TW201219379A - Liquid crystal-aligning agent, liquid crystal-aligning film, liquid crystal display element and method for producing liquid crystal display elements - Google Patents

Abstract

The liquid crystal-aligning agent comprises polyimide precursor with side chains that vertically orient liquid crystals and photoreactive side chains that contain at least one kind selected from methacrylic, acrylic, vinyl and cinnamoyl groups, as well as at least one kind of polymer selected from polyimides obtained by imidization of said polyimide precursors, a polymerizable compound having photopolymerizing or photo-crosslinking groups on each of two or more ends, and solvent.

Description

[Technical Field] The present invention relates to a liquid crystal alignment agent and a liquid crystal which can be used in the manufacture of 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. An alignment film, a liquid crystal display element, and a method of manufacturing a liquid crystal display element. [Prior Art] A liquid crystal display device in which a liquid crystal molecule that is aligned perpendicular to a substrate is subjected to an electric field (also referred to as a vertical alignment (VA) method) contains a voltage applied to the liquid crystal molecules in the manufacturing process. The step of irradiating ultraviolet rays. In the liquid crystal display device of the above-described vertical alignment type, it is known that a photopolymerizable compound is added to the liquid crystal composition, and a vertical alignment film such as polyimide is used, and a voltage is applied to the cell, and the ultraviolet ray is accelerated. The technique of the response speed (for example, refer to Patent Document 1 and Non-Patent Document 1) (PSA (Plaster sustained Alignment) liquid crystal display). Generally, the tilt direction of the liquid crystal molecules responsive to the electric field can be controlled by a protrusion provided on the substrate or a slit provided in the display electrode, but a photopolymerizable compound is added to the liquid crystal composition, and a voltage is applied to the cell side. Under the irradiation of ultraviolet rays, 'the tilt direction of the liquid crystal molecules is formed on the liquid crystal alignment film by the polymer structure of 100 million.' Therefore, the response speed of the liquid crystal display element is changed as compared with the method of controlling the tilt direction of the liquid crystal molecules only by the protrusions or slits. Faster. -5-201219379 The liquid crystal display element of the PSA type has a low solubility in a liquid crystal compound, and has a problem of low temperature when the amount of addition is increased. On the other hand, if the addition amount of the polymerizable compound is reduced, a good alignment state is obtained. Further, since the unreacted compound remaining in the liquid crystal becomes an impurity (contamination) in the liquid crystal, there is also a problem of reliability of the crystal display element. Further, in the PS A mode, when the irradiation amount is too large, the components in the liquid crystal are caused to have a low letterability. In addition, the photopolymerizable compound is not added to the liquid crystal composition and is added to the liquid crystal alignment film. The degree of liquid crystal display element can also be accelerated (SC-PVA type liquid crystal display) (for example, reference document 2). [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2003-307720 [Non-Patent Document] [Non-Patent Document 1] K. Hanaoka, SID 04 DIGEST, 1202 [Non-Patent Document 2] KH Y. -J.Lee, SID 09 DIGEST, 668 [Summary of the Invention] When the polymerization of the problem to be solved by the invention is precipitated, the polymerization is not reduced by the UV decomposition of the liquid g, and the response is accelerated by the non-specific. 1 200-P.666 - -6 - 201219379 However, it is expected to further accelerate the response speed of the liquid crystal display element. In addition, it is considered that the reaction rate of the liquid crystal display element can be accelerated by increasing the amount of the photopolymerizable compound to be added. However, when the photopolymerizable compound is left unreacted in the liquid crystal and remains directly, it becomes an impurity, and the reliability of the liquid crystal display element is lowered. For this reason, a polymerizable compound which accelerates the response speed with a small addition amount is expected. An object of the present invention is to provide a method for producing a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, and a liquid crystal display element, which can improve the response speed of a liquid crystal display device of a vertical alignment type, in order to solve the problems of the prior art described above. The liquid crystal alignment agent of the present invention which solves the above problems is characterized by having a polymer, a polymerizable compound and a solvent, wherein the polymer is selected from the group consisting of a polyimide precursor, and the polyimide precursor is passed through And at least one polymer obtained by imidization of the obtained polyimine; the polyimine precursor having a side chain having a liquid crystal alignment direction and containing a selected from the group consisting of a methacryl group, a propenyl group, a vinyl group, and a cassia A polyimine precursor of at least one photoreactive side chain of the group; the polymerizable compound is a polymerizable compound having a photopolymerization or photocrosslinking group at each of two or more terminals. Further, the photoreactive side chain preferably contains a group selected from the following formula (I). 201219379 [化1] (Ο ο C—C=CH:

-0 - C - G = CHi (wherein R11 is H or methyl) Further, the photopolymerization or photocrosslinking group is preferably selected from the following formula (Π) (II) (II)

(wherein R12 is an anthracene or an alkyl group having 1 to 4 carbon atoms, and oxime 1 is a divalent aromatic ring or a heterocyclic ring which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, Ζ2 a monovalent aromatic ring or a heterocyclic ring which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. The liquid crystal alignment film of the present invention is obtained by applying the above liquid crystal alignment agent onto a substrate. The characteristics obtained after firing are characteristic. The liquid crystal display device of the present invention is characterized in that it has a unit cell in which a liquid crystal layer is provided by contacting a liquid crystal alignment film which is applied to a substrate and is fired by the liquid crystal alignment agent, and the liquid crystal layer is provided on the liquid crystal layer. It is made by applying ultraviolet light to the upper side while applying a voltage. -8 - 201219379 In the method for producing a liquid crystal display device of the present invention, a liquid crystal layer is provided in contact with a liquid crystal alignment film obtained by applying the liquid crystal alignment agent onto a substrate and firing the film, and a voltage is applied to the liquid crystal layer. It is characterized by the irradiation of ultraviolet rays to produce a unit cell. EFFECT OF THE INVENTION The present invention is a liquid crystal display element which can improve the vertical alignment mode of the response speed. Further, in the liquid crystal alignment agent, even when the amount of the polymerizable compound added is small, the response speed can be sufficiently improved. Mode for Carrying Out the Invention The present invention will be described in detail below. The liquid crystal alignment agent of the present invention has a polyfluorene selected from a side chain having a side chain having a liquid crystal alignment direction and at least one photoreactive side chain selected from a methacryl group, a propenyl group, a vinyl group and a cinnamyl group. An imine precursor, and at least one polymer of the polyimine obtained by imidating the polyimine precursor with ruthenium, having a polymerization of photopolymerization or photocrosslinking at each of two or more terminals Sex compounds, and solvents. The liquid crystal alignment agent is a solution for forming a liquid crystal alignment film, and the liquid crystal alignment film is a film for aligning the liquid crystal in a predetermined direction. In the present invention, the film is oriented in a vertical direction. First, the polymerizable compound containing the liquid crystal alignment agent of the present invention will be described in detail. The liquid crystal alignment agent of the present invention is one which contains two or more polymerizable compounds each having a group which undergoes photopolymerization or photocrosslinking. In other words, the polymerizable compound contained in the liquid crystal alignment agent of the present invention is a compound having 2 -9 ** 201219379 or more terminals having a photopolymerization or photocrosslinking at the terminal. Here, the polymerizable compound having a group for photopolymerization is a compound having a functional group which is polymerized by irradiation of light. Further, the compound having a photocrosslinking group is a compound having a functional group which is a polymer of a polymerizable compound or a polyimine precursor selected by irradiation with light, and the polycondensation. The quinone imine precursor is reacted with at least one polymer of the polyimine obtained by hydrazine imidization to be crosslinked with them. Further, a compound having a group for performing photocrosslinking and a compound having a group for photocrosslinking also react with each other. The polymerizable compound is simultaneously contained in a liquid crystal alignment agent which is a polyimine precursor selected from the following, and a polycondensation obtained by imidating the polyimine precursor At least one polymer of ruthenium imide having a side chain having a vertical alignment with a liquid crystal to be described later and containing a methacryl group, a propylene group, a vinyl group, and a cinnamyl group. At least one photoreactive side chain polyimine precursor is used for the manufacture of a liquid crystal display element of a vertical alignment type such as an SC-PVA liquid crystal display by using the liquid crystal alignment agent, and has a liquid crystal display element for use alone When the polymer having a vertical side chain and a photoreactive side chain or a polymerizable compound is aligned, the response speed can be drastically increased, and the reaction rate can be sufficiently increased even if a small amount of the polymerizable compound is added. Examples of the group to carry out photopolymerization or photocrosslinking include a valent group of the above formula (II). Specific examples of the polymerizable compound include a compound having a group in which photopolymerization is carried out at each of two terminal groups of the following formula (III), and a light having a concentration of -10-201219379 as shown in the following formula (IV) The terminal of the polymerization group is a compound having a terminal having a photocrosslinking group or a compound having a photocrosslinking group at each of two terminal ends represented by the following formula (V). Further, in the following formulae (III) to (V), R12, Z1 and Z2 are the same as R12, Z1 and Z2 in the above formula (II), and Q1 is a divalent organic group. It is preferred that Q1 has a cyclic structure such as a phenyl (-C6H4-), a phenyl (-C6H4-C6H4-) or a cyclohexyl group (-C6H1Q-). Because of the large interaction with the liquid crystal. [Chemical 3] (III)

