TW201141912A - Liquid crystal display element and liquid crystal aligning agent - Google Patents

Abstract

Disclosed are: a vertically aligned liquid crystal display element which can be increased in the response speed without addition of a photopolymerizable compound; a method for producing the vertically aligned liquid crystal display element; and a liquid crystal aligning agent which is suitable for the vertically aligned liquid crystal display element. Specifically disclosed is a method for producing a vertically aligned liquid crystal display element wherein: liquid crystal alignment layers are respectively formed by coating two substrates with a liquid crystal aligning agent that contains at least one material that is selected from the group consisting of polyamic acids having a side chain (A) that vertically aligns liquid crystals and a photoreactive side chain (B) and polyimides obtained by imidizing the polyamic acids; the two substrates are arranged so that the liquid crystal alignment layers face each other; a liquid crystal layer is interposed between the two substrates; and the liquid crystal layer is irradiated with ultraviolet light while being applied with a voltage.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display element of a vertical alignment type which is produced by irradiating ultraviolet rays in a state where a voltage is applied to liquid crystal molecules, and is used in the manufacture of the liquid crystal display element. Liquid crystal alignment agent. [Prior Art] A liquid crystal display device in which a liquid crystal molecule that vertically aligns a substrate is responsive to an electric field (also referred to as a vertical alignment method) includes a step of irradiating ultraviolet rays to a liquid crystal molecule while applying a voltage thereto. By. In these liquid crystal display elements, a photopolymerizable compound is generally added to the liquid crystal composition in advance. In general, the tilt direction of the liquid crystal molecules in response to the electric field is controlled by a protrusion provided on the substrate or a slit provided on the display electrode, but a photopolymerizable compound is added to the liquid crystal composition and subjected to the above steps. In the liquid crystal display device, since a polymer structure in which the tilt direction of the liquid crystal molecules is stored is formed on the liquid crystal alignment film, the response speed of the liquid crystal display element is accelerated as compared with the method of controlling the tilt direction of the liquid crystal molecules only by protrusions or slits ( Refer to, for example, Patent Document 1). In addition, when the photopolymerizable compound is added to the liquid crystal alignment film without being added to the liquid crystal alignment film, the response speed of the liquid crystal display element which has undergone the above steps is also accelerated (see, for example, Non-Patent Document 1). As for the technique other than the above, there is a light alignment technique for controlling the tilt direction of liquid crystal molecules by ultraviolet irradiation (see, for example, Patent Document 2). However, in the photo-alignment technique, the technique of imparting an anisotropy to the liquid-based film of the liquid-5-201141912 is used in advance, and the technique of the direction of the liquid crystal molecules which are actually tilted as described above is completely different. [PRIOR ART DOCUMENT] Patent Document 1: JP-A-2003-307720 Patent Document 2: JP-A-2002-114437 Non-Patent Document Non-Patent Document 1: SID 09 Digest 45. 1 [Summary of the Invention] [ The object of the present invention is to provide a liquid crystal display element which is a liquid crystal display element of a vertical alignment type which is formed by irradiating ultraviolet rays while applying a voltage to liquid crystal molecules, in which liquid crystal composition or liquid crystal is not present. The addition of the photopolymerizable compound to the alignment film can still accelerate the response speed; a method for producing the same, and a liquid crystal alignment agent suitable for the liquid crystal display element. [Means for Solving the Problems] The features of the present invention are as follows. [1] A method for producing a liquid crystal display device of a vertical alignment type, comprising: a polylysine containing a side chain (A) having a liquid crystal alignment direction and a photoreactive side chain (B); At least one liquid crystal alignment agent selected from the group consisting of polyimine obtained by imidization is coated on two substrates 201141912 to form a liquid crystal alignment layer, so that the liquid crystal alignment layer is disposed in two opposite directions. In the sheet substrate, a liquid crystal layer is sandwiched between the two substrates, and on the one hand, a voltage is applied to the liquid crystal layer to irradiate ultraviolet rays. [2] The method for producing a liquid crystal display device according to the above [1], wherein the liquid crystal alignment agent is a liquid crystal alignment containing at least one of polyamic acid and polyamidene obtained by imidating the ruthenium The polyamine acid obtained by reacting a diamine component with a tetracarboxylic dianhydride, the diamine component comprising a diamine having a side chain (A) which vertically aligns the liquid crystal and having light The diamine of the reactive side chain (B). [3] The method for producing a liquid crystal display device according to the above [1], wherein the side chain (A) for vertically aligning the liquid crystal is represented by the following formula (a) [Chemical Formula 1] (a) ( In the formula (a), '1, m and η each independently represent an integer of 0 or 1. ' R1 represents an alkylene group having 2 to 6 carbon atoms, -0-, -COO-, -OCO-, -NHCO-, - CONH- or an alkyl-ether group having 1 to 3 carbon atoms, R2, R3 and R4 each independently represent a phenyl or cycloalkyl group, and R5 represents a hydrogen atom and a linear alkyl group having 5 to 18 carbon atoms. Or a fluorine-containing alkyl group, or an aromatic cyclic group, an aliphatic cyclic group, a heterocyclic group or a macrocyclic group composed of the above. [4] The method for producing a liquid crystal display device according to any one of the above aspects, wherein the photoreactive side chain (B) is represented by the following formula: Table 201141912 [Chem. 2] HR7- R8_R9 (b) (r6 袠 < only 7K - C Η 2 -, - Ο -, - C Ο Ο -, - NHC Ο -, - N Η -, -CH20- ' Λτ , , N(CH3)-, -CON(CH3)- or -N(CH3)CO-, R7 represents a linear alkyl group having a carbon atom of 1 W 1 to 20 (the alkyl group may be unsubstituted or substituted by a wear atom), and further Any -CH2- of the alkyl group may be substituted by -CF2-, -CH=C Η - Bfr e with the following substituents (the substituents are not adjacent), and the substituents are: -0-, -COO-, - NHCO-, -NH-, carbocyclyl or heterocyclic, R ^^'CH2-' -Ο- ' -coo-' -OCO- ' -NHCO- ' -NH-, -N(CH3)-,- c〇N(CH3)-, -N(CH3)CO-, carbocyclyl or heterocyclyl 'R9 represents a vinylphenyl group, a _CRiQ=CH2 group, a carbocyclic group, a heterocyclic group or a group represented by the following formula, R1Q represents a hydrogen atom or a methyl group which may be substituted by a fluorine atom), [Chemical 3]

-8 201141912

201141912 [Chemical 4]

[7] A liquid crystal display element of a vertical alignment type, comprising: two substrates having a liquid crystal alignment layer containing a side chain (A) having a vertical alignment of liquid crystals and a photoreaction Forming at least one liquid crystal alignment agent selected from the group consisting of polylysine of side chain (B) and polyamidimide obtained by imidization of ruthenium: in order to align said liquid crystal alignment layer The liquid crystal cell of the liquid crystal layer is sandwiched between the two substrates arranged in the manner; and a means for irradiating ultraviolet rays when a voltage is applied to the liquid crystal layer. [8] A liquid crystal alignment agent comprising a polyaminic acid having a side chain (A) in which a liquid crystal is vertically aligned and a photoreactive side chain (B), and a polyazide obtained by imidating the oxime At least one selected from the group consisting of amines. [9] A liquid crystal alignment agent comprising a diamine component and a tetracarboxylic acid comprising a diamine having a side chain (A) having a side chain (A) vertically aligned with a liquid crystal and a diamine having a photoreactive side chain (B) a liquid crystal alignment agent selected from the group consisting of polylysine obtained by the reaction of acid dianhydride and polyimine obtained by imidization of ruthenium, characterized by the above-mentioned photoreactive side chain (B) The diamine is represented by the following formula (2), -10-201141912 [Chemical 5] h2 1> H2N ^ • R7 to R8_R11 (2) i R 6 mourning, clothing 7κ · C Η 2 -, - Ο -, - C Ο _ _, - NHC Ο -, - Ν Η -, C Η Ο 2 ·,, N(CH3)-, -CON(CH3)- or -n(ch3)co-, R7 represents the number of carbon atoms • 20 a linear alkyl group (the alkyl group may be unsubstituted or may be passed through the stomach and stomach + $ generation), and further an alkyl group may be substituted with a substituent of -CF2-, _eH_eH' (the The substituents are not adjacent to each other, and the substituents are: -〇_, -COO-, -NHCO-, -NH-, carbocyclyl or heterocyclic, r8^tk-CH2-'-Ο-'-COO -' -OCO- ' -NHCO- ^ -NH-, -N(CH3)-, -c〇N(Ch3)- or -N(CH3)CO-, R11 represents vinylbenzene The liquid crystal alignment agent according to any one of the above [7] to [9], wherein the liquid crystal alignment agent according to any one of the above [7] to [9], The diamine having the side chain (A) in which the liquid crystal is vertically aligned is represented by the following #(1), [1] 0~ri~(r2Hr3Hr4)~r5 H2N lm π (Formula (a) Wherein m and η each independently represent an integer of 0 or 1, and Ri -11 - Table 201141912 shows an alkyl group having 2 to 6 carbon atoms, -0-, -COO-, ·〇(:0·, -:^(3) - (3) Anthracene- or a carbon atom (1) alkyl-ether group, !^2, 11- and R4 each independently represent a phenyl or cycloalkyl group, and R5 represents a hydrogen atom, and the number of carbon atoms is 5 to 18. a linear alkyl group or a fluorine-containing alkyl group, or an aromatic ring group, an aliphatic ring group, a heterocyclic group or a macrocyclic group composed of the above). [11] A liquid crystal alignment as described in the above [10] The above-mentioned diamine having a side chain (A) in which the liquid crystal is vertically aligned is represented by the above formula (1) and each of I, m and η is 1, R 2 is a phenyl group, and R 3 is a phenyl group or a stretching group. a cyclohexyl group, R 4 is a cyclohexyl group, R 5 is an alkyl group having 2 to 24 carbon atoms, or 1, 5 and η are 0, and R 5 is an alkyl group having 12 to 22 carbon atoms. The liquid crystal alignment agent of any one of the above-mentioned [8] to [1], wherein the diamine having a side chain (Α) in which the liquid crystal is vertically aligned has any of the following structures. Diamine, [Chemical 8]

