 11-C3H7 c2h5 30 ch2 1 I1-C3H7 11-C3H7 31 ch2 1 11-C3H7 11-C4H9 32 ch2 1 H-C3H7 n-CsHn 33 ch2 1 n-C3H7 n-QHu 34 ch2 1 11 -C3H7 η-〇7Ηΐ5 35 ch2 1 11-C3H7 n-CgHn 36 ch2 1 11-C3H7 11-C9H19 37 ch2 1 11-C3H7 n-Ci〇H2i 38 ch2 1 11-C3H7 11-C11H23 39 ch2 1 n-C3H7 11-C12H25 40 ch2 1 n-C4H9 11-C4H9 41 ch2 1 1SO-C4H9 1SO-C4H9 42 ch2 1 sec-C4H9 sec-C4H9 43 ch2 1 4 4 ch2 1 n-CgHn η-〇Η13 45 ch2 1 11-C12H25 11-C12H25 52 591056 9825 pifl Table 16

No. X3 ul R6 Rv 1 ch2ch2 1 H 11-C3H7 2 ch2ch2 1 H 1S0-C3H7 3 ch2ch2 1 H 11-C4H9 4 ch2ch2 1 H 1S0-C4H9 5 ch2ch2 1 H sec-C4H9 6 ch2ch2 1H 2 1 H n-C5Hn 8 ch2ch2 1 H η-〇6Ηΐ3 9 CH2CH2 1 H n-C7H15 10 ch2ch2 1 H n-C8H17 11 CH2CH2 1 H 11-C9H19 12 ch2ch2 1 H 11-C10H21 13 ch2ch2 1 H 11-C11H23 14 CH2CH2 1 H 11-C12H25 15 ch2ch2 1 CII3 11-C3H7 16 CH2CH2 1 ch3 1SO-C3H7 17 ch2ch2 1 ch3 11-C4H9 18 CH2CH2 1 ch3 IS0-C4H9 19 ch2ch2 1 ch3 sec-C4H9 20 ch2ch2 1 2 ch3 n-CsHn 22 ch2ch2 1 ch3 n-C6H13 23 CH2CH2 1 ch3 11-C7H15 24 ch2ch2 1 ch3 n-CsHn 25 CH2CH2 1 ch3 11-C9H19 26 CH2CH2 1 ch3 n-CioH2i 27 ch2 ch2C2 1H 1 ch3 11-C12H25 29 ch2ch2 1 I1-C3H7 c2h5 30 ch2ch2 1 I1-C3H7 11-C3H7 31 CH2CH2 1 11-C3H7 n-C4H9 32 ch2ch2 1 I1-C3H7 n-C5Hn 33 CH2CH2 1 I1-C3H3 11- 1 n-C3H7 n-C7H15 35 ch2ch2 1 n-C3H7 n-CgHn 36 ch2ch2 1 11-C3H7 11-C9H19 37 CH2CH2 1 n-C3H7 n-Ci〇H2i 38 ch2ch2 1 n-C3H7 n-CnH23 39 ch2 ch2 1 11-C3H7 11-C12H25 40 ch2ch2 1 11-C4H9 11-C4H9 41 CH2CH2 1 1SO-C4H9 1S0-C4H9 42 ch2ch2 1 sec-C4H9 sec-C4H9 43 ch2ch2 1 tert-C4H9 1 1 t-C4H9 11-C6H13 45 CH2CH2 1 n-Ci2H25 11-C12H25 53 591056 9825 pif 1 Table 17

No. X3 ul R6 Rv 1 0 1 Η n-C3H7 2 0 1 Η 1SO-C3H7 3 0 1 Η 11-C4H9 4 ο 1 Η 1SO-C4H9 5 0 1 Η sec-C4H9 6 ο 1 Η tert-C4H9 7 ο 1 Η n-C5Hn 8 ο 1 Η n-C6H13 9 0 1 Η n-C7H15 10 0 1 Η n-CgHn 11 0 1 Η 11-C9H19 12 0 1 Η 11-C10H21 13 0 1 Η n-CiiH23 14 0 1 Η 11-C12H25 15 ο 1 ch3 11-C3H7 16 ο 1 ch3 1SO-C3H7 17 ο 1 ch3 n-C4H9 18 0 1 ch3 1SO-C4H9 19 0 1 ch3 sec-C4H9 20 0 1 ch3 tert-C4H9 21 0 1 ch3 n-C5Hn 22 ο 1 ch3 n-C6H13 23 0 1 ch3 n-C7H15 24 ο 1 ch3 n-CsHn 25 ο 1 ch3 11-C9H19 26 ο 1 ch3 n-Ci〇H2i 27 0 1 ch3 n-CiiH23 28 ο 1 ch3 11-C12H25 29 0 1 11-C3H7 c2h5 30 0 1 I1-C3H7 11-C3H7 31 0 1 n-C3H7 11-C4H9 32 0 1 11-C3H7 n-C5Hn 33 ο 1 11-C3H7 n-CeH ^ 34 ο 1 n-C3H7 n-C7H15 35 0 1 11-C3H7 n-CsHp 36 ο 1 11-C3H7 11-C9H19 37 0 1 11-C3H7 n-Ci〇H2i 38 0 1 11-C3H7 n-CiiH23 39 0 1 11- C3H7 11-C12H25 40 0 1 11-C4H9 n-C4H9 41 0 1 1SO-C4H9 1SO-C4H9 42 ο 1 sec-C4H9 sec-C4H9 43 ο 1 tcrt-C4H9 tert-C4H9 44 ο 1 n-C6H13 II-C6H13 45 ο 1 11-C12H25 II -C12H25 54 9825 pif 1 Table 18

No. X3 ul R6 R1 1 0 1 H 11-C3F7 2 0 1 H 1SO-C3F7 3 0 1 H 11-C4F9 4 0 1 H 1SO-C4F9 5 0 1 H sec-C4F9 6 o 1 H tert-C4F9 7 0 1 H 11-C5F11 8 0 1 H n-C6F13 9 o 1 H n-C7F15 10 0 1 H n-C8Fn 11 o 1 H 11-C9F19 12 0 1 H n-Ci〇F2i 13 0 1 H n-CnF23 14 o 1 H 11-C12F25 15 0 1 cf3 11-C3F7 16 o 1 cf3 1SO-C3F7 17 0 1 cf3 11-C4F9 18 0 1 cf3 ISO-C4F9 19 0 1 cf3 sec-C4F9 20 0 1 cf3 tert-C4F9 21 0 1 cf3 11-C5F11 22 0 1 cf3 n-QF13 23 0 1 cf3 11-C7F15 24 o 1 cf3 n-CgFn 25 0 1 cf3 11-C9F19 26 0 1 cf3 11-C10F21 27 0 1 cf3 11-C11F23 28 0 1 cf3 11-C12F25 29 0 1 11-C3F7 c2f5 30 0 1 I1-C3F7 11-C3F7 31 0 1 H-C3F7 11-C4F9 32 0 1 11-C3F7 n-CsFn 33 0 1 I1-C3F7 n-CeFn 34 0 1 11-C3F7 11-C7F15 35 o 1 I1-C3F7 n-CgFn 36 0 1 11-C3F7 11-C9F19 37 0 1 11-C3F7 n-Ci〇F2i 38 0 1 11-C3F7 11-C11F23 39 0 1 n-C3F7 11-C12F25 40 o 1 11-C4F9 11-C4F9 41 0 1 1SO-C4F9 1SO-C4F9 42 o 1 sec-C4F9 sec-C4F9 43 0 1 tcrt-C4F9 tert-C4p9 44 o 1 n-C6F13 n-C6Fi3 45 0 1 n-Ci2F25 n-Ci2F25 55 591056 9825 pifl Table 19

No. XJ ul R6 Ry 1 0 2 ch3 n-C3H7 2 0 2 ch3 11-C4H9 3 0 2 ch3 n-C5H „4 0 2 ch3 II-C6H13 5 ο 2 ch3 II-C7H15 6 0 2 ch3 n-C8H17 7 0 2 ch3 11-C9H19 8 ο 2 ch3 11-C10H21 9 0 2 ch3 11-C11H23 10 0 2 ch3 11-C12H25 11 0 2 ch3 11-C3H7 12 0 2 ch3 11-C4H9 13 0 2 ch3 n-C5H „14 ο 2 ch3 n-C6H13 15 0 2 ch3 11-C7H15 16 0 2 ch3 n-CgHn 17 0 2 ch3 11-C9H19 18 0 2 ch3 11-C10H21 19 0 2 ch3 11-C11H23 20 0 2 ch3 11-C12H25

The diamine compound represented by the formula (22) is not limited to the compounds shown in the above examples. Two or more of the above compounds may be used in combination. In such a diamine compound, when R6 and R7 are hydrogen or a small carbon number group, the liquid crystal alignment agent of the present invention thus obtained is used to obtain a liquid crystal alignment film having a slightly smaller pretilt angle on the liquid crystal. The diamine compound capable of providing an organic residue represented by the formula (5) is as represented by the formula (23).