-11 - 201219379 [5] (V)

Specific examples of the polymerizable compound represented by the formula (111) include a polymerizable compound represented by the following formula (1). For the following formula (1), V is a single bond or -R1. - ' R1 is a linear or branched carbon number of 1 to 1 Å. The alkyl group is preferably -R1. - No" R1 is a linear or branched carbon group having 2 to 6 carbon atoms. Further, 'W is a single bond or is represented by -OR2-, and R2 is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably represented by -OR2., and R2 is a linear or branched carbon number of 2 ~6 alkylene. Moreover, V and W may be the same or different structures, but they are easy to synthesize at the same time. Further, the polymerizable compound represented by the following formula (1) can be removed by the present invention because of another application. [Chemical 6]

The polymerizable compound represented by the above formula (1) is a specific structural compound having an α-methyl-γ-butyrolactone group having a polymerizable group (a group for photopolymerization) at both terminals, so the polymer is a rigid structure having excellent liquid crystal alignment immobilization ability, as shown in the later-described embodiment, by using a polyfluorene obtained by subjecting a polyimine precursor to a polyimide precursor and imidating the polyimine precursor In the production of a vertical alignment type liquid crystal display element such as an SC-PV(R) liquid crystal display used as a liquid crystal alignment film material, at least one type of polymer of the imine can greatly improve the response speed. Further, in the liquid crystal distribution -12-201219379, the film formation process includes a high-temperature firing step in which the solvent is completely removed, but has an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, and an epoxy group. The compound of the polymerizable group is one in which heat stability is lacking, and it is difficult to withstand high temperature firing. On the other hand, the polymerizable compound represented by the above formula (1) may have a structure which lacks thermal polymerization property, and thus can sufficiently withstand high temperatures, for example, a firing temperature of 200 ° C or higher. Further, as a group for photopolymerization or photocrosslinking, it is not a CK-extended methyl-γ-butyrolactone group, even if it is a polymerizable compound having an acrylate group or a methacrylate group, if it has the acrylate group Or a polymerizable compound having a structure in which a methacrylate group and a phenyl group are bonded to a phenyl group, and a polymerizable compound having a methyl-γ-butyrolactone group at both ends; In particular, the response speed can be greatly improved. Further, in the case of a polymerizable compound having a structure in which an acrylate group or a methacrylate group is bonded to a phenyl group via a spacer such as an oxyalkylene group, heat stability can be improved and the temperature can be sufficiently maintained at a high temperature, for example. The firing temperature above 20CTC. Among the polymerizable compounds, the compound represented by the following formula is a novel compound. -13- 201219379 [化7]

The method for producing the polymerizable compound is not particularly limited, and it can be produced, for example, according to a synthesis example described later. For example, the polymerizable compound represented by the above formula (1) can be synthesized by a combination of methods in organic synthetic chemistry. For example, the method of P. Talaga, M. Schaeffer, C. Benezra and JLStamp f, Synthesi s, 5 3 0 (1 990 ) proposed by Talaga et al. (Bromomethyl)propenoic acid (2-( bromomethyl ) propenoi c aci d ) is synthesized with awake or ketone. The Amberlyst 15 is a strong acid ion exchange resin manufactured by Rohm and Haas Company. -14- 201219379 [Chem. 8]

(wherein R' is not a valence organic group) Further, 2-(bromomethyl)acrylic acid can be reversed by the following, Ramarajan^^K.Ramarajan, K.Kamalingam, DJO and K.D.B er 1 i η, Organic Synthesis, vol. 61, 56-59 The proposed method was synthesized. [Chemical 9] As shown by Donnell 1 98 3 )