[13] A liquid crystal alignment film obtained by using the liquid crystal alignment agent according to any one of the above [8] to [12]. [Effect of the Invention] According to the present invention, there is provided a liquid crystal display element which can accelerate the response speed (shortening response time) even when no photopolymerizable compound is added to the liquid crystal composition or the liquid crystal alignment -12-201141912 film. Further, the liquid crystal alignment agent of the present invention is used in a liquid crystal display device of a vertical alignment type which is formed by applying ultraviolet rays to a liquid crystal molecule while applying a voltage to the liquid crystal composition or the liquid crystal alignment film without adding a photopolymerizable compound. A liquid crystal display element in which the response speed of the liquid crystal is fast (the reaction time is shortened) can still be obtained. [Embodiment] <Side chain in which the liquid crystal is vertically aligned> The side chain (also referred to as side chain A) which vertically aligns the liquid crystal is a side chain having the ability to vertically align liquid crystal molecules with respect to the substrate, and the structure thereof is as long as This ability is not limited. As the side chain A, for example, an alkyl group having a long chain, a fluoroalkyl group having a long chain, a cyclic group having an alkyl group or a fluoroalkyl group at the terminal, a steroid group and the like are known, and are also preferably used in the present invention. These groups may be directly bonded to the main chain of polyperuric acid or polyimine, or may be bonded through a suitable bonding group as long as they have the above-mentioned ability. The side chain A can be exemplified by the following formula (a). [Chemistry 9]

R1 in the above formula (a) represents a carbon atom number of 2 to 6, preferably 2 to 4, a stretching group, -0-, -COO-, -OCO-, -NHCO-, -CONH-, or a carbon number. 1 to 3 alkyl-ether group (-CC-0-), wherein in terms of ease of synthesis -13-201141912, -Ο-, -COO-, -CON Η-, or the number of carbon atoms The alkylene-ether group of 1 to 3 is preferred. The above R2, R3 and R4 each independently represent a phenyl or a cycloalkyl group. From the viewpoints of the easiness of synthesis and the ability to align the liquid crystal vertically, it is preferable to use a combination of 1, m, η, R2, R3 and R4 shown in the following table: Table 1] I m η R2 R3 R4 1 1 1 phenyl extended phenylcyclohexyl 1 1 1 phenyl extended cyclohexyl extended cyclohexyl 1 1 1 phenyl extended cyclohexyl extended cyclohexyl 1 1 0 phenyl extended phenyl 1 1 phenyl extended cyclohexyl - above R5 represents a hydrogen atom, an alkyl group having 2 to 24 carbon atoms, preferably 5 to 8 or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring or a macrocyclic group constituted by the above. When at least one of l, m, and η is 1, the structure of R5 is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms, or a fluorine-containing alkyl group having 2 to 14 carbon atoms, more preferably a hydrogen atom. Further, when the number of carbon atoms is 2 to 12, preferably 2 to 10, or the fluorine-containing alkyl group, when l, m, and η are fluorene, the structure of R5 is preferably 12 to 22' in carbon. a -20 alkyl group or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a large cyclic group composed of the above, more preferably an alkyl group having 12 to 20 carbon atoms, preferably 12 to 18 carbon atoms. Base or fluorine-containing alkyl group. The ability to make the liquid crystals vertically aligned varies with the structure of the side chain '. However, in general, when the amount of the side chain A contained in the polymer is more than -14,194,912, the ability to vertically align the liquid crystal is also improved. The less the less, the lower. Further, the side chain A having a cyclic structure tends to vertically align the liquid crystal even when the content is small compared to the side chain A of the long-chain alkyl group. The amount of the side chain A in the polyamic acid or the polyimine used in the present invention is not particularly limited as long as it is a range in which the liquid crystal alignment film can vertically align the liquid crystal, but is relatively larger than the total amount of the diamine used. Good for 5~50%, better for 1〇~3 0%. However, the amount of the side chain A is present in the liquid crystal display element having the crystal alignment film, and in the case where the response speed of the liquid crystal is made faster, the amount of the side chain A is exhausted in the range in which the vertical alignment can be maintained. It may be less preferred. <Photoreactive side chain> The above-mentioned photoreactive side chain (also referred to as side chain B) is a side chain having a functional group capable of causing a photoreaction by irradiation of ultraviolet rays to form a covalent bond, and its structure is as long as it is There is no limit to this ability. As for the side chain B, for example, it is known to have a vinyl group, an acrylic group, a methacryl group, a fluorenyl group, a cinnamyl group, a cholesterol cyloid group, a coumarin group, a maleimine group, a stilbene group (stilbene). A side chain or the like of a group or the like is preferably used as the photoreactive group in the present invention. These groups may be directly bonded to the main chain of polyperuric acid or polyimine, as long as they have the above-mentioned ability, or may be bonded through a suitable bond group. The above-mentioned side chain B can be exemplified by the following formula (b): [Chemical Formula 10] A r6-r7-r8-r9 (b) -15- 201141912 R6 in the above formula (b) represents -(^2-, - 0-, -]^-, -1^((:113)-, -CONH-, -NHCO-, -CH2〇-, -COO-, -oco-, -CON(CH3)-, or -N( CH3)CO-.R6 can be formed by general organic synthesis method, but from the viewpoint of easiness of synthesis, -CH2-, -ο-, -COO-, -NHCO-, -ΝΗ-, or -CH20- R7 in the above formula (b) represents a linear alkyl group having 1 to 20 carbon atoms (the alkyl group may be unsubstituted or substituted by a fluorine atom), and further an alkyl group may be -CH2 - may be substituted by -CF2-, -CH=CH-' or with the substituents described below (the substituents are not adjacent). Substituents: -Ο-, -COO-, -NHCO-, -NH-, Carbocyclic group and heterocyclic group. The carbocyclic group and the heterocyclic group are specifically exemplified by the following structures, but are not limited thereto. [Chemical 11] Ο Ο ΟΌ 00 0-0 0^-0

[化 12]

The above alkyl group of R7, in order to make the response speed faster, is preferably -16 201141912 R6 and R8 between the soft spacer (connecting the base of R6 and R8)' to improve the reaction efficiency of the photoreactive group, r7 It is preferably a linear chain extending to the base of the carbon atom number 丨20, preferably 2~8. R8 in the above formula (b) represents -匸1^-, -. -, -!^-, -!^^!^)-, -CONH-, -NHCO-, -CH20-, _COO-, -OCO-, -CON(CH3)-, -N(CH3)CO-, Carbocyclyl or heterocyclic group. Among them, -CH2-, -〇-, -COO-, -OCO-, -NHCO-, -NH-, carbocyclic or heterocyclic groups are preferred from the viewpoint of ease of synthesis. Preferred specific examples of the carbocyclic group and the heterocyclic group are as described above. R8 is preferably -CH2-'-〇-, -coo-, -OCO-, -NHCO- or -NH- from the viewpoint of response speed. R9 in the above formula (b) represents a vinylphenyl group, -CR1 (I = CH2, a carbocyclic group, a heterocyclic group, or a group represented by the following formula: Rig represents a hydrogen atom or a methyl group which may be substituted by a fluorine atom. 13]

-17- 201141912 [Chem. 16]

[Chem. 19]

[化2Π

From the viewpoint of photoreactivity, R9 is more preferably a vinylphenyl group, CH=CH2, -C(CH3)=CH2 or a group described below. • 18 - 201141912 [Chem. 22]

[Chem. 23] [Chem. 24]

From the viewpoint of the response speed, R9 is preferably a vinyl group, a group of -C(CH3) = CH2 or less. [Chem. 25] - 0

The amount of the side chain B in the polyacrylic acid or the polyimine used in the present invention is not particularly limited as long as it can accelerate the range of the liquid crystal response speed in the liquid crystal display element, but is used in comparison with the second used. The total amount of the amine is preferably from 10 to 95 mol%, more preferably from 60 to 95 mol%. The amount of the side chain B present In the case where the liquid crystal response speed in the liquid crystal display element is made faster, it is preferably as much as possible within a range that does not affect other characteristics. <Polyuric acid> The above polylysine having a side chain A and a side chain B in the present invention may be -19-201141912 by a diamine having a side chain A and/or a diamine having a side chain B and four By reacting a carboxylic acid dianhydride or by reacting a diamine with a tetracarboxylic dianhydride having a side chain A and/or a tetracarboxylic dianhydride having a side chain B, thereby allowing a diamine having a side chain A And/or a reaction of a diamine having a side chain B with a tetracarboxylic dianhydride having a side chain A and/or a tetracarboxylic dianhydride having a side chain B. Among them, in terms of easiness of synthesis of the starting material, it is preferred to carry out the reaction by a diamine having a side chain A and/or a diamine having a side chain B and a tetracarboxylic dianhydride. <Diamine Compound Having Side Chain A> A diamine compound having a side chain A (hereinafter also referred to as diamine A) may, for example, be an alkyl group, a fluorine-containing alkyl group or an aromatic ring in a side chain of a diamine. An aliphatic ring, a heterocyclic ring, or a diamine having a large cyclic substituent consisting of the above. Specifically, it may be mentioned as a diamine having a side chain represented by the above formula (a). More specifically, the diamine represented by the following formula (1), (3), (4), or (5) is exemplified, but it is not limited thereto. [Chem. 26]