The symbol is the same, and the bonding position of the substituent group and the amine group of the benzene ring is arbitrary. 56 591056 9825 pifl The specific examples of the diamine compound represented by formula (23) are obtained in part from the combination of X5, R8, m and η, as shown in Tables 20 to 21. In this table, "-" indicates a single bond. In addition, the diamine compounds described in this table are compounds in which two amine groups are respectively bonded to the parasite of the phenyl ring by a para phase, and are bonded to the same normal phase with cyclohexene.

57 591056 9825 pif 1 Table 20

No. R " XD mn 1 H-0 1 2 ch3-0 1 3 C2H5-0 1 4 n-C3H7-0 1 5 n-C4H9-0 1 6 n-CsHn-0 1 7 Π-〇6Ηΐ3-0 1 8 n-C7H15-0 1 9 n-CgHn-0 1 10 11-C9H19-0 1 11 11-C10H21-0 1 12 11-C11H23-0 1 13 11-C12H25-0 1 14 H-1 1 15 ch3- 1 1 16 C2H5-1 1 17 n-C3H7-1 1 18 H-C4H9-1 1 19 n-C5Hn-1 1 20 n-C6H13-1 1 21 n-C7Hi5-1 1 22 n-CsHn-1 1 23 11-C9H19-1 1 24 11-C10H21-1 1 25 n-CnH23-1 1 26 11-C12H25-1 1 27 H-2 1 28 ch3-2 1 29 C2H5-2 1 30 11-C3H7-2 1 31 n-C4H9-2 1 32 n-CsHn-2 1 33 nC ^ Hn-2 1 34 11-C7H15-2 1 35 n-CgHn-2 1 36 11-C9H19-2 1 37 11-C10H21-2 1 38 n -CnH23-2 1 39 11-C12H25-2 1 58 591056 9825 pif 1 Table 21