As a specific synthesis example, when V is -Rh- and W is -OR2 and R2 is the same polymerizable compound represented by the above formula (1), the two methods shown in the above reaction formula are shown. [化10] -,R1 and "raise the next Η

K^Oj/Acctcae ►OHC-R1

PyrijiaiucD C ,ch,Pj

5payio%RCK«]} .THF/Hi〇 -15- 201219379 [化11] η^〇-〇-°η

SoCyiOHHl THF/H3p [〇(»<]) Further, the above formula (wherein R1 and R2) are different (the method shown by the following reaction formula is mentioned) [ y 12 ] y〇V ya=v HO- CHjrRirBr H〇~^ KfCOyAcctanc · ι,^〇-〇^-Λΐ^ The polymerizable compound shown » HO-CHi-R*

PyrfiiehuB CUcrodnoBule

When the polymerizable compound represented by the above formula (1) wherein V and W are a single bond is synthesized, a method represented by the following reaction formula may be mentioned. [Chemical 13] 〇η〇-〇-〇^*°

Further, the liquid crystal alignment agent of the present invention is at least one selected from the group consisting of a polyimine precursor and a polyimine obtained by imidating the polyimide precursor with ruthenium. The liquid crystal is aligned with a polymer having a vertical side chain and a photoreactive side chain. Further, examples of the polyimine precursor include polyglycine (also referred to as polyglycolic acid) or polyphthalamide. -16-201219379 The liquid crystal having the polymer is aligned in a vertical direction, and the liquid crystal is perpendicular to the substrate, and is not particularly limited. For example, a long-chain alkyl group or a long-chain alkane is exemplified. A hydrocarbon group having a ring structure or a branched structure in the middle, a hydrocarbon group such as a steroid group, or a part or all of hydrogen of these groups is substituted with a group of a fluorine atom or the like. Of course, it is also possible to have a side chain in which two or more types of liquid crystals are aligned vertically. The vertical side chain of the liquid crystal alignment can be directly bonded to the polyimine precursor such as polylysine or polyphthalate or the main chain of the polyimine, and can be directly bonded to the polyamine skeleton or The polyimine skeleton or the like may be bonded via a suitable bonding group. Examples of the side chain in which the liquid crystal is aligned vertically may, for example, be a hydrocarbon group having a carbon number of 8 to 30, preferably 8 to 22, which may be substituted by fluorine, and specific examples thereof include an alkyl group, a fluoroalkyl group, an alkenyl group and a benzene group. Ethyl, styrenealkyl, naphthyl, fluorophenylalkyl, and the like. Examples of the side chain in which the other liquid crystals are aligned are, for example, those represented by the following formula (a). - (a) I m η (In the formula (a), 1, m and n each independently represent an integer of 〇 or 1, and R3 represents a stretching number of 2 to 6 carbon atoms, -〇-, -COO -, -OCO-, -NHCO-, -CONH- or an alkylene-ether group having a carbon number of 1 to 3, R4, R5 and R6 each independently represent a phenyl or cycloalkyl group, and R7 represents hydrogen or carbon. a number of 2 to 24 alkyl groups or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring or a monovalent large cyclic substituent thereof; and, in the above formula (a) R3 is preferably an alkyl-ether group having -0-, -COO-, -CONH-, or a carbon number of 1 to 3 from the viewpoint of easiness of synthesis. Further, R4, R5 and R6 in the formula (a) are preferably a combination of R4, R5 and R6 as shown in the following Table i from the viewpoints of easiness of synthesis and ability to align the liquid crystal -17-201219379. [Table 1] 1 m η R4 R5 R6 1 1 1 phenyl extended phenyl ring hexyl 1 1 1 phenyl ring hexyl ring hexyl 1 1 1 ring hexyl ring hexyl ring hexyl 1 1 0 benzene Base phenyl 1 1 0 phenyl ring hexyl 1 1 0 ring hexyl - cyclohexyl _ while at least one of 1, m, η is 1, R7 in formula (a) is preferably hydrogen or carbon number The alkyl group of 2 to 14 or the alkyl group containing fluorine is more preferably hydrogen or an alkyl group having 2 to 12 carbon atoms or an alkyl group containing