The definitions of l, m, n, and R1 to R5 in the formula (1) are the same as those in the above formula (a). -20- 201141912 [化27]

In the formula Ο) and in the formula (4), Α!. Represents -(:00-,-0€:0-, -(:01^11-, -NHC〇-, -ch2-, _〇-, -CO., or _NH_, and Ah represents a single bond or extension Phenyl.a represents a side chain A, and a' represents an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a large cyclic group composed of the groups.) CH2)a1—Ai7~(CH2)a2-A1s-A15-{ V~(~( ))^3~Al4 (5) In the formula (5), A14 represents a carbon atom which can be substituted by a fluorine atom: 3~20 In the courtyard, A15 represents 1,4 -cyclohexylene, or 1,4_phenyl. A16 represents an oxygen atom or -COO-* (however, a bond bond of "*" is added to bond with A3), and a17 is an oxygen atom or -COO-* (however, a bond of "*" is added and ( CH2) a2 bond)). Further, a is an integer of 0 or 1, a2 is an integer of 2 to 1 ,, and a3 is an integer of 0 or 1. The bonding position of the two amine groups (-NH2) in the formula (1) is not limited. Specifically, it is listed as the position of 2, 3 of the bonding group on the benzene ring with respect to the side chain, the position of 2, 4, the position of 2, 5, the position of 2, 6, the position of 3, 4, 3, 5 position. Among them, from the viewpoint of the reactivity in synthesizing polyamic acid, the position of 21 - 201141912 2, 4, the position of 2, 5, or the position of 3, 5 is preferable. When considering the easiness of synthesizing a diamine compound, the position of &amp; 2, 4 and the position of $ 3, 5 are better. The specific structure of the formula (1) can be exemplified by the diamine represented by the following formula [A] [A24], but is not limited thereto. [化29]

(10) Xincheng, Feifei

[A-1J [Ap2] [A&gt;3J In the formula [A-1]~[A·5], Ai is an alkyl group having 2 to 24 carbon atoms or a fluoroalkyl group.

As

A3 In the formula [A-6] and the formula [A-7], A2 represents -〇-, -OCH2-, -CH2〇_, -COOCH2-, or -CH2OCO-, and A3 represents an alkyl group having 1 to 22 carbon atoms. , alkoxy, fluoroalkyl or fluoroalkoxy. -22- 201141912 [Chem. 31]

[A-8] [A-9] [A-10] In the formula [A-8]~[A-10], A4 represents -COO-, -OCO-, -CONH- '-NHCO- ' -COOCH2 - ' -CH2OCO- ' -CH2O- ' -OCH2-, or -CH2-. A5 represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a gas-containing base or a fluorine-containing (homo-oxyl group).

In the formula [A-11] and the formula [A-12], A6 represents -COO-, -OCO-, -CONH-, -NHCO- '-COOCH2-, -CH2OCO-, -CH20-, -OCH2-, - CH2-, -0-, or -NH-, A7 represents a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxy group. [化33]

-23- 201141912 In the formula [A -13] and the formula [A-l4], 'As represents a hospital group having 3 to 12 carbon atoms, and the cis-trans isomerization of 1,4-cyclohexylene is respectively Trans isomer. [n34] nh2 nh2

h^&quot;I^-Q-〇-〇-a9 h2n [Α·15] In the formula [A-15] and the formula [A-16], 'A9 represents an alkyl group having 3 to 12 carbon atoms, and 1, The cis-trans isomerism of the 4-cyclohexylene group is a trans isomer, respectively. [化35]

[化36]

[A-21] -24- 201141912 [Chem. 37]

Specific examples of the diamine represented by the formula (3) include diamines represented by the following formula [A 25] [A-30], but are not limited thereto. [化38]

In the formula [A-25]~form [A-30], A12 represents -COO·, -OCO-, -CONH-, -NHCO-, -CH2-, -0-, -CO-, or -NH-, Αι; (indicating an alkyl group having 1 to 2 carbon atoms or a fluorine-containing alkyl group. Specific examples of the diamine represented by the formula (4) can be exemplified by the following formula [A·31] to the formula [A-32] ] is a diamine, but is not limited to these. [Chem. 39]

-25- 201141912 where 'the ability to make the liquid crystal vertical alignment and the liquid crystal response speed' are preferably [eight-1], [eight-2], [eight-3], [eight-4], [ 8-5], [8-25], [A-26], [A-27], [A-28], [A-29], [A-30]. The diamine compound may be used singly or in combination of two or more kinds depending on the characteristics of liquid crystal alignment, pretilt angle, voltage holding property, and accumulated electric charge when used as a liquid crystal alignment film. For the purpose of the present invention, it is preferred that 5 to 50 mol% of the diamine component used in the synthesis of the polyamic acid is diamine A. Further, preferably 5 to 30 mol% of the diamine component is diamine A, preferably 5 to 15 mol%. <Diamine Compound Having Side Chain B> The diamine compound (also referred to as diamine B) having a side chain B may, for example, be a vinyl group, an acrylic group or a methacryl group on the side chain of the diamine. A photoreactive group of a sulfhydryl group, a cinnamyl group, a cholesterol oxime, a coumarin group, a maleimide group, a distyryl group or the like. Specifically, a diamine having a side chain represented by the above formula (b) can be mentioned. More specifically, for example, a diamine represented by the following formula (2) is exemplified, but it is not limited thereto. [40]

In the formula (2), R6 represents -CH2-, -0-, -COO-, -NHCO-, -NH-, -CH20-, -N(CH3)-, -CON(CH3), or -N(CH3) ) CO-. R7 represents a linear alkyl group having 1 to 20 carbon atoms (the alkyl group may be unsubstituted or substituted by a fluorine atom), and any -CH2- of the alkyl group may be subjected to -CF2--26-201141912 , -CH = CH-, or substituted by the substituents described below (the substituents are not adjacent). Substituents: -0-, -COO-, -NHCO-, -NH-, carbocyclic or heterocyclic groups. R8 ^t^-CH2- ' -〇- ' -COO- ' -OCO- ' -NHCO- ' -NH- , -N(CH3)-, -CON(CH3)- or -N(CH3)CO-, R11 represents a vinylphenyl group, -CH=CH2, -C(CH3) = CH2, or any of the following groups. The bonding position of the two amine groups (-NH2) in the formula (2) is not particularly limited. Specifically, it is listed as the position of 2, 3 of the bonding group with respect to the side chain on the benzene ring, the position of 2, 4, the position of 2, 5, the position of 2, 6, the position of 3, 4, 3,5 position. Among them, in terms of reactivity in synthesizing polyamic acid, the position of 2, 4, 2, 5, or 3, 5 is preferable. In consideration of the easiness in synthesizing the diamine compound, the position of 2, 4 or 3, 5 is more preferable. Specifically, the compounds are listed below, but are not limited thereto. [化42] Η2ν^^&gt;ΙΗ2 Η2Ν^^ΝΗ2 Η2Ν^^ΝΗ2

-27- 201141912 [Chem. 43]

[化44]