No. R8 X) mn 1 Η CH2CH2 1 1 2 ch3 CH2CH2 1 1 3 C2H5 CH2CH2 1 1 4 n-C3H7 ch2ch2 1 1 5 11-C4H9 CH2CH2 1 1 6 n-C5H „CH2CH2 1 1 7 η-〇6Ηΐ3 CH2CH2 1 1 8 n-C7H15 CH2CH2 1 1 9 n-CgHn CH2CH2 1 1 10 11-C9H19 CH2CH2 1 1 11 11-C10H21 CH2CH2 1 1 12 n-CnH23 CH2CH2 1 1 13 11-C12H25 CH2CH2 L 1 14 H CH2CH2 1 2 15 ch3 CH2CH2 1 2 16 C2H5 CH2CH2 1 2 17 11-C3H7 CH2CH2 1 2 18 11-C4H9 CH2CH2 1 2 19 n-C5Hn CH2CH2 1 2 20 n-C6H13 CH2CH2 1 2 21 n-C7H15 CH2CH2 1 2 22 n-C8H17 CH2CH2 1 2 23 11-C9H19 CH2CH2 1 2 24 11-C10H21 CH2CH2 1 2 25 11-C11H23 CH2CH2 1 2 26 11-C12H25 CH2CH2 1 2 27 H CH2CH2 1 4 28 ch3 CH2CH2 1 4 29 C2H5 CH2CH2 1 4 30 n-C3H7 CH2CH2 1 4 31 11-C4H9 CH2CH2 1 4 32 n-C5Hu CH2CH2 1 4 33 n-C6H13 CH2CH2 1 4 34 n-C7H, 5 CH2CH2 1 4 35 n-CgHn CH2CH2 1 4 36 11-C9H19 CH2CH2 1 4 37 n-Ci〇H2i CH2CH2 1 4 38 11-C11H23 CH2CH2 1 4 39 11-C12H25 CH2CH2 1 4 The diamine compound represented by formula (23) is not limited to the compounds shown in the above examples. The above-mentioned compounds can also be used in combination 2 or more. In this type of diamine compound of 59 504056 9825 pif 1, when m is 0 and R8 is hydrogen or a short-chain radical, when X5 is a single bond or a short-chain alkylene , The rake angle will become slightly smaller. When m is 1 to 3, R8 is hydrogen, and X5 is a single bond, the forward tilt angle becomes larger. The specific examples shown above are only a part of the diamine compounds that can provide the organic residues represented by the formulas (2) to (5), respectively. In addition, there are diamine compounds having a side chain group having 3 or more carbon atoms. For example, a phenylene diamine derivative having a side chain in a nest system. As long as the diamine compound used in the present invention can achieve the purpose of the present invention, it can be selected from a wide range containing the diamine compound. In the present invention, in order to adjust the required inclination angle 値, the above-mentioned diamine compound having a side chain group having a carbon number of 3 or more (hereinafter referred to as the first group of diamine compounds) and a carbon number not having a number of 3 or more are used simultaneously. The side chain group of the diamine compound (hereinafter referred to as the second group of diamine compounds) to effectively increase the forward tilt angle. Among the second group of diamine compounds used in the present invention, they can be divided into aromatic diamine compounds, alicyclic diamine compounds, and aliphatic diamine compounds, and the aforementioned compounds are selected from various conventional methods. Substances recorded in the literature. An example of the conventional literature is, for example, the diamine compounds described in pages 19 to 20 and pages 34 to 37 of the W001 / 00732A1 publication. In addition, the substances related to the diamine compounds described in this bulletin are, for example, substances having different amine bond positions, and different alkyl and / or alkylene carbon numbers in their structures. Substances, substances in which arbitrary hydrogen is replaced with fluorine, and substances in which the number of alkyl substituents of the aromatic ring are different. Furthermore, it is, for example, a diamine compound having an ether group. In the foregoing, the second group of diamine compounds used in the present invention may be used arbitrarily by selecting one of a large number of compounds of 60 591056 9825 pif 1, or may be used in combination of two or more. It is preferred that the aliphatic-based substance in the second group of diamine compounds is used within a range that can maintain good liquid crystal alignment. Furthermore, among the second group of diamine compounds, substances having groups such as ether, ester, thioether, thioester, etc., in order to maintain high electrical properties of the liquid crystal display element, it is necessary to limit the amount of use thereof. When the N-substituted polyamidoamine-iminomine of the present invention is produced, and when the first group of diamine compounds and the second group of diamine compounds are used together, a Mohr ratio (the first group) The diamine compound 7 diamine compound of the second group) is (100/0) to (1/99). The preferred range is (100/0) to (10/90), and the more preferred range is (100/0) to (20/80). However, this range may vary depending on the type of compound used and the 之前 of the required previous inclination, rather than a definite 値. Moreover, as the ratio of the first diamine compound increases, the forward tilt angle also increases. In the N-substituted polyamidoamine-iminomine of the present invention, more than 30 mol% of N of all the amidine bonds present in the molecule is bonded to a monovalent organic group. This monovalent organic group is composed of an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, and a carbon group having 2 to 15 carbon atoms. Saturated aliphatic groups, alicyclic groups, aromatic hydrocarbon groups, nested skeleton groups, carbonyl groups, organosilyl groups, and organosilyl groups. Select more than one group from the group of the composition. Arbitrary hydrogen contained in the radicals and the radicals contained in such organic radicals can also be replaced with fluorine. In the aromatic hydrocarbon group, any hydrogen of the 'aromatic ring' may be replaced with an alkyl group, an alkoxy group, or -CN. Any hydrogen of this alkyl group and alkane 61 591056 9825 pif 1 oxygen group may be replaced with fluorine. Moreover, an alkylene group on an aromatic compound, which is an aromatic hydrocarbon group, may be bonded to an aromatic ring through an oxygen atom. However, when a highly flexible group is used as a monovalent organic group, the alignment of the liquid crystal will be extremely deteriorated. Therefore, when considering the effect on the alignment of the liquid crystal, an organic group with a carbon number of 5 or less is used. Preferably, an alkyl group having a carbon number of 5 or less is used. Furthermore, any -CH2_ in this alkyl group is not limited to two consecutive -0_, but may be replaced with -0, -CO- or -COO-. However, as long as the valence organic group does not cause a problem in the alignment of the liquid crystal, the aforementioned organic group can also be used. The substitution ratio of the monovalent organic group is preferably 50 mol% or more. This ratio is more preferably 70 mol% or more. When such a monovalent organic group is introduced into polyamidoamine-iminomine to be used as a liquid crystal alignment agent varnish ', a large effect of improving electrical characteristics can be obtained. In order to fully exert this effect, it is necessary that the proportion of the monovalent organic group in the N-substituted polyamidine-iminomine is 30 mol% or more. Examples of this monovalent organic group are as follows. Examples of academic groups are, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-, n-nonyl, n-decyl, n-undecyl, n-decyl Dialkyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosane Base, isopropyl, isobutyl, isobutyl, tert-butyl, isopentyl, neopentyl, terpentyl, methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl Methylpentyl, isohexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 'ethylpentyl, 2,4-monomethylhexyl, 2,3,5-di Ethylheptyl, fluoren (methyl), perfluoro (substituted) 62 9825 pifl Ethyl, n-perfluoro (substituted) propyl, n-perfluoro (substituted) butyl, n-perfluoro (substituted) pentyl , N-perfluoro (generation) hexyl, n-perfluoro (generation) heptyl, n-perfluoro (generation) octyl, n-perfluoro (generation) nonyl, n-perfluoro (generation) decyl, n-perfluoro (generation) ) -J——Fundamental base, Zhengquan wins (on behalf of) Twelve Faculty bases, Full perfluorinated (on behalf) Thirteen homestead bases, Full perfluorinated (on behalf) ) Tetradecyl, n-perfluoro (substituted) pentadecyl, n-perfluoro (substituted) cetyl, n-perfluoro (substituted) heptyl, n-perfluoro (substituted) octadecyl, N-perfluoro (substituted) nonadecanyl, n-perfluoro (substituted) eicosyl, etc. Examples of the hydroxyalkyl group are, for example, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl. Examples of alkoxyalkyl are, for example, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, ethoxymethyl, ethoxyethyl, ethoxy Propyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, hexylhydroxymethyl, hexylhydroxyethyl, hexylhydroxypropyl, hexylhydroxybutyl, hexylhydroxypentyl, hexylhydroxyhexyl, and the like. Examples of unsaturated aliphatic groups are, for example, vinyl, ethynyl, IE alkenyl, 2-propenyl, isopropenyl, 2-butenyl, butadiene- [1,3] -yl, 2-pentyl Alkenyl, 2-pentene-4yne, 2-nonyl-2-butenyl, and the like. Examples of the group having an alicyclic group are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclohexane, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl , Cyclohexylmethyl, bicyclohexylmethyl, 2-cyclopentene-1-yne, 2,4-cyclopentadiene-1-yne, and the like. Examples of the aromatic hydrocarbon group are, for example, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, bibenyl, monobenzyl, dibenzyl, card Group, biphenylmethyl, diphenylmethyl, bitriphenylmethyl, 4-methylbenzyl, 4- (tert-butyl) benzyl, α-63 591056 9825 pif 1 methylbenzyl, 1-naphthyl, 2-naphthyl, 9-anthrylmethyl, 4-methoxybenzyl, phenoxymethyl, benzylhydroxymethyl, diphenylhydroxymethyl, naphthylhydroxymethyl, 4-trifluoromethylbenzyl, cyanophenyl, cyanobiphenyl, cyanobitriphenyl, cyano, cyanophenylmethyl, cyanobiphenylmethyl, cyanobitri Phenylmethyl and the like. Examples of the oxygen-containing heterocyclic group are furfuryl, (3-furyl) methyl, 2-oxetanylmethyl, 3-oxetanylmethyl, oxolanyl methyl, dioxolanyl methyl, and the like. Examples of nested skeletons are, for example, biliary, basal, β-biliary, epistasyl, Ergostery, Ilex-hydroxymethyl nest, Ilex luteal nest, wool nest, Methyltestosteryl, Norethisteryl, Pregnostyl, Beta-Nestyl, Bean-Nestyl, Testostery Cholesterol Acetate, etc. Examples of the carbonyl-containing group are, for example, methylamidino, ethylamido, phenylamidino, methoxycarbonyl, phenylmethoxycarbonyl and the like. Examples of the organosilyl group and the group containing an organosilyl group are, for example, trimethylsilane, triethylsilane, triphenylsilane, 4-trimethylsilyl, and the like. Among the above-mentioned preferred examples, a monovalent organic group having a carbon number of 5 or less is preferred. Specifically, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopropyl, isobutyl, isobutyl, tert-butyl, isopentyl, neopentyl, tert-pentyl Base, vinyl, ethynyl, 1-propenyl, 2-propenyl, isopropenyl, 2-butenyl, butadiene- [1,3] -yl, 2-pentenyl, 2-pentene -4 alkyne, cyclopropyl, cyclobutyl, cyclopentyl, cyclopropylmethyl, cyclobutylmethyl, 2-cyclopentene-1-yne, 2,4-cyclopentadiene-1-yne, tris Fluoro (methyl), perfluoro (ethyl), methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, Hydroxymethyl, hydroxyethyl 64 59 ^^ 98 98 pif 1 group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, furfuryl group, (3-pyranyl) methyl group, 2-oxetanylmethyl group, 3 -Oxetanylmethyl, oxolanyl methyl, dioxolanyl methyl, formamyl, ethenyl and the like. The N-substituted polyamidoamine-iminomine of the present invention is synthesized by the following method. First, the first method was to synthesize polyamidoamines by using diamine compounds and carboxylic acids. Next, a method of substituting the hydrogen atom of the amidine bond (CONH) of the obtained polyamidine-imideneamine (CONH) with a monovalent organic group is performed. In the following description, this method is called a post-replacement method. After the polyamidoamine-iminomine reacts with a salt group dissolved in a solvent, the N-substituted polyamidoamine-iminomine is obtained through a reaction with a halogenated compound of a monovalent organic group. Examples of the solvent to be used at this time are, for example, dimethylmethylene maple, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylformamide, and the like. Examples of the base are, for example, sodium methoxide, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, butyllithium, and triethylamine. Another method for synthesizing the N-substituted polyamidoamine-iminomine of the present invention is to use a diamine compound (N-substituted diamine compound) in which an amino group (NH2) is replaced with a monovalent organic group in advance, to produce polyamidoamine-iminomine. Method (hereinafter referred to as pre-replacement method). This N-substituted diamine compound can be easily obtained by referring to a conventional organic synthesis method. An example is dehydration polymerization reaction of (0 diamine compound with aldehydes (such as propionaldehyde, benzaldehyde, etc.) or ketones (such as methyl ethyl ketone, cyclohexanone, etc.) to obtain an imine compound, and then this imine Method for reducing double bond; (2) Diamine compound reacts with acid halide (such as acetamidine oxide, benzoic acid oxide, etc.) to obtain amidine compound, and then the carbonyl group of this amidine is lithium aluminum hydride And other reduction methods; and (3) N-substituted anilines (such as 65 591056 9825 pif 1 N-methylaniline, N, N-diphenylamine, N-methyl-3-toluidine, etc.) and formaldehyde in acid A method of performing a reaction in the presence of a catalyst to obtain N, N,-substituted diamido diphenylmethanes, etc. Next, a method for producing polyamidoamine-iminomine is described. The reaction is a reaction of a carboxylic acid halide and an amino group in a temperature range of 0 ° C to 300 ° C. This reaction can also use dimethylsulfenyl, N-methylpyrrolidone, N, N-di Solvents for methylformamide, N, N-dimethylformamidine, ethamidine, etc. Furthermore, it may be in pyridine or triethyl And so on_ to carry out the reaction. Another method to generate amidine bonding is a method of reacting a carboxyl group with an amino group in the presence of pyridine at a temperature of 0 ° C to 300 ° C. At this time, the foregoing can also be used As the solvent, a condensing agent such as (PhO) 3P, (PhO) PCl2, PhPOCl2, or (C3H7) 3P (〇) 〇 etc. may be used. On the other hand, the formation of amidine bond: first, in the presence of the necessary solvent Then, in the range of 0 ° C to 100 ° C, the cyclic dicarboxylic anhydride is reacted with the amino group to obtain amidinic acid. Then, pyridine and anhydrous acetic acid are added, and the range is from 0 ° C to 200 ° C. It can be produced by reaction within ®. It is also possible to use a diisocyanate compound obtained from the reaction of diammonium compounds and phosgene (phosgene), etc., to carry out the reaction to form amidine bonds and to form sulfonium Amine bonding reaction. The reaction to form amidine bond is the reaction of carboxyl group and diisocyanate group in the aforementioned diisocyanate compound in the range of 0 ° C to 300 ° C. In this reaction, the aforementioned solvent can also be used Agent or solvent of ethylene glycol (mono) methyl ether, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, or r-butyrolactone, etc. 66 591056 9825 pif 1 tertiary amines, alkali metals Catalysts of compounds, alkaline earth metal compounds, etc., or a small amount of water or aromatic hydrocarbons such as xylene, toluene, etc. In addition, when a cyclic dicarboxylic anhydride is used instead of a carboxyl group, it is also the same as the reaction for forming an amidine bond. Therefore, the sulfonamide bond is directly formed. Therefore, in order to synthesize the carboxylic acid raw material of the polyfluorenamine-sulfonimide of the present invention, it is preferable to use a combination of the following ⑴ ~ (V). ⑴ The anhydride structure and the acid halide group (H) At least one type of carboxylic acid having an acid anhydride structure and an acid halide group, and at least one type of dicarboxylic acid diacid halide. (iii) At least one of carboxylic acids having an acid anhydride structure and an acid halide group, and tetracarboxylic acids (tetracarboxylic acid diacid anhydride, tetracarboxylic acid tetraacid halide, or two carboxyl groups of the tetracarboxylic acid acid anhydride structure and remain At least one of the two carboxylic acid halide derivatives). (iv) at least one dicarboxylic acid diacid halide and at least one of the foregoing tetracarboxylic acids. (v) At least one of carboxylic acids having a cyclic dicarboxylic anhydride structure and an acid halide group, at least one of dicarboxylic acid diacid halides, and at least one of the aforementioned tetracarboxylic acids. Any of the carboxylic acid raw materials obtained in combination with the diamine compound is used, and the initial acid anhydride structure is reacted with the amino group in the presence of a solvent. Next, pyridine, triethylamine, or the like is added to react the acid halide with the amino group to synthesize polyamine-amidate. After that, anhydrous acetic acid was added and heated to dehydration and ring-closing the amido acid structure to synthesize polyamidamine 67 591056 9825 pifl imidoamine. A next example of the method for synthesizing polyamidoamine-iminomine is a method using a combination (Vi) to (X) of the carboxylic acid raw materials described below. (Vi) A carboxylic acid having at least one of an acid anhydride structure and a carboxyl group. ㈣ has at least one of Suipu and __guan and at least one of dicarboxylic acids. (vm) At least one type of carboxylic acid having an acid anhydride structure and a carboxyl group, and at least one type of tetracarboxylic dianhydride. (Ix) at least one type of dicarboxylic acid and at least one of the aforementioned tetracarboxylic acid dianhydride. (X) At least one type of carboxylic acid having an acid anhydride structure and a carboxyl group, at least one type of dicarboxylic acid, and at least one type of the aforementioned tetracarboxylic acid dianhydride. Any one of the combinations (vi) to (x) and a diisocyanate compound, in the presence of a solvent, and corresponding necessary catalysts (such as tertiary amines, alkali metal compounds, alkaline earth metal compounds, etc.) Or, together with a small amount of water or aromatic hydrocarbons (such as xylene, toluene, etc.), the reaction is performed in a range of 0 ° C to 300 ° C. Furthermore, using any of the aforementioned combinations (vi) to (X) with a diamine compound, in the presence of a solvent, 'reacting from the initial anhydride structure with the amino group, and then · with a condensing agent such as (PhO) 3P, ( PhO) PCl2, PhPOCl2 or (C3H7) 3P02, etc.) and pyridine are reacted at a temperature ranging from 0 ° C to 300 ° C, and polyamine-amidate can also be synthesized. After that, anhydrous acetic acid was added and heated to make the ammonium acid structure undergo dehydration and ring closure, and 68 9825 pifi was synthesized to polyamide-sulfuramide. When the N-substituted polyamidoamine-iminomine of the present invention is synthesized using a pre-substitution method, the polyamidoamine-iminomine synthesis method uses the aforementioned N-substituted diamine compound as a raw material instead of a diamine compound. Initially, a carboxylic acid derivative having an N-substituted amidine bond as shown in formula (24) is synthesized by using an acid having an acid anhydride structure and an acid halide group and the aforementioned N-substituted diamine compound. Then, this carboxylic acid derivative is subjected to polycondensation reaction with a diamine compound to obtain polyamidamine-amidate having a N-substituted amidine bond. Thereafter, amidine is bonded to amidine to obtain amidine_imidoamine. Can also be expressed by