fluorine. Further, when 1, m and η are all 0, R7 is preferably an alkyl group having 12 to 22 carbon atoms or an alkyl group containing fluorine, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, and the like. The monovalent large cyclic substituent is more preferably an alkyl group having 12 to 20 carbon atoms or an alkyl group containing fluorine. The amount of the side chain in which the liquid crystal is aligned in the vertical direction is not particularly limited as long as it is a liquid crystal alignment film in which the liquid crystal alignment direction is vertical. However, in the liquid crystal display element including the liquid crystal alignment film, it is preferable that the amount of the vertical alignment of the liquid crystal alignment is as small as possible within a range that does not impair the display characteristics of the voltage holding ratio or the accumulation of the residual DC voltage. . Moreover, the ability of the polymer having the side chain of the liquid crystal alignment to be perpendicular to the liquid crystal alignment is different depending on the structure in which the liquid crystal is aligned in a vertical side chain. Generally, if the liquid crystal is aligned in a vertical side chain, When the amount of change is large, '-18" 201219379 The ability to make the liquid crystal alignment vertical will increase, and decrease will decrease. Further, if it has a ring structure, the ability to align the liquid crystal in a vertical direction tends to be higher than that of a person having no ring structure. Further, a polymer obtained by at least one of a polyimine precursor such as polylysine or a polyphthalamide contained in the liquid crystal alignment agent of the present invention and a polyimine has a photoreactive side chain. The photoreactive side chain is a side chain which is reacted by irradiation of light such as ultraviolet rays (UV), and has a functional group capable of forming a covalent bond (hereinafter also referred to as a photoreactive group). In the present invention, as a light The reactive group contains at least one selected from the group consisting of a methacryl group, a propylene group, a vinyl group, and a cinnamyl group. The polymer obtained by at least one of a polyimine precursor such as polylysine or a polyphthalate contained in the liquid crystal alignment agent and a polyamidene has a content selected from the group consisting of a methacryl group, When at least one of the photoreactive side chain of the acryl group, the vinyl group and the cinnamyl group is used together with the above polymerizable compound in the liquid crystal alignment agent, the response speed can be improved as shown in the examples described later. The photoreactive side chain may be directly bonded to the main chain of the polyimine precursor or the polyimine, or may be bonded via a suitable bonding group. Examples of the photoreactive side chain include those represented by the following formula (b). - R8 - R9 - R10 (9) (In the formula (b), R8 represents a single bond or -CH2-, -0-, -COO-, -〇c〇_, -NHCO-, -CONH-, - Any of NH-, -CH2〇-, -N(CH3)-, -CON(CH3)-, -N(CH3)CO-, R9 represents a single bond or a carbon number substituted by a fluorine atom or substituted by a fluorine atom ～20 alkylene, alkylene-CH2- can be 201219379 optionally substituted by -CF2 - or -CH=CH-, and can be substituted for any of the following groups when they are not adjacent to each other; 〇_, _c〇〇_, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, a divalent heterocyclic ring. R1Q represents a methyl propyl group, a propyl group, an aryl group, Cassia ruthenium) and R8 in the above formula (b) can be formed by a general organic synthesis method, but from the viewpoint of easiness of synthesis, _CH2-, -〇-, -COO-, -NHCO-, - Further, NH- or -CH20- is preferably a carbon ring or a heterocyclic ring which is a divalent carbocyclic ring or a divalent heterocyclic ring of any -CH2- which is substituted for R9, and specifically includes the following structures, but is not limited thereto. This is the case. [化 16] Ο O CK) Ch〇 0-00