HjN^^NHz Η2Ν-^^ΝΗ2

Wherein X independently represents a bond group selected from the group consisting of -c-, -〇-, -NHCO-, -CONH-, -COO-, -OCO-, and -NH-, 1, m, and η Each independently represents an integer from 0 to 20. The diamine compound may be used singly or in combination of two or more kinds depending on the characteristics of the liquid crystal alignment, the pretilt angle, the voltage holding property, the accumulated electric charge, and the like, and the response speed of the liquid crystal when the liquid crystal display element is used as the liquid crystal display element. For the purpose of the present invention, it is preferred that 1 to 95 mol% of the diamine component used in the synthesis of the polyamic acid is diamine β. Further, the diamine component -28-201141912 40-95 mol% is preferably diamine B, preferably 70 to 95 mol%. <Other diamine compound> The polyamine compound used in the present invention may be a diamine component other than the diamine A and the diamine B as long as the effects of the present invention are not impaired. Specific examples thereof are listed below. p-Benzyldiamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl Base-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diamine Phenolic, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3' -Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'- Diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl -4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'- Diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'- Diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3' - Aminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane , dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine , 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- -29 - 201141912 diaminodiphenylamine, 2,2'-di Aminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl (3,3'-di Aminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl (2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3.'-diaminobenzophenone, 3,4'-diamine Benzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1 ,6-Diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diamine Keine, 2,8-two Naphthyl, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis (3) , 5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1, 4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-double (4 -aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methyl)diphenylamine, 4,4'-[1,3-phenylene bis(methyl) )]Diphenylamine, 3,4'-[1,4-phenylenebis(methyl)diphenylamine, 3,4'-[1,3-phenylenebis(methyl)diphenylamine , 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3,3'-[1,3-phenylenebis(methyl)diphenylamine, 1,4 - phenyl bis[(4-aminophenyl)methanone], I,4-phenylphenylbis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4 -aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone] , 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis (4- Amino benzoate), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, -30- 201141912 double (3 -aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, oxime &gt; 1' -(1,4-phenylene) bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N, N'-(1,4-phenylene) bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis (4 -aminophenyl)m-xylyleneamine, N,N'-bis(3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4 , 4'-bis(4-aminophenoxy)diphenyl milling, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4 -(4.Aminobenzene Oxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2' - bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane , 2,2'-bis(3-Amino-4-methylphenyl)propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis(4- Aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-amine Phenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis (4- Aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)gum, 1,7-bis (3) -aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octyl, 1,8-bis(3-aminophenoxy)octane, 1,9-bis ( 4-aminophenoxy) brothel, 1,9·bis(3-aminophenoxy)decane, 〗,! 〇_Bis(4-aminophenoxy) brothel, 1,1 〇 bis(3-aminophenoxy)decane, l,n_bis(4-aminophenoxy)undecene Alkane, l, n-bis(3-aminophenoxy)decane, 1'12-bis(4-aminophenoxy)dodecane, 1,12 bis(3aminophenoxy Base) -31 - 201141912 An aromatic diamine such as dodecane, an alicyclic diamine such as bis(4-aminocyclohexyl)methane or bis(4-amino-3-methylcyclohexyl)methane, l , 3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, i,6-diaminohexane, 1,7-diaminoheptane, 1, 8-Diaminooctane, 1,9-diaminodecane, 1,1.0-diaminodecane, 1,11-diaminoundecane, 1,1 2-diamino-12 An aliphatic diamine such as a carbon alkane. The other diamine compound may be used singly or in combination of two or more kinds depending on the characteristics of the liquid crystal alignment property, the pretilt angle, the voltage holding property, and the accumulated electric charge when the liquid crystal alignment film is used. <terephthalic acid dianhydride> In the synthesis of the polyamic acid used in the present invention, the tetracarboxylic dianhydride which reacts with the above diamine component is not particularly limited. Specific examples of the tetracarboxylic acid used as a raw material for obtaining tetrahydrous acid di-hepatic are listed below. Pyromellitic acid, 2,3,6,7-naphthalenetetradecanoic acid, 1,2,5,6-naphthalene tetraresidic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6, 7-decanetetracarboxylic acid, 1,2,5,6-indenic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid , bis(3,4_di residue phenyl)ether, 3,3',4,4'-benzophenone tetranic acid, bis(3,4-di residuephenyl)anthracene, bis(3) , 4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propyl, 1,1,1,3,3,3-hexafluoro-2,2·bis (3 , 4-di residue phenyl) propyl, bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4.dicarboxyphenyl)diphenyl fluorene, 2,3,4 , 5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)disgravity, 3,3',4,4'-diphenylphosphonium tetradecanoic acid, 3,4,9, 10-Indigo diterpenic acid, 1,3 -diphenyl-1,2,3,4-cyclobutanine tetradecanoic acid, oxydiphenyldimethyltetramine-32- 201141912 acid, 1,2 , 3,4-cyclobutane tetracarboxylic acid, hydrazine, 2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4- Tetramethyl-l,2,3,4-cyclobutanetetracarboxylic acid ' 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 13 -dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3, 4-dicarboxy-i-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentaacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo[ 3.3.0] Octane-2,4,6,8-tetracarboxylic acid, bicyclo[4.3.0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4.4_0]decane-2, 4,7,9-tetracarboxylic acid, bicyclo[4.4.0]decane-2,4,8,10-tetracarboxyindole, tricyclo[6.2.〇.&lt;2,6&gt;]~|--carbon Alkane-3,5,9,1 1 -tetracarboxyindole, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-l,2, 3,4-tetrahydronaphthalene-l,2-dicarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxo) Tetrahydrofuranyl 3 -methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1, fluorene, 2,7]dodecan-4,5,9, 10-tetracarboxylic hydrazine, 3,5,6-tricarboxy orthobornane-2: 3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc. Tetracarboxylic dianhydride It can be used in combination of two or more kinds depending on the characteristics of liquid crystal alignment, voltage holding characteristics, and accumulated electric charge when used as a liquid crystal alignment film. Synthesis of> by reaction of a diamine component and a tetracarboxylic acid dianhydride of the polyamide acid obtained by conventional synthetic methods may be used. In general, it is a method of reacting a diamine component with a tetracarboxylic dianhydride in an organic solvent. The reaction of the diamine component with the tetracarboxylic dianhydride is relatively easy to carry out in an organic solvent, and it is advantageous in terms of the production of by-products. 33-201141912 is advantageous. The organic solvent used in the above reaction is only a polylysine which is formed. There is no particular limitation on the dissolver. Further, even if it is an organic solvent which does not dissolve polyamic acid, it can be used in the above solvent without being precipitated in the range in which the produced polyaminic acid is precipitated. Further, since the water in the organic solvent is a cause of hindering the polymerization reaction and further hydrolyzing the produced polylysine, the organic solvent is preferably used by dehydration. Specific examples of the organic solvent are listed below. N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N-A Benzo decylamine, dimethyl argon, tetramethyl urea, pyridine, dimethyl milling, hexamethylarylene, 7-butyrolactone, isopropanol, methoxymethylpentanol, dipentane Alkene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve Acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoiso Propyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene Alcohol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, two Propylene glycol mono-34- 201141912 Acetate monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl 3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene , propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate , ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3 -ethyl methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme Ether, 4-hydroxy-4-methyl- 2-pentanone, 2-ethyl-1-hexanone. These organic solvents may be used singly or in combination. When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and then the tetracarboxylic dianhydride component is directly added, dispersed or dissolved. a method of adding to an organic solvent, and conversely, adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent, and adding a tetracarboxylic dianhydride component and a diamine component Any of these methods can be used. Further, when the diamine component or the tetracarboxylic dianhydride component is composed of a plurality of compounds, it may be reacted in a state of being mixed in advance, or may be reacted individually, and a low molecular weight compound which is individually reacted may be mixed into a high molecular weight body. . The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted may be selected to any temperature, for example, from _2 ° C to 150 ° C, preferably from 5 ° C to 100 ° C. -35- 201141912 Further, the reaction can be carried out at any concentration, for example, 1 to 50% by mass, preferably 5 to 30% by mass. In the above polymerization reaction, the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component may be selected depending on the molecular weight of the polyamic acid to be obtained. As with the general polycondensation reaction, the molar ratio is closer to 1. The poly-proline which is formed by hydrazine is distributed. If it is necessary to display the preferred range, it is 0.8~1.2. The method for synthesizing the poly-proline used in the present invention is not limited to the above method, and similar to the general method for synthesizing polyamide, a tetracarboxylic acid such as a tetracarboxylic acid or a tetracarboxylic acid dihalide having a corresponding structure may be used. Instead of the above tetracarboxylic dianhydride, the corresponding polylysine can be obtained by a conventional method of reaction. <Polyimine> The method for imidating the polyamic acid into a polyimine is exemplified by hot hydrazylation of a solution of poly-proline, and addition of a solution of poly-proline. The catalyst of the catalyst is imidized. In the polyimine used in the present invention, the ruthenium imidization ratio from polyproline to polyimine is not necessarily required to be 100%. The temperature at which the polyaminic acid is thermally imidized in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water formed by the hydrazide reaction is excluded from the system. The method performed on the outer side is preferred. The ruthenium imidization of polylysine can be carried out by adding a basic catalyst and an acid anhydride to the solution of polyamic acid, and stirring at -20 to 250 ° C, preferably at 〇 180 ° C. . The amount of the alkaline catalyst is 0.5-30 mol-36-201141912 times, preferably 2-20 mol times, and the amount of the acid anhydride is 1 to 50 mol times of the proline group. Good for 3 to 30 moles. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has a basicity suitable for the reaction. The acid anhydride may, for example, be acetic anhydride, trimellitic anhydride or pyromellitic anhydride. Among them, acetic anhydride is preferred because it is easier to purify after completion of the reaction. The imidization ratio obtained by imidization of the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. When the polyamine or polyimine is recovered from the reaction solution of polyphosphoric acid or polyimine, the reaction solution may be poured into a weak solvent and precipitated. The weak solvent used for the precipitation may, for example, be methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene or water. After the precipitated polymer is recovered by filtration in a weak solvent, it can be dried under normal pressure or reduced pressure at room temperature or under heat. Further, the precipitate-recovered polymer is redissolved in an organic solvent, and the reprecipitation recovery operation is repeated 2 to 10 times to reduce impurities in the polymer. The weak solvent at this time is, for example, an alcohol, a ketone or a hydrocarbon. When three or more kinds of weak solvents selected from the above are used, the efficiency of purification can be further improved, which is preferable. <Liquid crystal alignment agent> The liquid crystal alignment agent is a coating liquid for forming a liquid crystal alignment film, and is a solution in which a resin component for forming a liquid crystal alignment film is dissolved in an organic solvent. Here, the resin component is a resin component containing a polymer selected from the group consisting of polyphosphonic acid and polyamidene described above. When the ratio is -37 to 201141912, the content of the resin component is preferably from 1% by mass to 20% by mass, more preferably 3% by mass. ~15% by mass, preferably 3 to 10% by mass. In the liquid crystal alignment agent used in the present invention, all of the above resin components may be a polyamic acid having a side chain A and a side chain B, or a polyimine obtained by imidating the oxime. Mixtures of the polyamic acid and the polyimine, or other polymers other than the above. In this case, the content of the other polymer in the resin component is preferably from 0.5% by mass to 15% by mass, more preferably from 1% by mass to 10% by mass. The other polymer is exemplified by, for example, polyamic acid or polyimine which does not have a side chain A and a side chain B at the same time. When the molecular weight of the polymer of the above resin component is determined by the strength of the coating film obtained and the workability at the time of formation of the coating film, and the uniformity of the coating film, the weight average molecular weight measured by GPC (gel permeation chromatography) is preferred. It is 5,000 to 1,000,000, more preferably 10,000 to 150,000. The organic solvent used in the liquid crystal alignment agent used in the present invention is not particularly limited as long as it is an organic solvent capable of dissolving the above resin component. The organic solvent may be an organic solvent or a mixture of two or more. Specific examples of the organic solvent include organic solvents exemplified in the synthesis of the polyamic acid. Wherein N-methyl-2-pyrrolidone, γ-butyrolactone, Ν-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-oxime, Ν-二Methylpropionamide or the like is preferred from the viewpoint of solubility of the resin component. Further, since the solvent shown below can improve the uniformity or smoothness of the coating film, it is preferably used in a solvent having a high solubility in a resin component, and is exemplified by, for example, isopropanol or methoxymethylpentanol. , methyl cellosolve, ethyl-38 - 201141912 cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl card Alcohol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol diethylene glycol Ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol single B Acid ester monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl Acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl Ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate Ester, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxy Ethyl propyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2- Propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol- 1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, Ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, 2-ethyl-1-hexanol, and the like. These solvents may be mixed in plural. When a solvent such as -39-201141912 is used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. The liquid crystal alignment agent may contain components other than the above. Examples thereof include a compound which improves the film thickness uniformity or surface smoothness when a liquid crystal alignment agent is applied, and a compound which improves the adhesion between the liquid crystal alignment film and the substrate. The compound which improves the film thickness uniformity or the surface smoothness is exemplified by a fluorine-based surfactant, a polyoxyalkylene-based surfactant, a nonionic surfactant, and the like. More specifically, for example, EFTOP EF301, EF303, EF3 52 (manufactured by TOKEMU PRODUCTS), MEGAFAC F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), FLUORAD FC430, FC431 (manufactured by Sumitomo 3 Co., Ltd.), ASA ΗI GUARD AG710, SURFLON S -3 82, SC10 1, SC102, SC103, SCI 04, SC 105, SC 106 (made by Asahi Glass Co., Ltd.). When the surfactant is used, the use ratio is preferably from 0.01 to 2 parts by mass, more preferably from 0.01 to 1 part by mass, based on 1 part by mass of the resin component contained in the liquid crystal alignment agent. Specific examples of the compound having a film-substrate adhesion property include a functional decane compound or a compound containing an epoxy group. Listed as, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N -(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureido Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethyl-40- 201141912 Oxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl -1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9·trimethoxydecyl-3,6-diazaindole Acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3- Aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxy-ethyl) Base)-3- Propyltrimethoxydecane, N-bis(oxyethylidene)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol dihydrate Glycerol ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2- Dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-inter-di Toluene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diamino Diphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, etc. . Further, in order to further improve the friction resistance of the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention, 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane or tetra(a) may be added. A phenolic compound such as oxymethyl)bisphenol. When the compound is used, the amount of the resin component contained in the liquid crystal alignment agent is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass. The liquid crystal alignment agent used in the present invention may be added with a dielectric or a conductive material for changing the dielectric properties or electrical conductivity of the liquid crystal alignment film as long as it does not impair the effects of the present invention -41 - 201141912. Further, the above liquid crystal alignment agent contains {polyimide obtained by reacting a diamine component containing diamine A and diamine B with tetracarboxylic dianhydride} and {polyimide obtained by imidating the oxime A liquid crystal alignment agent of at least one of quinone imine}, the diamine B is a diamine represented by the above formula (2), and R8 of the formula (2) is · CH2-, -Ο- '-COO-'-OCO - '-NHCO- or -NH-, R11 is -. Ruler 1() = (: 112 base, R&quot; A liquid crystal alignment agent which is a hydrogen atom or a methyl group which may be substituted by a fluorine atom is a liquid crystal alignment agent newly provided by the present invention (also referred to as a liquid crystal alignment agent of the present invention). The liquid crystal alignment agent of the invention can be used not only as a liquid crystal alignment agent for producing a liquid crystal display element of the present invention, but also as a liquid crystal alignment film produced by a rubbing treatment or a photoalignment treatment. <Liquid Crystal Alignment Film> The present invention The liquid crystal alignment agent can be applied to a substrate, fired, and then subjected to an alignment treatment by rubbing treatment or light irradiation, or can be used as a liquid crystal alignment film in a non-alignment treatment such as a vertical alignment application. The substrate having high transparency is not particularly limited, and a plastic substrate such as a glass substrate, an acrylic substrate, or a polycarbonate substrate can be used. Further, a substrate on which an ITO electrode or the like for driving a liquid crystal is formed is used, and the process is simplified. Further, in the reflective liquid crystal display device, an opaque film such as a single-sided substrate may be used, and in this case, the electrode may be used. A material that reflects light such as aluminum is used. -42- 201141912 The method of applying the liquid crystal alignment agent is not particularly limited, but industrially, it is generally carried out by screen printing, lithography, soft printing, inkjet, etc. The coating method includes dipping, roll coating, slit coating, spin coater, etc., and the like can be used according to the purpose. The baking after coating the liquid crystal alignment agent can be carried out at any temperature of 10 ° C to 3 50 ° C. However, it is preferably from 120 to 300 ° C, more preferably from 150 to 250 ° C. The firing can be carried out by heating a plate, a hot air circulating furnace, infrared rays, etc. The thickness of the film after firing is not particularly limited, but is preferably 5 ~300nm, more preferably 10~100nme When the liquid crystal is horizontally aligned or obliquely aligned, the film after firing is treated by rubbing treatment or polarized ultraviolet irradiation. <Liquid Crystal Display Element> The liquid crystal display element of the present invention is characterized by having a two-piece substrate having a liquid crystal alignment layer containing polyacrylic acid having a side chain (A) and a photoreactive side chain (B) which vertically aligns the liquid crystal and a quinone imine Composition of polyimine Forming at least one liquid crystal alignment agent selected from the group; sandwiching a liquid crystal cell of the liquid crystal layer between the two substrates disposed in such a manner that the liquid crystal alignment layer is opposed to each other; and irradiating a voltage on the liquid crystal layer The substrate for liquid crystal display of the present invention is not particularly limited as long as it is a substrate having high transparency, but a substrate for driving a transparent electrode for driving liquid crystal is usually formed on the substrate. The substrate described in the liquid crystal alignment film is the same as that described in the above-mentioned. The liquid crystal display device of the present invention can also use a substrate having an electrode pattern or a convex pattern. However, the liquid crystal display of the present invention is Forming a line/slit electrode pattern of 1 to ΙΟ/zm on the single-sided substrate, and still operating on the opposite substrate without forming a slit pattern or a convex pattern, by the liquid crystal display element of the structure, The process at the time of manufacture can be simplified, and a high transmittance can be obtained. Further, a high-functional element such as a TFT-type element is used for forming an element such as a transistor between an electrode for driving a liquid crystal and a substrate. In the case of a transmissive liquid crystal element, a substrate as described above is generally used. However, in the case of a reflective liquid crystal display element, an opaque film such as a single-sided substrate may be used. At this time, the electrode formed on the substrate may also be made of a material such as aluminum which reflects light. The above-mentioned liquid crystal alignment layer is a resin film which vertically aligns the liquid crystal with respect to the substrate, and is formed by using the liquid crystal alignment agent. The step of forming the liquid crystal alignment layer on the substrate can be carried out by the coating method described in the above [Liquid Crystal Alignment Film] and the firing method after coating. A method of sandwiching a liquid crystal layer between two substrates can be exemplified as a conventional method for producing a liquid crystal cell. An example of the liquid crystal cell production is exemplified by preparing a pair of substrates on which a liquid crystal alignment layer is formed, and spreading a spacer on the liquid crystal alignment layer of the single substrate so that the liquid crystal alignment layer is inside. The substrate, a method of injecting a liquid crystal into a vacuum and encapsulating it, or a method in which a liquid crystal is dropped on a liquid crystal alignment layer in which a spacer is dispersed, a substrate is bonded, and a method of packaging is performed. The thickness of the spacer at this time is preferably from 1 to 30/zm, more preferably from -44 to 201141912. The liquid crystal used in the liquid crystal display device of the present invention accelerates the response speed of the liquid crystal even if the liquid crystal is not added with the photopolymerizable compound. However, it is also possible to use a liquid crystal to which a photopolymerizable compound is added. The step of applying a voltage to the liquid crystal layer and irradiating the ultraviolet light while forming an electric field is, for example, a method of applying a voltage between electrodes provided on the substrate to apply a voltage to the liquid crystal layer, and directly irradiating the ultraviolet light at the voltage. Here, a function of applying a voltage to the liquid crystal layer may be performed using a function generator, and an apparatus for irradiating ultraviolet rays may be an existing device such as a high pressure mercury lamp. The voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The wavelength of the ultraviolet light is preferably from 250 to 400 nm, more preferably from 300 to 400 nm. The irradiation amount of the ultraviolet ray is, for example, 1 to 60 J/cm 2 , preferably 40 Å/cm 2 or less, and the less the amount of the ultraviolet ray irradiation, the decrease in the reliability due to the destruction of the member constituting the liquid crystal display, and the reduction of the irradiation time of the ultraviolet ray can be suppressed. It is better to improve manufacturing efficiency. By the above steps, the reaction speed of the liquid crystal display element is accelerated by reacting the photoreactive group of the side chain B and memorizing the tilt direction of the liquid crystal molecules. The invention is more specifically illustrated by the following examples of the invention, but should not be construed as being limited thereto. [Synthesis of Poly-Proline] The abbreviations of compounds such as tetracarboxylic dianhydride used are shown below. (tetracarboxylic dianhydride) Cl : 1,2,3,4-cyclobutane tetracarboxylic dianhydride-45- 201141912 (diamine compound) DA-6 : p-phenylenediamine DA-7: 1,3 -diamino-4-octadecyloxybenzene DA-8 : 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene DA-9 : 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene [45]