In formula (24), T1, D1, and R1 have the same definitions as the symbols shown in formula (1), respectively. However, in comparison with the pre-substitution method, the aforementioned post-substitution method has better reactivity, and thus it is possible to obtain N-substituted polyamidoamine-iminomine having a higher molecular weight. Since a liquid crystal alignment film with better mechanical properties can be obtained by using this, the film is not damaged during the honing process for imparting liquid crystal alignment. In this way, the problem that the alignment of the liquid crystal is disturbed can be avoided. The preferred molecular weight of the N-substituted polyamidoamine-iminomine of the present invention is a weight average molecular weight (Mw) obtained by conversion of polystyrene such as gel permeation chromatography (GPC). It is 69 59 ^ 056 9825 pif 1 around 10,000 ~ 500,000. A more preferable molecular weight is 20000 ~ 200,000. The liquid crystal alignment agent lacquer of the present invention is a homogeneous solution composed of a composition containing the above-mentioned N-substituted polyamidamine-imide and a solvent. The liquid crystal alignment agent varnish may contain other polymers within a range that does not impair the effect of the present invention. Other polymers which can be used in combination with the N-substituted polyamidoamine-iminomine of the present invention are polyamidic acid, soluble polyamidoamine, polyamidoamine, and the like generally used in liquid crystal alignment agent lacquers. It is also possible to use other polyamidoamines. By using other polymers in combination, the characteristics of the liquid crystal # alignment agent can be further improved. In the liquid crystal alignment agent lacquer of the present invention, the preferred concentration of the polymer compound (N-substituted polyfluorene-amidine or a mixture of the substituted polyfluorene-imino and other polymers) is lacquer. The total weight is 0.1 to 40% by weight. When the liquid crystal alignment agent varnish is applied on the substrate, in order to adjust the film thickness, the varnish may be diluted with a solvent in advance if necessary. In order to make the solvent uniformly mixed in the varnish for easier dilution, it is necessary to ensure that the concentration of the polymer compound is within a range of not more than 40% by weight. When coating is performed by a spin coating method or a printing method, in order to maintain a good film thickness, the concentration of the local molecular compound is usually 10% by weight or less. When other coating methods such as a dip coating method are used, lower weights can be obtained by using 10% by weight. On the other hand, in order to prevent the film thickness of the liquid crystal film from doubling, the concentration of 1¾ molecular compound is at least G1% by weight. That is, in a general spin coating method or a printing method, the concentration of the polymer compound is more preferably 0.% by mass. The bone marrow of bribe g. 5 ~ i〇 weight%. However, with the lacquer coating method, a thinner concentration of 70 9825 pif 1 can also be used. In the liquid crystal alignment agent lacquer of the present invention, the solvent used to dissolve the N-substituted polyamide-imide is only required to be a liquid having the ability to dissolve the polymer compound, and there is no other special limitation. Therefore, when manufacturing polyamidoamines, polyamidoamines, polyamidoacids, soluble polyamidoamines, polyamidoamines, etc., or when using such polymers, it is preferable to use the commonly used solvents. Make appropriate selection according to the purpose of use. This solvent is a solvent having affinity for the above-mentioned polymers and is an aprotic polar organic solvent. Examples are N-methyl-2-orbitanone, Dimethylimidazolidinorie, N-methylcaprolactam, N-methylpropylamine, N, N-dimethylacetamide, dimethylsulfo Oxides, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, r-butyllactone, and the like. Further, for the purpose of improving the coatability and the like, a mixed solvent obtained by adding other solvents to the above solvents may be used. Examples of other solvents used for this purpose are alkane lactate, 3-methyl-3-methoxy, tetralin, isophorone, ethylene glycol (mono) alkyl ethers (such as ethylene glycol ( A) butyl ether, etc.), diethylene glycol (a) alkyl ether (such as diethylene glycol (a) ethyl ether, etc.), ethylene glycol (a) alkyl acetate, ethylene glycol (a) Phenyl acetate, triethylene glycol (a) alkyl ether, propylene glycol (a) alkyl ether (such as propylene glycol (a) butyl ether, etc.), dipropylene glycol (a) alkyl ether (such as dipropylene glycol (a) Methyl ether, etc.), malonic acid dioxane (diethane malonate), a compound obtained by esterifying OH acetate with the aforementioned solvent, and the like. The liquid crystal alignment agent varnish of the present invention may contain various additives if necessary. For example, when it is desired to improve the coating property, 71 591056 9825 pif 1 and a surfactant suitable for this purpose may be added. When it is necessary to improve the antistatic property, an antistatic agent may be blended. When it is desired to improve the adhesion to the substrate, an organic silane coupling agent or a titanium-based coupling agent may be blended. The liquid crystal alignment agent varnish obtained as described above is more suitable as a material mainly composed of a liquid crystal alignment film for a TFT. In addition, since it can provide a moderate forward tilt angle, when forming a normal liquid crystal alignment film for a TN liquid crystal display element, a liquid crystal alignment film for a STN liquid crystal display element, a liquid crystal alignment film for an IPS liquid crystal display element, VA In the case of a liquid crystal alignment film for a liquid crystal display device, a liquid crystal alignment film for a OCB liquid crystal display device, a liquid crystal alignment film for a ferroelectric liquid crystal, or a liquid crystal alignment film for an anti-ferroelectric liquid crystal display device, etc., Department is useful. In addition, since the liquid crystal display element has good electrical characteristics, a protective film or an insulating film is also used. The liquid crystal display element of the present invention is produced by using a substrate on which a liquid crystal alignment film coated with the liquid crystal alignment agent of the present invention is formed. This substrate and a substrate on which a liquid crystal alignment film different from this substrate is formed are arranged so that the alignment films face each other, and liquid crystal is interposed therebetween to obtain a liquid crystal display element obtained by a conventional method. Alternatively, a liquid crystal display element may be manufactured using only this substrate. The liquid crystal alignment film is formed by a coating process of applying a liquid crystal alignment agent to a substrate, a subsequent drying process, and a heat treatment process necessary for dehydration and closed-loop reactions. Generally known coating methods are spin coating, printing, dip coating, and dropping. The aforementioned method is also applicable to the present invention. The general method of heating treatment necessary for drying, dehydration, and closed-loop reaction is a heating method in a heating furnace or an infrared heating furnace, or a heating method using 72 591056 9825 pif on a hot plate. The aforementioned method is also applicable to the present invention. The preferable temperature in the drying process is only required to be a temperature slightly lower than the range in which the solvent can be evaporated. The preferred temperature in the heat treatment process is 150 ° C to 300 ° C. The preferred liquid crystal composition used in the liquid crystal display element of the present invention is, for example, used in STN type liquid crystal display elements, such as Japanese Patent Laid-Open No. 8-157828, Japanese Patent Laid-Open No. 8-231960, and Japan The liquid crystal compositions disclosed in Patent Publication No. 9-241644 and Japanese Patent Publication No. 9-302346. In addition, for the TFT-type liquid crystal display element (TN type, IPS type, VA type, OCB type), for example, Japanese Patent Laid-Open No. 8-199168, Japanese Patent Laid-Open No. 9-235552, and Japan Patent Publication No. 9-241643, Japanese Patent Publication No. 10-204016, Japanese Patent Publication No. 10-204436, Japanese Patent Publication No. 10-231482, and Japanese Patent Publication No. 2000-087040 The disclosed liquid crystal composition. It is preferable to use a liquid crystal composition mainly composed of the composition disclosed above. Furthermore, a single optically active compound may be added to the liquid crystal composition. [Best method for implementing the present invention] Next, the present invention will be described in more detail with examples, but the present invention is not limited to the examples described. In the example, 'is an example of a case where N is substituted for polyamidoamine and polyamidoamine for the purpose of further improving the characteristics, but it is not limited thereto, and may be Without impairing the effect of the present invention, N is used instead of polyamidoamine-iminomine. 73 591056 9825 pif 1 In the following description, "liquid crystal alignment agent paint" is represented by "paint paint". The abbreviations of the raw materials used in the examples and comparative examples and their corresponding compound names are shown below. TPA: terephthalic acid dichloride TMA: trimellitic anhydride chloride PMDA: pyromellitic acid anhydride CBDA: cyclobutanetetracarboxylic acid anhydride BDA: butanetetracarboxylic acid anhydride DPM: 4, 4'-Diaminodiphenylmethane 4CB1B: 1,1_bis (4-((4-aminophenyl) methyl) phenyl) -4-butylcyclohexane 5CCBOB: 1,1_bis (4 -(4-aminophenoxy) phenyl) -4- (4-pentylcyclohexyl) cyclohexane 5CCB1P: 5-(-(4- (4-pentylcyclohexyl) cyclohexyl) phenyl) methyl -1,3-diaminobenzene 6BOB: 2,2-bis (4- (4-aminophenoxy) phenyl) -hexane 5CCDPM: 1- (4-pentylcyclohexyl) · 4 · (5_ Aminobenzyl-2-aminophenyl) cyclohexane NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve [Example 1] (Synthesis of polyamidoamine-iminomine) With a thermometer, A 300 ml four-necked flask with a mixer, condenser, raw material inlet and nitrogen 74 5 91-9825 pifl gas inlet was charged with DPM (5.001g), 4ChBlB (6.828g), and dehydrated NMP (100.Og), It was stirred and dissolved under a stream of dry nitrogen. The solution was cooled to 5 ° C, TMA (& 171g) was added, and the reaction was performed at 25 ° C for 4 hours. Then, pyridine (15.34 g) was added, and the reaction was carried out at 25 ° C for 15 hours to synthesize and obtain a viscose solution of polyamide-fluorine. Then, dehydrated NMP (64.66 g) and anhydrous acetic acid (27.74 g) were sequentially added thereto, and the reaction was performed at 50 ° C for 3 hours. Thereafter, the obtained reaction solution was poured into a large amount of methanol, and then filtered to obtain a polymer that had been precipitated. After the obtained polymer was dissolved in NMP again, it was reprecipitated with pure water and filtered, and after that, it was dried under reduced pressure to obtain 16.5 g of polyamidamine-moximine. This polyamidamine-amidamine system is referred to as PAI-1. Except changing the type and composition of carboxylic acids and diamine compounds, the other conditions were all operated under the same conditions, and the polyamidoamine-iminomine of PAI-2 ~ PAI-8 was synthesized. Table 22 shows the raw material composition of the obtained polyamidamine-imidate. Table 22 Raw material composition of Polyamidamine-Imidamine (unit ·· mole%)