R is preferably a methacryl group, a propylene group or a vinyl group from the viewpoint of photoreactivity. Further, the above formula (b) is more preferably a structure containing a group selected from the above formula (I). The photoreactive side chain is present in a range in which the reaction speed of the liquid crystal can be accelerated by reacting with ultraviolet rays to form a covalent bond, and it is preferable to further accelerate the response speed of the liquid crystal so as not to affect other characteristics. The next 'as much as possible is better. -20- 201219379 Manufactured from a polyfluorene imine having a side chain having a liquid crystal alignment direction perpendicular thereto and a photoreactive side chain containing at least one selected from the group consisting of a methacryl group, a propenyl group, a vinyl group, and a cinnamyl group The method of the precursor and the at least one polymer of the polyimine obtained by imidating the polyimine precursor with ruthenium is not particularly limited, for example, by the reaction of a diamine with a tetracarboxylic dianhydride to obtain a poly In the method of proline, a diamine having a side chain in which a liquid crystal is aligned in a vertical direction or a tetracarboxylic dianhydride having a side chain in which a liquid crystal is aligned vertically or having a methacryl group, a propylene group, or the like a diamine of a photoreactive side chain of at least one of a vinyl group and a cinnamyl group or a tetracarboxylic acid having a photoreactive side chain containing at least one selected from the group consisting of a methacryl group, a propenyl group, a vinyl group, and a cinnamyl group The dianhydride can be copolymerized. Examples of the diamine having a side chain in which the liquid crystal is aligned perpendicularly include a long-chain alkyl group, a group having a ring structure or a branched structure on the middle of a long-chain alkyl group, a hydrocarbon group such as a steroid group, or a hydrogen group of these groups. A diamine which is partially or wholly substituted with a fluorine atom as a side chain, and examples thereof include a diamine having a side chain represented by the above formula (a). More specifically, for example, a diamine such as a hydrocarbon group having a carbon number of 8 to 30 in which hydrogen is replaced by fluorine, or a diamine represented by the following formulas (2), (3), (4), and (5) may be mentioned. It is not limited to this. [化17] 0^, 侦朴Η (7)

HjN I m rt (1, m, n, R3 to R7 in the formula (2) have the same definition as the above formula (a)) -21 - 201219379 [Chem. 18]

(In the formulas (3) and (4), A10 represents -COO-'-OCO-'-CONH-, -NHCO-, -CH2-, -〇-, -CO- or -NH-, and Ah represents a single bond. Or the phenyl group 'a' represents a structure in which the liquid crystal alignment is perpendicular to the side chain shown in the above formula (a), and a 'is the same as the side chain perpendicular to the liquid crystal alignment shown in the above formula (a). The structure takes out a divalent group of the structure of an element such as hydrogen) [Chem. 19]

(In the formula (5), A14 represents an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom. A15 represents a 1,4-cyclohexyl group or a 1,4-phenylene group, and A16 represents an oxygen atom or -COO-. * (However, the bond with "*" is combined with Al5), and Al7 represents an oxygen atom or -COO-* (however, the bond with "*" is combined with (CH2) a2). Also, ai An integer representing 0 or 1, a2 represents an integer of 2 to 10, and a3 represents an integer of 0 or 1. The bonding position of the two amine groups (-NH2) in the formula (2) is not limited. Specifically, for the bonding group of the side chain, the position of 2, 3 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 location. Among them, from the viewpoint of reactivity in synthesizing poly-proline, the position of 2, 4, the position of 2, 5, or the position of 3, 5 is preferable. Further, when the ease of synthesizing the diamine is added, the position of 2, 4 or the position of 3, 5 is preferable. [2012] The specific structure of the formula (2) is exemplified by the following formula [A-1] to the formula, but is not limited thereto. [Chem. 20]

(Formula [A Fluorine Institute -1]~ In the formula [A-5], A! is an alkyl group or a group having a carbon number of 2 to 24) [Chem. 21]

(In the formula [A-CH20-, alkoxy-6] and the formula [A-7], A2 represents -0-'-OCH2-, -COOCH2- or -CH2OCO-, and A3 is a carbon number of 1 to 22. An alkyl group, a hospital containing fluorine or a oxy group containing fluorine) (formula [άτονη-, -OCH2- or an alkyl group or

8]~ In the formula [A-10], A4 represents -COO·, -OCO-, -NHCO-, -COOCH2-, -CH2OCO-, -CH20-, -CH2-, and A5 is an alkane having 1 to 22 carbon atoms. Base, hospital oxygen 'containing alkoxy containing fluorine and fluorine) 23- 201219379 [Chem. 23]

(In the formula [A-11] and the formula [A-12], A6 represents -COO-, -OCO-, -CONH- '-NHCO- ' -COOCHz- ' -CH2OCO- ' -CH2O- ' -OCH2·, -CH2-, -O- or -NH-, A7 is a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxyl group) 24] ΗίΝ^δ°-Ό-00Α· ΗϊΝ^δ°-〇-00Λ. [~1 sentence] CA-14] (in the formula [Α-13] and [Α-14], Α8 is the carbon number 3 Cis-trans isomers of ~12 alkyl, I,4-cyclohexyl are each a trans isomer) [Chem. 25]