〇

DA-6 .rj^V〇^18H37 Η2Ν·^^ΝΗ2 H2N People^^SsIHz DA-7 DA-8 /mm,\ /~'\ Λ&quot;&quot;\ CsHi1 DA-9 -46 · 201141912 ο

(Organic solvent) ΝΜΡ: Ν-methyl-2-pyrrolidone BCS: butyl cellosolvin Further, among the above diamine compounds, DA-2 and DA-3 are obtained by referring to the synthesis examples described below. (Reference Synthesis Example 1) Synthesis of DA-2 In a 500 mL (ml) three-necked flask, 5.94 g of tetramethyl glycol monoethyl ether, 5.70 g of triethylamine, and 30 mL of toluene were added. The system was heated to 1 〇〇 ° (:, 2,4-dinitrofluorobenzene 1 〇 8 dissolved in 2 〇 1111 mmol of toluene was added dropwise, and stirred at 100 ° C for 6 hours. After the reaction, pure water was added. 50 mL, after stirring, ethyl acetate was added and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to dehydrate and dry, and filtered, and then evaporated to a solvent using a rotary evaporator. The mixed solvent of /3 (volume ratio, the same applies hereinafter) was recrystallized to obtain 13.2 g of 2,4-dinitro-1-(4-vinyloxy)butoxybenzene (yield 90%). To the 500 mL three-necked flask, 2.12 g of the above-mentioned dinitro compound, 20 mL of toluene, and 80 mL of a 10% by mass aqueous solution of chlorinated money were added. The inside of the system was heated to 70 ° C, and 4.2 g of iron (electrolytic iron) was added. After stirring at 70 ° C for 2.5 hours, after completion of the reaction, 30 mL of a 5 mass % sodium carbonate-47-201141912 aqueous sodium hydrogen solution was added, and the precipitate was filtered and washed with toluene. The filtrate was extracted with ethyl acetate, and anhydrous sulfuric acid was added to the organic layer. Magnesium dehydration and drying, after filtration, solvent distillation using rotary evaporation. The residue was ethyl acetate / hexane = The mixed solvent of 7/3 was recrystallized to obtain 0.59 g of the objective compound (yield: 38%). The result of the 1H-NMR measurement of the target product is shown below. From the result, the obtained solid was confirmed to be the intended diamine compound. That is, 4-(4-vinyloxy)butoxy)benzene-1,3-diamine *H NMR (400 MHz, CDC13): &lt;5 = 6.60-6.62 (d, 1 Η), 6.44-6.51 (m, lH), 6.13-6.14 (d, lH), 6.03-6.07 (m, lH), 4-14-4.21 (d, lH), 3.96-4.00 (d, lH), 3.9 2 - 3.9 6 ( t, 2 H ), 3.73 - 3.73 (m, 4H), 3.34 (s, 2H), 1.85 - 1.87 (m, 4H). (Reference Synthesis Example 2) Synthesis of DA-3 To a 300 mL three-necked flask was added 10-undecen-1-ol 5.1 lg, 2.37 g of pyridine, and 100 mL of tetrahydrofuran. The system was placed at 〇 ° C with ice cooling, and 8.3 g of 3,5-dinitrobenzimid chloride was added and stirred at room temperature for 2 hours. After completion of the reaction, 20 mL of pure water was added, and after stirring, ethyl acetate was added and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to dehydrate and dry, and after filtration, solvent distillation was carried out using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate/hexane = 7/3 to obtain 6.9 g of undec-10-benzol-3,5-dinitrobenzoate (yield: 63%). . 6.55 g of the above dinitro compound, 50 mL of tetrahydrofuran, and 50 mL of pure water were placed in a three-necked flask of 3,000 mL, and the inside of the system was stirred, and 17.6 g of tin chloride was added, and the mixture was stirred at 60 ° C for 2 hours. After the completion of the reaction, -48-201141912 was added to 400 mL of a 5 mass% sodium hydrogencarbonate aqueous solution to adjust the pH to 7-8. Subsequently, 16 mL of ethyl acetate was added, and the white precipitate was removed by filtration, and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer to remove water, and after filtration, solvent distillation was carried out using rotary evaporation. The residue was recrystallized using a mixed solvent of ethyl acetate / hexane = 7 / 3 to obtain 4.5 g of the object (yield: 82%). The results of 1H-NMR measurement of the target substance are shown below. From the results, it was confirmed that the obtained solid was the intended diamine compound, that is, undecyl-10-alkenyl-3,5-diaminobenzoic acid ester. *H NMR (400 MHz, [D6]-DMSO): δ = 6.41 (s, 2H) * 6.01 (s, lH), 5.73-5.84 (m, lH), 4.91-5.01 (m, 6H), 4.13 4.16(t, 2H), 1.98-2.02 (m, 2H), 1.6 0 -1.6 7 (m, 2 H), 1.27-1.37 (m, 12H). <Measurement of Molecular Weight of Polylysine and Polyimine] The molecular weight of polylysine in the following synthesis example is a room temperature gel permeation chromatography (GPC) device (GPC-101) manufactured by Showa Denko Co., Ltd., Shodex The column (KD-803, KD-805) manufactured by the company was measured as follows.