No. Carboxylic acid diamine compound TMA TPA BDA DPM 4CB1B 5CCBOB 5CCB1P 6BOB 5CCDPM PAI-1 50.0 32.5 17.5 PAI-2 25.0 25.0 32.5 17.5 PAI-3 25.0 25.0 32.5 17.5 PAI-4 25.0 25.0 32.5 17.5 PAI-5 50.0 32.5 17.5 PAI -6 50.0 32.5 17.5 PAI-7 50.0 32.5 17.5 PAI-8 50.0 32.5 17.5 [Example 2] (Synthesis of N-substituted polyamide-imide) In a thermometer, mixer, condenser, raw material input port and nitrogen 75 591056 A 100 ml four-necked flask with 9825 pif 1 gas inlet was charged with PAI-1 (3.00 g) and dehydrated NMP (47.00 g) obtained in Example 1, and stirred and dissolved at 25 ° C for 1 hour. Thereafter, sodium hydride (0.565 g) was added to the solution, and the reaction was performed at 25 ° C for 15 hours, and further, the reaction was performed at 50 ° C for 3 hours, and then methyl iodide (2.402 g) was added to the reaction solution And further reacted for 15 hours. Using the obtained final reaction solution, and by the same reprecipitation operation as the aforementioned polyamidoamine_amidoamine (PAI-1), a polymer can be obtained, and then the polymer is dried under reduced pressure to obtain 2.2 g of N replaces polyamidamine-imidate. This N-substituted polyamidamine L imidate system is referred to as NPAI-1. Except for the replacement of the raw material polyamidoamine-iminomine or the replacement of methane iodide with other halides, the rest of the sequence is exactly the same as that of NPAI-1, and NPAI-2 ~ NPAI-12 can be synthesized. N replaces polyamidamine-imidate. Table 23 shows the substitution groups and weight average molecular weights of the obtained N-substituted polyamidoamines and imidates. Among them, NPAI-9 to NPAI-12 in Table 23 are substituted with ethane bromide, heptane, benzyl bromide, and anthracene bromide to replace methyl iodide to synthesize N substituted polyfluorene- Information on imine. 76 591056 9825 pif 1 Table 23 N-substituted polyamidoamines