HjN (In the formula [A-15] and the formula [A-16], A9 is an alkyl group having a carbon number of 3 to 12, and the cis-trans isomer of the 1,4-cyclohexyl group is a trans isomer) -24 - 201219379 [Chem. 26]

Specific examples of the diamine represented by the formula (3) include a diamine represented by the following formula [A-25] to the formula [A-30], but are not limited thereto. [化27]

(In the formula [A-25] to the formula [A-30], A12 represents -COO-, -OCO-, -CONH-, -NHCO-, -CH2-, -0-, -CO- or -NH-, A13 represents an alkyl group having 1 to 22 carbon atoms or an alkyl group containing fluorine. Specific examples of the diamine represented by the formula (4) include the following formula [A-31] to formula [A-32]. Diamine, but is not limited to this. -25- 201219379

Among them, [A-1], [A-2], [A-3], [A-4], [A-5] from the viewpoint of the ability of the liquid crystal alignment to be perpendicular and the response speed of the liquid crystal. The diamines of [A-25], [A-26], [A-27], [A-28], [A-29], [A-30] are preferred. When the diamine is used as the liquid crystal alignment film, the liquid crystal alignment property, the tilt angle, the voltage holding property, and the storage charge can be used in one type or in a mixture of two or more types. The diamine having such a side chain in which the liquid crystal is aligned vertically is preferably used in an amount of 5 to 50 mol% of the diamine component used for the synthesis of the polyamic acid, preferably 10 to 40 mol of the diamine component. The ear % is a diamine having a side chain in which the liquid crystal is aligned vertically, and particularly preferably 15 to 30 mol%. The amount of the diamine having such a side chain in which the liquid crystal is aligned vertically is an increase in the response speed or the alignment of the liquid crystal when the amount of the diamine component used for the synthesis of the polyamic acid is 5 to 50% by mole. Excellent immobilization ability. The diamine having a photoreactive side chain containing at least one selected from the group consisting of a methacryl group, a propylene group, a vinyl group, and a cinnamyl group may, for example, be a diamine having a side chain represented by the above formula (b). . More specifically, for example, a diamine represented by the following general formula (6) is mentioned, but it is not limited thereto. -26- 201219379 [Chem. 29]

R8 — R9_R1. (6) The definition of R8, R9 and 11| in the formula (6) is the same as the above formula (b). The bonding position of the two amine groups (-NH2) in the formula (6) is not limited. Specific examples thereof include a bonding group for a side chain, a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, a position of 3, 4, and a position of 3, 5. position. Among them, the position of 2, 4, the position of 2, 5 or the position of 3, 5 is preferable from the viewpoint of reactivity in synthesizing polyamic acid. Further, in the case of the ease of synthesizing the diamine, it is preferred to have a position of 2, 4 or a position of 3, 5. The diamine having at least one photoreactive side chain selected from the group consisting of a methacryl group, a propenyl group, a vinyl group and a cinnamyl group may specifically be a compound as described below, but is not limited thereto. [化30]