Column temperature: 50 ° C Dissolution: N,N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr, H20) is 30 mmol / L 'phosphoric acid • anhydrous crystals (0-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10 ml/L) Flow rate: 1.0 m 1 /min Calibration line for standard preparation: TSK standard manufactured by TOSOH-49 · 201141912 Polyethylene oxide (molecular weight about 900,000, 1 50,000, l〇 〇,〇〇〇' 3 0,00 0), and polyethylene glycol manufactured by Polymer Laboratories, Inc. (molecular weight: about 12,000 '4,000 '1,000) 0 <Synthesis Example 1> 0.78 g (3.96 mol) of C- was used. 1 As a tetracarboxylic dianhydride, 0.85 g (3.20 mmol) of DA1 and 0.30 g (0.80 mmol) of DA-7 were used as a diamine component, and reacted in NMP 7.69 g at room temperature for 16 hours to obtain a polyamine. The concentration of the acid (PAA-1) was 20% by mass. The polyacrylamide solution (PA Al) was diluted with 8.0 g of NMP 12.0 g and BCS 5.3 g to obtain a liquid crystal alignment of polyamine acid (PAA-1) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%. Agent (A1). Further, PAA-1 has an average molecular weight of 20,500 and a weight average molecular weight of 63,000. <Synthesis Example 2> 0.78 g (3.96 mol) of C-1 was used as the tetracarboxylic dianhydride'. 0.95 g (3.60 mmol) of DA1 and 0.15 g (0.40 mmol) of DA-7 were used as the diamine component in NMP. 7_: 51 g, and reacted at room temperature for 6 hours to obtain a solution having a polyamine acid (PAA-2) concentration of 20% by mass. The polyacrylic acid solution (PAA-2) was diluted with 8.0 g of NMP 12.2g and BCS5_3g to obtain polyglycine (PAA-2) of 6% by mass, NMP of 74% by mass/d, and BCS of 20% by mass. Liquid crystal alignment agent (A2). Further, the average molecular weight of PAA-2 is 2 5,200, and the weight average molecular weight is 8,600 ° C -50 - 201141912 <Synthesis Example 3> C-1 using 49.49 g (2.48 mol) As a tetracarboxylic dianhydride, 0.59 g (2.25 mmol) of DA1 and 95 g (0.25 mmol) of DA-8 were used as a diamine component, and reacted in NMP 4.70 g at room temperature for 16 hours to obtain a polyfluorene. The concentration of the amino acid (PAA-3) was 20% by mass. The polyamino acid solution (PAA-3) was diluted with 4.7 g of NMP 7.8 g and BCS 3.1 g to obtain polyamine acid (PAA-3) of 6% by mass, NMP of 74% by mass, and BCS of 20% by mass. Liquid crystal alignment agent (A3). Further, the PAA-3 had an average molecular weight of 20,400 and a weight average molecular weight of 57,800. <Synthesis Example 4> 0.49 g (2.48 mol) of C-1 was used as the tetracarboxylic dianhydride'. 0.59 g (2-25 mmol) of DA1 and 0.11 g (0-25 mmol) of DA-9 were used as the diamine component in NMP 4.75 g. The mixture was reacted at room temperature for 16 hours to obtain a solution having a concentration of polyamidamine (PAA-4) of 20% by mass. The polyamino acid solution (PAA-4) 4.7 g' was diluted with NMP 7.9 g and BCS 3.2 g to obtain polyamine acid (PAA-4) of 6% by mass 'NMP was 74% by mass' and BCS was 20% by mass. Liquid crystal alignment agent (A4). Further, the average molecular weight of PAA-4 was 1,900, and the weight average molecular weight was 5 5,0 0 〇 ° <Synthesis Example 5> 0.47 g (2.40 mol) of C-1 was used as the tetracarboxylic acid For the anhydride, 0.39 g (1.75 mmol) of DA2 and 0.28 g (0.75 mmol) of DA-7 were used as the diamine component, and reacted in NMP 4.75 g at room temperature for 16 hours to obtain -51 201141912 poly-proline (PAA). -5) A solution having a concentration of 20% by mass. 4.5 g of the polyaminic acid solution (PAA-5) was diluted with 7.6 g and BCS 3.0 g, polyglycine (PAA-5) was 6 mass%, NMP was 74 mass%, and 20 mass% of liquid crystal alignment was used. Agent (A5). Further, the PAA-5 had an amount of 16,700 and a weight average molecular weight of 52,900. <Synthesis Example 6> 0.47 g (2.40 mol) of C-1 was used as tetracarboxylic dianhydride '0.44 g (2.00 mmol) of DA2 and 0.19 g (0.50 mmol) of DA-7 diamine component in NMP 4.41 g The solution was reacted at room temperature for 16 hours at a concentration of 20% by mass of polyglycine (PAA-6). 4.4 g of the polyaminic acid solution (PAA-6) was diluted with 7.3 g and BCS 2.9 g, polyglycine (PAA-6) was 6 mass%, NMP was 74 mass%, and liquid crystal alignment was 20 mass%. Agent (A6). Further, the PAA-6 had an amount of 24,400 and a weight average molecular weight of 93,500. <Synthesis Example 7> 〇.49 g (2.48 mol) of C-1 was used as tetracarboxylic dianhydride '0.5 3 g (1.7 5 m τη ο 1) of DA 3 and 0 · 2 8 g (0 · 7 5 mm) ο 1) The DA-7 component of the diamine was reacted in NMP 5.2 Og at room temperature for 16 hours. The concentration of polyamine acid (PAA-7) was 20% by mass. Using 9.0 g and BCS 3.6 g to dilute the polyaminic acid solution (PAA-7) 5.4 g to obtain polyglycine (PAA-7) to be 6 masses of 11%, NMP of 74% by mass, and BCS of 20% by mass of liquid crystal alignment. Agent (A7). In addition, the NMP of PAA-7 was obtained by using BCS as the NMP to obtain the BCS. The NMS was obtained as the NMP, and the average molecular weight was 20,900, and the weight average molecular weight was 78,900°. 8> Using 0.49 g (2.48 mol) of C-1 as tetracarboxylic dianhydride '0.61 g (2.00 mmol) of DA3 and 0.19 g (0.50 mmol) of DA-7 diamine component at NMP 5.13 g A solution in which the concentration of polyglycine (ΡΑΑ-8) is 20% by mass in a reaction at room temperature for 1 hour. The polyplysine solution (ΡΑΑ-8) 5.3 g was diluted with 8.8 g and BCS 3.5 g to obtain a polyamine acid (PAA-8) of 6 mass% and an NMP of 74 mass%. BCS is a 20% by mass liquid crystal alignment agent (A8). Further, the average molecular weight of PAA-8 was 18,800' and the weight average molecular weight was 67,300» <Synthesis Example 9> 0.49 g (2.48 mol) of C-1 was used as the tetracarboxylic dianhydride, 0.46 g (2 · 0 0 mm). 1) D A4 and 0 · 1 9 g (0.5 Ommo 1) of DA - 7 diamine component, reacted in NMP 4.55g at room temperature for 16 hours' concentration of polyamine (PAA-9) is 20 Mass % solution. The polyamic acid solution (PAA-9) 4.5 g was diluted with 6.5 g and BCS 3.0 g to obtain a polyamine acid (PAA-9) of 6 mass% 'NMP of 74 mass%/. BCS is a 20% by mass liquid crystal alignment agent (A9). Further, PAA-9 had an average molecular weight of 17,600 and a weight average molecular weight of 47,100. <Synthesis Example 1 〇> 0.49 g (2.48 mol) of C-1 was used as the tetracarboxylic dianhydride, and it was used as the NMP, and the number was used as the NMP, and the number was used. 53-201141912 0.52g (2.25 mmol) of DA4 and 0.09 g (0.25 mmol) of DA-7 as a diamine component, reacted in NMP 4.41 g at room temperature for 10 hours to obtain a concentration of polyglycine (ΡΑΑ-10) of 20 masses. % solution. 4.3 g of the polyaminic acid solution (PAA-10) was diluted with 6.1 6.1 g and BCS 2.8 g to obtain polyglycine (PAA-10) of 6% by mass, NMP of 74% by mass ' and BCS of 20% by mass. Liquid crystal alignment agent (A10). Further, the average molecular weight of PAA-10 was 1,900, and the weight average molecular weight was 5 5,500. » Synthesis Example 1 1 Using 0.49 g (2.48 mol) of C-1 as a tetracarboxylic acid The dianhydride's use 0-82 g (2.00 mmol) of DA5 and 0.19 g (0.50 mmol) of DA-7 as the diamine component, and reacted in NMP 5.99 g at room temperature for 16 hours to obtain poly-proline (PAA- 11) A solution having a concentration of 20% by mass. The polyacrylic acid solution (PAA-11) 5.0 g' was diluted with NMP 6.3 g and BCS 3.3 g to obtain polyglycine (PAA-1 1) of 6 mass%, NMP of 74 mass% ' and BCS of 20 masses. % of liquid crystal alignment agent (All). Further, the average molecular weight of PAA-11 was 17, 〇〇〇, and the weight average molecular weight was 56,00 () ° <Synthesis Example 1 2> 0.49 g (2.48 mol) of C -1 was used as the tetracarboxylic dianhydride. 'Using 93.93g (2.25mmol) of DA5 and 0.19g (0.25mmol) of DA-7 as a diamine component, reacting in NMP 6.03g at room temperature for 16 hours to obtain poly-proline (PAA-12) The solution has a concentration of 20% by mass. The polyacrylic acid solution (PAA-12) 5.0g' was obtained by using NMP 6.3g and BCS 3.3g to obtain -54-201141912. The polyamic acid (PAA-12) was 6 mass%, and the NMP was 74 mass%. BCS is a 20% by mass liquid crystal alignment agent (A12). Further, the average molecular weight of PAA-12 was 1,900, and the weight average molecular weight was 59, 〇〇〇. <Synthesis Example 1 3> 0.49 g (2.48 mol) of C-1 was used as the tetracarboxylic dianhydride, and 0.64 g (2.00 mmol) of DA-10 and 〇.19 g (0.50 mmol) of DA-7 were used as the diamine. The component was reacted in NMP 5.26 g at room temperature for 16 hours to obtain a solution having a polyglycine (PAA-14) concentration of 20% by mass. 5.0 g of the polyaminic acid solution (PAA-14) was diluted with NMP 6.3 g and BCS 3.3 g to obtain polyglycine (PAA-14) of 6% by mass, NMP of 74% by mass, and BCS of 20% by mass. Liquid crystal alignment agent (A13). Further, the number average molecular weight of PAA-14 was 17,500, and the weight average molecular weight was 57,000 Å. <Synthesis Example 1 4> 0.49 g (2.48 mol) of C-1 was used as the tetracarboxylic dianhydride'. 0.72 g (2.25 mmol) was used. DA-10 and 〇.〇9g (0.25mmol) of DA-7 as a diamine component, reacted in NMP 5·20g at room temperature for 16 hours to obtain the concentration of poly-proline (PAA-15). 20% by mass solution. The polyplycosic acid solution (?8-8-15) 5.0 g was diluted with NMP 6.3 g and BCS 3.3 g to obtain polyglycine (PAA-15) of 6% by mass 'NMP was 74% by mass, and BCS was 20%. % by mass of liquid crystal alignment agent (A14). Further, the number average molecular weight of PAA-15 was 18,500' and the weight average molecular weight was -55-201141912 59,000. <Comparative Synthesis Example 1> 1.30 g (6.65 mol) of C-1 was used as tetraterpene acid two fields' using 0.68 g (6-30 mmol) of DA-6 and 0.26 g (0.7 mmol) of DA-7 as a diamine component, reacted in NMP 12.74 g at room temperature for Ιό hours to obtain a concentration of polyglycine (PAA-13) of 20 Mass % solution. The polyamic acid solution (PAA-13) 10.Og was diluted with NMP 16.7g and BCS 6.7g to obtain polyglycine (PAA-1 3) of 6% by mass, NMP of 74% by mass, and BCS of 20%. % by mass of liquid crystal alignment agent (A1 5). Further, the number average molecular weight of PAA-13 was 1,800, and the weight average molecular weight was 58,000 » <Example 1> The ITO electrode substrate of the ITO electrode pattern having a wire/space of 5 μm was formed at a pixel size of 1 00 x 300 μm. The liquid crystal alignment agent [A1] obtained in Synthesis Example 1 was spin-coated on the ITO surface. After drying on a hot plate at 80 ° C for 90 seconds, it was baked in a hot air circulating oven at 160 ° C for 60 minutes to form a liquid crystal alignment film having a film thickness of 10 nm. Further, the liquid crystal alignment agent [A1] obtained in Synthesis Example 1 was spin-coated on the ITO surface on which the electrode pattern was not formed, and dried on a hot plate at 80 ° C for 90 seconds, followed by a hot air circulating oven at 160 ° C. The firing was carried out for 60 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. These two substrates were prepared, and a 6#m bead spacer was spread on the liquid crystal alignment film surface of one of the substrates, and then a sealant was printed thereon. The liquid crystal alignment film surface of the other substrate is made to be inside, and after bonding -56 - 201141912, the sealant is cured to form an empty liquid crystal cell. Liquid crystal MLC-6608 (trade name, manufactured by Merck Co., Ltd.) was injected into the empty liquid crystal cell by a vacuum injection method to prepare a liquid crystal cell. The response speed of the liquid crystal cells is measured by a method described later. Subsequently, 20 J of UV (ultraviolet rays) was irradiated from the outside of the liquid crystal cell in a state where a voltage of 20 Vp-p was applied to the liquid crystal cell. Subsequently, the response speed characteristics were measured to compare the response speeds before and after UV irradiation. The results are shown in Table 2. <Examples 2 to 14> and <Comparative Example 1> The liquid crystal alignment agent [A1] was changed to the liquid crystal alignment agents [A2] to [A14] obtained in Synthesis Examples 2 to 14 shown in Table 2, respectively. The liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment agent [A15] obtained in Synthesis Example 1 was compared, and the response speed was measured. The results are shown in Table 2. [Response Velocity Characteristics] The oscilloscope (Oscilloscope) obtains the change in brightness of the liquid crystal panel with time when a rectangular wave of a voltage of ±4 V and a frequency of 1 kHz is applied to a liquid crystal cell to which no voltage is applied. The luminance when no voltage is applied is 〇%, a voltage of ±4 V is applied, and 饱和 of saturation luminance is taken as 1〇〇%, and the time from the change of luminance from 10% to 90% is used as the starting response speed. -57- 201141912