No. Raw material polyamidoamine-iminomine substitution weight average molecular weight NPAI-1 PAI-1 methyl 59000 NPAI-2 PAI-2 methyl 72500 NPAI-3 PAI-3 methyl 45000 NPAI-4 PAI-4 methyl 57000 NPAI-5 PAI-5 methyl 66000 NPAI-6 PAI-6 methyl 52000 NPAI-7 PAI-7 methyl 53000 NPAI-8 PAI-8 methyl 48500 NPAI-9 PAI-1 ethyl 60000 NPAI-10 PAI -1 heptyl 59000 NPAI-11 PAI-1 T-based 60,000 NPAI-12 PAI-1 anthracene methyl 62000

[Synthesis Example 1] (Synthesis of Polyamic Acid) In a 500-ml four-necked flask equipped with a thermometer, a stirrer, a condenser, a raw material input port, and a nitrogen introduction port, DPM (4.891 g) and dehydrated NMP (90.0 g) were added. And dissolved under stirring under a stream of dry nitrogen. Keep the temperature of the solution at 5 ° C, then add PMDA (2.690g) and CBDA (2.419g) in this order, and react at 25 ° C for 30 hours. Thereafter, BC (100.0 g) was added to the reaction solution to obtain a polyamine solution (200 g) having a polymer concentration of 5.0% by weight. This polyamic acid solution was used as PA acid-1. The weight average molecular weight of the obtained polyamic acid was about 75,000. [Synthesis Example 2] (Synthesis of Polyamide) In a 500-ml four-necked flask equipped with a thermometer, a stirrer, a condenser, a raw material input port, and a nitrogen introduction port, TPA (3.216 g), 77 591056 9825 pifl DPM (1.919 g) and 4CB1B (4.866 g), and then added dehydrated NMP (8.63 g) and pyridine (9.33 g) to obtain a uniform solution. To this solution were sequentially added triphenyl phosphite (12.01 g), lithium chloride (4 g), and calcium chloride (I 2 g), followed by a reaction at 100 ° C for 2 hours. Using the obtained reaction solution, the polymer can be obtained by the same reprecipitation operation as the aforementioned polyamido-iminomine (PAM), and the polymer can be dried under reduced pressure to obtain 7.9 g of the polymer. Lamine. This polyamine system is referred to as PA-i. The weight average molecular weight of the obtained polyamide was about 88,000. [Synthesis Example 3] (Synthesis of N-substituted polyamide) In a 200-ml four-necked flask equipped with a thermometer, a stirrer, a condenser, a raw material input port, and a nitrogen introduction port, PA-1 (5.026 g) obtained in Synthesis Example 2 was added. ) And dehydrated NMP (26.39 g), and dissolved by stirring at room temperature. After adding sodium hydride (0.934 g) to the solution and reacting for 40 minutes, methane iodide (3.037 g) was further added and reacted for 1 hour. Using the obtained reaction solution, the polymer can be obtained by the same reprecipitation operation as the aforementioned polyamidoamine-iminomine (PAI-1), and the polymer can be dried under reduced pressure to obtain 3.5 g. N displacement polyamidamine. This N-substituted polyamine system is referred to as NPA-1. The weight-average molecular weight of the obtained N-substituted polyamine was about 52,000. [Synthesis Example 4] (Synthesis of soluble polyamide) In a 300-ml four-necked flask equipped with a thermometer, a stirrer, a condenser, a raw material inlet, and a nitrogen inlet, DPM (5.125 g) and 78 591056 9825 pif 1 4CBlB were added. (6.997g) and dehydrated NMP (100.Og), and dissolved by stirring under a stream of dry nitrogen. This solution was cooled to 5 degrees Celsius, and after adding BDA (7.879 g), it was reacted at 25 degrees Celsius for 15 hours to obtain a thick polyamic acid solution. To this solution were sequentially added dehydrated NMP (64.66 g) and anhydrous acetic acid (27.74 g), followed by a reaction at 100 ° C for 3 hours. Using the obtained reaction solution, the polymer can be obtained by the same reprecipitation operation as the aforementioned polyamidoamine-iminomine (PAI-1), and then the polymer is dried under reduced pressure to obtain 16.0g. Of soluble polyamidamine. This soluble polyamidine system is referred to as PI-1. The weight average molecular weight of the obtained polyamide was about 49,000. [Example 3-1] (Blend of lacquer) The NPAI-1 (0.10 g) obtained in Example 2 was added to the PA acid-1 (18.0 g) obtained in the synthesis example, and dissolved. The resulting solution was diluted into an NMP-BC mixed solvent (weight ratio 1/1) to obtain a varnish having a polymer concentration of 3% by weight. For the polyamic acid in this varnish, the ratio of N-exchanged polyamidamine-iminomine NPAI is 1/9 by weight. [Examples 3-2 to 3-12 and Comparative Examples 1 to 3] (The blending of lacquer) Except for NPAI-2 to 12 obtained in Example 2, PA-1 obtained in Synthesis Example 2, and NPA obtained in Synthesis Example 3 Except that -1 and PM obtained in Synthesis Example 4 replace NPAI-1, the rest are exactly the same as in Example 3-1, so that the corresponding polymers can be blended. In addition, PA-1 corresponds to Comparative Example 79 9825 pifl 1, NPA-1 corresponds to Comparative Example 2, and PI-1 corresponds to Comparative Example 3. [Example 4] (Production of cell for evaluation of alignment film) (1) Production of cell for evaluation of residual charge and voltage retention (cell for measuring electrical characteristics) Production of spin coating on a glass substrate with transparent electrode ITO attached The varnish containing the NPAI-1 obtained in Example 3-1 was applied, and after preliminary sintering at 80 ° C for about 5 minutes, heat treatment was performed at 250 ° C for 30 minutes. The surface of the substrate on which the alignment film is formed is placed on a honing apparatus to perform an alignment process by honing. Then, a gap material for 7 // is spread on the alignment film surface of the substrate, and then a substrate obtained in the exact same manner is overlapped with the surface formed with the alignment film facing inward. In addition, a sealant made of an epoxy resin hardener is formed around the two overlapping substrates with a liquid crystal injection hole remaining, so that an autoparallel cell having a gap of 7 / zm can be obtained. The following liquid crystal composition was injected into the cell, and then a light curing agent was applied to the liquid crystal injection hole, and then UV light was irradiated to harden it to close the injection port. Next, a heat treatment was performed at 100 ° C for about 30 minutes to serve as a cell for evaluating the residual charge and the voltage retention rate. The varnishes obtained in Examples 3-2 to 3-12 and Comparative Examples 1 to 3 were prepared in the same manner as the cells for evaluating the residual charge and the voltage holding ratio. The composition of the liquid crystal composition used is as follows. The NI point of this composition is 100.0 degrees Celsius, and the refractive index anisotropy is 0.093. 591056