Beach 3 Directions m CQ CO CO KT&gt; CM CO oo CO c〇to o Ο CO C^3 OO CS5 CS5 CO C^5 ΙΛ OO s Stepping CO C£&gt; to c〇t/» LT3 CO 03⁄4 CO «〇oo 寸 CO LA CO CO u-» IS&gt; ¢0 un C^3 CO «〇OO CO CO &lt;〇OO «〇CO oo CO LO &lt;〇CO Μ key 骟 habitat _芎ing -N cn A o oo ca aso S ssos O soo IwH tm State CO JW1&lt;&gt; m draw crane og ΙΛ gsogs A s SS gs § sm CO ΙΛ CO oo o *^1 c«a CO tn mm face CO IT3 CO卜Q〇σ&gt; ca CO 镒:H It can be understood from Table 2 that the response speed of the liquid crystal cell of the example after UV irradiation is increased. On the other hand, in the comparative example, no change in response speed was observed before and after UV irradiation. In Examples 1, 2, and Examples 5 and 6, and Examples 7, 8 and 9 and 10, and Examples 1 and 12, the degree of response speed after UV irradiation was less than the amount of introduction of the side chain exhibiting inclination. Larger. In the case of the examples 2, 3, and 4, when the side chain exhibiting the same amount of the inclined side chain and having a low vertical alignment energy is used, the degree of the response speed after the UV irradiation is also large. Further, even in the same Examples 13 and 14 as described above, the amount of introduction of the side chain which exhibited the inclination was small, and the response speed after UV irradiation was increased to a large extent. Further, in Examples 1, 13 and Examples 2 and 14, the introduction amount of the side chain exhibiting the inclination was the same, the photoreactive group was also the same, and the alkyl spacer group was long, compared with the DA-10. In the case, the response speed after UV irradiation is increased to a large extent. [Industrial Applicability] The liquid crystal display element of the present invention can be used as a screen of a liquid crystal television or a screen of various material display apparatuses. Further, the liquid crystal alignment agent of the present invention can be used not only in the liquid crystal display element of the vertical alignment type which is produced by applying ultraviolet rays while applying a voltage to the liquid crystal molecules, but also can be used for liquid crystal display elements which are produced without such steps. Further, the entire disclosure of the specification of the Japanese Patent Application No. 20 1 0-04 3372, the entire disclosure of which is hereby incorporated by reference. -59.

Claims (1)

201141912 VII. Patent application scope 1. A method for manufacturing a liquid crystal display device of a vertical alignment type, characterized in that: a side chain (B) having a side chain (A) having a liquid crystal alignment direction and a photoreactive side chain (B) a liquid crystal alignment agent selected from the group consisting of polylysine and a polyimine obtained by imidization of the ruthenium, coated on two substrates to form a liquid crystal alignment layer, so that the liquid crystal alignment layer is formed Two substrates are disposed in a facing manner, and a liquid crystal layer is sandwiched between the two substrates, and on the one hand, a voltage is applied to the liquid crystal layer to irradiate ultraviolet rays. 2. The method for producing a liquid crystal display device according to claim 1, wherein the liquid crystal alignment agent is a liquid crystal alignment agent containing at least one of polyamic acid and polyamidene obtained by imidating the oxime. The polyamic acid is a polylysine obtained by reacting a diamine component with a tetracarboxylic dianhydride, the diamine component comprising a diamine having a side chain (A) which vertically aligns the liquid crystal and having a photoreaction a diamine of the side chain (B). 3. The method of manufacturing a liquid crystal display element according to claim 1 or 2, wherein the side chain (A) for vertically aligning the liquid crystal is represented by the following formula (a), (In the formula (a), 1, m and η each independently represent an integer of 0 or 1 'R1 represents an alkylene group having 2 to 6 carbon atoms, -〇-, -COO-, -OCO-, -60-201141912 -NHCO-, -CONH- or an alkyl-ether group having 1 to 3 carbon atoms, R2, r3 and R4 each independently represent a phenyl or cycloalkyl group, and R5 represents a hydrogen atom and has 5 to 18 carbon atoms. a linear alkyl group or a fluorine-containing alkyl group, or an aromatic ring group, an aliphatic ring group, a heterocyclic group or a macrocyclic group composed of the above. 4. The method for producing a liquid crystal display device according to any one of claims 1 to 3, wherein the photoreactive side chain (B) is represented by the following formula (b), [Chem. 2] - Re- R7-R8^R9 (b) (R6 represents -CH2-, -〇-, -COO-, -NHCO-, -NH-, -CH20-, -N(CH3)-, -CON(CH3)- or - N(CH3)CO-, R7 represents a linear alkyl group having 1 to 20 carbon atoms (the alkyl group may be unsubstituted or substituted by a fluorine atom), and further an alkyl group may be -CH2- -CF2-, -CH=CH- or a substituent (the substituents are not adjacent) substituted, substituent: -0-, -COO-, -NHCO-, -NH-, carbocyclyl or hetero Ring group, R8 ^7jK-CH2- ' -〇- ' -COO- ' -OCO- ' -NHCO- ' -NH-, -N(CH3)-, -CON(CH3)-, -N(CH3)CO - a carbocyclic group or a heterocyclic group, R9 represents a vinylphenyl '-CR1G = CH2 group, a carbocyclic group, a heterocyclic group or a group represented by the following formula: R1G represents a hydrogen atom or a methyl group which may be substituted by a fluorine atom ), • 61 - 201141912 [Chem. 3] 5. The method of manufacturing a liquid crystal display device according to any one of claims 2 to 5, wherein the side chain (A) for vertically aligning the liquid crystal is represented by the above formula (a), wherein 1, m and η All are 1, R2 is a phenyl group, R3 is a phenyl or cyclohexyl group, R4 is a cyclohexyl group, R5 is an alkyl group having 2 to 24 carbon atoms, or l, m and η are both 0. R5 is an alkyl group having 12 to 22 carbon atoms. The method for producing a liquid crystal display element according to any one of claims 3 to 5, wherein the photoreactive side chain (Β) is represented by the above formula (b) Is a vinyl phenyl group, _ch = ch2, -C(CH3) = CH2 or any of the following groups, [Chemical 4] 7. A liquid crystal display element of a vertical alignment type, comprising: two substrates having a liquid crystal alignment layer containing a side chain (A) having a vertical alignment of liquid crystals and photoreactivity Forming at least one liquid crystal alignment agent selected from the group consisting of polylysine of side chain (B) and polyamidimide obtained by imidization of ruthenium to form opposite layers of said liquid crystal alignment layer a method of arranging the liquid crystal cells of the liquid crystal layer between the two substrates; and a means for irradiating the ultraviolet rays by applying a voltage to the liquid crystal layer. 8. A liquid crystal alignment agent comprising a polyaminic acid having a side chain (A) in which a liquid crystal is vertically aligned and a photoreactive side chain (B), and a polyimine obtained by imidating the oxime At least one of the selected groups is selected. A liquid crystal alignment agent characterized by containing a diamine component and a tetracarboxylic acid comprising a diamine having a side chain (A) having a side chain (A) vertically aligned with a liquid crystal and a diamine having a photoreactive side chain (B) At least one liquid crystal alignment agent selected from the group consisting of polyamic acid obtained by dianhydride reaction and polyimine obtained by imidization of ruthenium, the above-mentioned diamine having a photoreactive side chain (B) For the following _ 63 _ (2) (2) 201141912, the expression (2), [Chemical 5] (R6 represents -Ch2-, -0-, -COO-, -NHCO-, -NH-, -CH20-, -N(CH3)-, -CON(CH3)- or -N(CH3)CO-, R7 A linear alkyl group having 1 to 20 carbon atoms (the alkyl group may be unsubstituted or substituted by a fluorine atom), and any -CH2- which may be extended to an alkyl group may be -CF2-, -CH=CH Or a substituent substituted by the substituent: -Ο-, -COO-, -NHCO-, -NH-, carbocyclyl or heterocyclyl, R8 represents -CH2 -, -0-, -COO-, -0C0_, -NHCO-, -NH-, -N(CH3)-, -CON(CH3)- or -N(CH3)CO-, R11 represents a vinylphenyl group, -CH = CH2, -c(ch3) = ch2 or any of the following), [Chem. 6] 10. The liquid crystal alignment agent of any one of Items 7 to 9 wherein the diamine having the side chain (A) which vertically aligns the liquid crystal is represented by the following formula (1), -64-201141912 [ 7] fe-R.2KR3H 十 R5 (1) H2N^ I mn (In the formula (a), 1, m and n each independently represent an integer of 〇 or 1 'R1 represents an alkylene group having 2 to 6 carbon atoms, - 〇-, -COO-, -OCO-, -NHCO-, -CONH- or an alkyl-ether group having 1 to 3 carbon atoms, and R2, R3 and R4 each independently represent a phenyl or a cycloalkyl group. R5 represents a hydrogen atom, a linear alkyl group having 5 to 18 carbon atoms, a fluorine-containing alkyl group or an aromatic ring group, an aliphatic ring group, a heterocyclic group or a large cyclic group composed of the above. 11. The liquid crystal alignment agent of claim 10, wherein the diamine having a side chain (A) in which the liquid crystal is vertically aligned is represented by the above formula (1), and 1, m and η are both 1, R2 Is a phenyl group, R3 is a phenyl or cyclohexyl group, R4 is a cyclohexyl group, R5 is an alkyl group having 2 to 24 carbon atoms, or when l, m and η are both 0, R5 is a carbon atom number 12 a diamine of an alkyl group of ~22. 12. The liquid crystal alignment agent according to any one of claims 8 to 11, wherein the diamine having a side chain (Α) in which the liquid crystal is vertically aligned is a diamine having any of the following structures, 65·201141912 [化8] A liquid crystal alignment film obtained by using a liquid crystal alignment agent according to any one of claims 8 to 12. -66- 201141912 Four designated representative maps: (1) The designated representative circle of this case is: None (2) The symbol of the symbol of this representative figure is simple: No 201141912 If the case of this case is 彳b, please reveal the characteristics that can best display the invention. Chemical formula: none