9825 pif 1

17wt.% 17wt.% 16wt.%

lOwt.%

5wt.%

lOwt.%

6wt.%

6wt.% 13wt.% 81 591056 9825 pifl (2) Production of cells for forward leaning measurement is the same as that for the production of cells for electrical characteristics, except that the gap material is replaced by 20 // Way, an autoparallel cell with a cell thickness of 20 // is produced, wherein the cell line is used as a cell for measuring the anteversion angle. The liquid crystal composition used in the production of this cell is the same liquid crystal composition used in the production of the cell for measuring electrical characteristics. 4 [Example 5] ^ (Evaluation of lacquer) (1) Evaluation method i) Measurement of residual charge (Residual charge was measured by the method described in "Miyake et al.'S Gazette EID91-U1, P19") Hysteresis. Furthermore, an alternating current of 50 mV and 1 kHz was applied to the liquid crystal cell to measure a direct current triangular wave having a frequency of 0,0036Ηζ. ii) Measurement of voltage holding rate

The voltage holding ratio was measured by the method described in "Minamata et al., Proceedings of the 14th LCD Symposium, p78". The measurement conditions are a gate width of 69 // s, a frequency of 60 Hz, a wavelength height of ± 4.5 V, and a measurement temperature of 60 degrees Celsius. -

Hi) Measurement of rake angle The rake angle of the liquid crystal is measured by a rotating crystal method. iv) Evaluation of liquid crystal alignment The liquid crystal alignment is observed under a polarization microscope 82 591056 9825 pif 1 when measuring the forward tilt angle, and the presence or absence of domain is determined. V) Evaluation of applicability Coating the lacquer with a spin-coating method, pre-rolling at 80 ° C for about a minute, and then visually observing the alignment film after heating at 250 ° C for 30 minutes. Surface, and determine whether there is uneven cloth. ~ ~ (2) Evaluation results The evaluation liquid crystal cells corresponding to the lacquer obtained in Example 4 were evaluated by the above method. The results are shown in Table 24. Table 24 Evaluation results Liquid crystal alignment agent lacquer polymer residual electricity f (mV) Voltage retention (%) Forward tilt angle (degrees) Liquid crystal alignment coating property Example 3-1 NPAI-1 6 98.4 3.0 Good Good Example 3-2 NPAI-2 12 98.6 2.6 Good example 3-3 NPAI-3 8 98.2 3.1 Good example 3-4 NPAI-4 3 98.2 3.2 Good example 3-5 NPAI-5 15 98.0 5.5 Good example 3-6 NPAI-6 26 98.4 8.4 Good Good Example 3-7 NPAI-7 12 98.8 5.6 Good Good Example 3-8 NPAI-8 18 98.2 7.7 Good Good Example 3-9 NPAI-9 14 98.5 3.0 Good Good Example 3-10 NPAI-10 8 98.6 2.2 Good Good Example 3-11 NPAI-11 10 Γ 98.5 2.5 Good Good Example 3-12 INPAI-12 8 98.5 2.5 Good Comparative Example 1 PA-1 133 95.2 3.2 Good Poor Comparative Example 2 Wide NPA-1 15 98.4 2.2 Slightly Bad Good Comparative Example 3 PI-1 23 98.8 3.5 Good Bad Residual Charge: The lower the better, the higher the voltage retention, the better. In addition, from the above results, it can be seen that the varnish using the N-substituted polyamidoamine-iminomine of the present invention and the polyamidoamine of the comparative example, the N-substituted polyamidoamine, and the fluorene of 83 591056 9825 pif 1 soluble polyamidoamine In comparison with lacquers, it is a substance having a better total and average among the electrical characteristics such as the residual electric charge, the voltage holding ratio, etc., or the orientation characteristics such as the tilt angle, the liquid crystal alignment, and the coating properties. [Industrial Applicability] The advantages of using the N-substituted polyamidoamine-iminomine of the present invention are as follows. The coating property of the obtained liquid crystal alignment agent lacquer is better. The obtained liquid crystal alignment film has good alignment, and its forward tilt angle can be arbitrarily adjusted. Moreover, the liquid crystal display element having the liquid crystal alignment film does not need to undergo sintering, that is, it has a large voltage holding ratio and a small residual charge. The liquid crystal alignment agent paint 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). Since the forward tilt angle can be arbitrarily adjusted to obtain better electrical characteristics, it can also be used as an alignment agent in STN-type liquid crystals, ferroelectric liquid crystals, or anti-ferroelectric liquid crystals. In addition, the thin film composed of the liquid crystal alignment agent varnish has good electrical characteristics, so it can also be used as a protective film or an insulating film. 84

Claims (1)

591056 9825 pifl revised and replaced the scope of the application for patents: 1. A polyamidoamine-iminomine, characterized by: having the structural unit represented by formula (1-1), or having formula (1-2) And the structural unit represented by formula (1-3), 0 In the above formula, the symbols used are defined as follows: τ1, T2, and T3 refer to organic residues derived from carboxylic acids, and D1, D2, and D3 refer to organic residues derived from diamine compounds. Among them, T1, T2, and T3 At least one of D1, D1, D2, and D3 is an organic residue having a side chain group having a carbon number of 3 or more; R1, R2, and R3 refer to independent hydrogen or a monovalent organic group, and the monovalent organic group is selected from It has an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an unsaturated aliphatic group having 2 to 15 carbon atoms, and an alicyclic ring. Formula group, aromatic hydrocarbon group, oxygen-containing heterocyclic group, group having nest skeleton, group having carbonyl group, organosilyl group, and group having organosilyl group, etc. In the group 85 591056 9825 pif 1 of the composition, any hydrogen of the alkyl group and alkylene group contained in such organic groups can also be replaced with fluorine; in the aromatic hydrocarbon group, any hydrogen of the aromatic ring can also be replaced with alkyl group, Alkoxy or -CN; any hydrogen of the aforementioned alkyl and alkoxy groups can also be replaced with fluorine; as an aromatic hydrocarbon group The alkylene group on the aralkyl group can also be bonded to the aromatic ring by an oxygen atom; and 30 mol% or more of the total amount of R1 to R3 in the polyamidoamine-iminomine molecule is a monovalent organic group . 2. The polyamidoamine-iminomine according to item 1 of the scope of the patent application, characterized in that at least one of the organic residues derived from the diamine compound is selected from the group consisting of formulae (2) to (5), respectively. Groups of groups, < The symbols used in formula (2) are defined as follows: R4 means hydrogen or an alkyl group having 1 to 12 carbons; ring A means 1,4-phenylene or 1,4-cyclohexylene, And any hydrogen of the aforementioned ring can also be replaced with an alkyl group having 1 to 4 carbon atoms; Z1 and Z2 are individually independent single bonds, -CH2-, -CH2CH2- or Is an integer from 0 to 5, tl is an integer from 0 to 3, and t2 is an integer from 0 to 3; and when tl is 2 or 3, a plurality of Z1 may be the same as each other, It can also be different from each other. When t2 is 2 or 3, the plurality of Z2 can be the same as each other or different from each other. 86 591056 9825 pifi χ ~ σ ^ χ— (tr The position of the radical in the 'benzene ring in formula (3) is arbitrary, and the symbols in this formula are defined as follows: X1 and X2 are individual independent single bonds, _ 〇_, -00-, -NH-, -CONH-, or an alkylene group having 1 to 12 carbon atoms; G1 and G2 are individually independent single bonds or divalent groups containing 1 to 3 rings, and The aforementioned ring system is selected from the group consisting of an aromatic ring and an alicyclic ring; R5 means hydrogen, fluorine, -CN, ^ -0H, an alkyl group having 1 to 12 carbons, or 1 to 12 carbons And any hydrogen of this alkyl group can be replaced with fluorine; and when G2 is a single bond and X2 is not a single bond or alkylene, R5 is hydrogen or alkyl, and when G1 and G2— In the case of the same single bond, the total carbon number of X1, X2 and R5 is 3 or more; In formula (4), any hydrogen of 1,4-phenylene can also be replaced with an alkyl group having 1 to 4 carbon atoms, And the symbols in this formula are defined as follows: 撝 X3 and X4 are individual independent single bonds, -CH2-, -CH2CH2- or; R6 and R7 are individual independent hydrogen, alkyl groups having 1 to 12 carbons Or a fluoroalkyl group with a carbon number of 1, 12; ul and u2 are independent of each other An integer of 0 to 3; and at least one side of R6 and R7 is an alkyl group having a carbon number of 3 or more or a fluoroalkyl group having a carbon number of 3 or more. When ul is 2 or 3, a plurality of X3 may be the same as each other or different from each other. When u2 is 2 or 3, a plurality of X4 may be the same as each other or different from each other; 87 (5) 591056 9825 pif 1 In formula (5), the bonding position of the substituent and the free group with respect to the benzene ring is arbitrary, and the symbol in this formula is defined as follows: R8 is hydrogen or a radical with 1 to 12 carbon atoms And arbitrary -CH2- can also be replaced by; X5 means a single bond or an alkylene having 1 to 5 carbon atoms, and any -CH2- in this alkylene can also be replaced by; m is an integer of 0 to 3, and η is 1 to An integer of 5. 3. The polyamidoamine-iminomine as described in item 1 or 2 of the scope of the patent application, characterized in that R1 in formula (1-1) and R2 and R3 in formula (1-2) are Individually independent monovalent organic groups having a hydrogen or carbon number of 5 or less, and more than 50 mol% of the total amount of R1 to R3 in the molecule are monovalent organic groups. 4. The polyamidoamine-iminomine as described in item 3 of the scope of patent application, characterized in that the monovalent organic group having a carbon number of 5 or less is selected from an alkane having a carbon number of 5 or less A group consisting of a hydroxyl group, a hydroxyalkyl group having a carbon number of 5 or less, and an alkoxyalkyl group having a carbon number of 5 or less, in which 70% by mole or more of the total amount of R1 to R3 in the molecule is the carbon The number is a monovalent organic group of 5 or less. 5. A liquid crystal alignment agent lacquer, which is characterized in that it contains a polymer compound and a solvent, and the proportion of the polymer compound is 0.1% to 4% based on the total weight of the lacquer. % By weight, where the polymer compound is N-substituted polyamidoamine-iminomine or a mixture of N-substituted polyamidoamimine and other polymers, and the N-substituted polyamidoamine-amidomine is as described in the application The other polymers of polyamidoamine-iminomine described in item 1 of the patent scope are selected from the group consisting of polyamic acid, soluble polyamidoamine, polyamidoamine, and other polyamidoamines-88 9825 pif 1 Select at least one of the amine groups. 6. A liquid crystal alignment agent lacquer, characterized in that it contains a polymer compound and a solvent, and the proportion of the polymer compound is 0.1 to 40% by weight based on the total weight of the lacquer. %, Wherein the polymer compound is N-substituted polyamidoamine-iminomine or a mixture of N-substituted polyamidoamine-iminomine and other polymers, and the N-substituted polyamidoamine-iminomine is as described in the application The other polymers are selected from the group consisting of polyamic acid, soluble polyimide, polyamidine, and other polyamidamine-imidamine groups described in item 2 of the patent scope. Choose at least one group. 7. A liquid crystal alignment agent lacquer, characterized in that it contains a polymer compound and a solvent, and the proportion of the polymer compound is 0.1% to 40% by weight based on the total weight of the lacquer. Wherein, the polymer compound is N-substituted polyamidoamine-iminomine or a mixture of N-substituted polyamidoamine-iminomine and other polymers, and the N-substituted polyamidoamine-iminomine is as described in the patent application scope. The polyamidoamine-iminomine described in item 3, and other polymers are selected from the group consisting of polyamic acid, soluble polyamidoamine, polyamidoamine, and other polyamidoamine-amidoamine groups. Select at least one of the ethnic groups. 8_—A kind of liquid crystal alignment agent lacquer, characterized in that it contains a polymer compound and a solvent, and the proportion of the polymer compound is 0.1% to 40% by weight based on the total weight of the lacquer, wherein The polymer compound is an N-substituted polyamidoamine-iminomine or a mixture of N-substituted polyamidoamine-iminomine and other polymers, and the N-substituted polyamidoamine-iminomine is as described in the patent application. Polyamine-imidoamine according to item 4, the other polymer is selected from the group consisting of polyamic acid, soluble polyimide, polyamidine, and other polyamines-89 594 ^ §4 9825 pif 1 Select at least one of the tribes group. 9. A liquid crystal display element, a transparent electrode is provided on a pair of transparent substrates, a liquid crystal alignment film is formed on the transparent electrodes, and the substrates are combined face-to-face through a gap material, and then a liquid crystal is sealed. To obtain the liquid crystal display element, at least one of the liquid crystal alignment films formed on the substrates is a liquid crystal alignment film formed using a liquid crystal alignment agent paint as described in item 5 of the patent application scope. 10 · —A kind of liquid crystal display element, a transparent electrode is provided on a pair of transparent substrates, a liquid crystal alignment film is formed on the transparent electrodes, and the substrates are combined in a face-to-face manner through a gap material and then sealed. A liquid crystal display element is obtained by using a liquid crystal material. At least one of the liquid crystal alignment films formed on the substrates is a liquid crystal alignment film formed by using a liquid crystal alignment agent paint as described in item 6 of the patent application scope. . 11. A liquid crystal display device, a transparent electrode is provided on a pair of transparent substrates, a liquid crystal alignment film is formed on the transparent electrodes, and the substrates are combined face-to-face through a gap material, and then a liquid crystal material is sealed. To obtain the liquid crystal display element, at least one of the liquid crystal alignment films formed on the substrates is a liquid crystal alignment film formed by using a liquid crystal alignment agent paint as described in item 7 of the scope of patent application. I2. A liquid crystal display element, a transparent electrode is provided on a pair of transparent substrates, a liquid crystal alignment film is formed on the transparent electrodes, and the substrates are combined in a face-to-face manner with a gap material, and then sealed in a The liquid crystal display element is obtained by half-doping a liquid crystal material, and at least one of the liquid crystal alignment films formed on the substrates is formed by using as described in item 8 of the scope of patent application; 90 591056 9825 pif 1 crystal alignment agent paint Liquid crystal alignment film.