a bonding group of NHCO-, -NH-, Y represents an alkyl group having 1 to 20 carbon atoms which are unsubstituted or substituted by a fluorine atom) -27-201219379 having a methacryl group, a propylene group, an ethylene group selected from the above The diamine of the photoreactive side chain of at least one of the base and the cinnamyl thiol group, and the liquid crystal alignment property, the tilt angle, the voltage holding property, the storage charge, and the like when used as a liquid crystal alignment film, and the liquid crystal response speed when used as a liquid crystal display element For example, one type or a mixture of two types or more can be used. Further, it has a diamine containing a photoreactive side chain selected from at least one of a methacryl group, a propylene group, a vinyl group and a cinnamyl group, and is used in a diamine component used for the synthesis of polylysine. The amount of 10 to 70 mol% is preferably, preferably 20 to 60 mol%, and particularly preferably 30 to 50 mol%. Further, the polyamine can be used as the diamine component other than the diamine having the above-mentioned side chain of the liquid crystal alignment or the diamine having a photoreactive group, without impairing the effects of the present invention. Use. Specifically, 'p-phenylenediamine, 2,3,5,6-tetramethyl-P-phenylenediamine, 2,5-dimethyl-P-phenylene Amine, m-phenylenediamine, 2, dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diamino Phenol, 2,4-diaminoguanidine, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diamine Resorcinol, 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'--28 201219379 diamine Diphenylmethane, 4,4'-diaminodiphenyl ether 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl 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'-di Aminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3' -diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-A (3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl (2,3'-diaminodiphenyl) Amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diamine Naphthyl, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthyl, 1,6-diaminonaphthyl, 1 , 7- Aminonaphthyl, 1,8-diaminonaphthyl, 2,5-diaminonaphthyl, 2,6-diaminonaphthyl, 2,7-diaminonaphthyl, 2,8-diamine 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, I,4·bis(3-aminophenyl)butane, double ( 3,5-Diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, I , 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 double Methyl)]diphenylamine, 3,4'-[ 1,4-Extension -29- 201219379 Phenyl bis(methyl)diphenylamine, 3,4'-[l,3-phenylene bis(... Methyl)]diphenylamine, 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3,3'-[1,3-phenylenebis(methyl) Diphenylamine, 1,4-stretch Bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-amino) Phenyl) ketone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylphenylbis(4-aminobenzoate), I,4 - phenyl bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoate) Acid ester), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalic acid Ester, bis(3-aminophenyl)isophthalate, \氺'-(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, hydrazine, Ν'-double (3 -aminophenyl)terephthalamide, hydrazine, Ν'-bis(4-aminophenyl)isophthalamide, hydrazine, Ν'-bis(3-aminobenzene Isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-double 4-(4-Aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)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-diamino benzoic acid, 2,5-diaminobenzoic acid, 1,3-bis(4--30-201219379 aminophenoxy)propane, 1,3-double (3) -aminophenoxy)propane, n-bis(4-aminophenoxy)butane, anthracene, 4-bis(3-aminophenoxy)butane, 1,5-bis(4-amine Phenoxy)pentane, 15-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, bismuth (3-aminophenoxy)垸, 1,7-bis(4-aminophenoxy)gum, hydrazine, 7-(3-aminophenoxy)heptane, 1,8-bis(4-amine Octyloxy)octane, anthracene, 8-bis(3-aminophenoxy)octane' 1,9-bis(4-aminophenoxy)decane, 19-bis(3-amino group Phenoxy)decane, iota, ι〇_(;4_aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, I,〗 〖" Phenoxy group) - Institute, 1,11-(3-aminophenoxy)decane, iota, 12-(4.aminophenoxy)dodecane, 1,12-(3-amine An aromatic diamine such as phenoxy)dodecane, an alicyclic diamine such as bis(4-aminocyclohexyl)methine or bis(4-amino-3-methylcyclohexyl)carboxamidine, 1 , 3-diaminopropane, iota, diaminobutane, I,5-diaminopentane, 1,6-diaminohexane, iota, 7-diaminoheptane, I , 8-diaminooctane, 1,9-diaminodecane, l,i-diaminodecane, iota,11-diaminoundecane, 1,1 2-diamine An aliphatic diamine such as dioxane. The above-mentioned other diamines are used in combination with two or more types of liquid crystals, such as a liquid crystal alignment film, a tilting angle, a voltage holding property, and a storage charge. The tetrahydrous dianhydride is not particularly limited in its synthesis with polyamine. Specific examples thereof include pyromellitic acid and 2'3'6'7 $ < P3 acid, tetracarboxylic acid, 1,2,5,6-naphthyltetracarboxylic acid, 1,4,5,8-naphthyl, λ,-biphenyltetra-2,3,6,7 - indole tetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4yl) acid carboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid, double (3,4_Dicarboxyze " -31 - 201219379 , 3,3',4,4'-benzophenone tetracarboxylic acid, bis(3,4-di residuephenyl)anthracene, double (3 , 4-dimercaptophenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3 , 4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyloxane, bis(34-dicarboxyphenyl)diphenylnonane, 2,3,4,5-pyridinetetracarboxylic acid Acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4,-diphenylfengtetracarboxylic acid, 3,4,9,1〇•茈tetracarboxylic acid , I,3·diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid 'oxydi-phthalic acid, 1,2,3,4-cyclobutanetetracarboxylic acid,丨'2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4·tetramethyl-perylene cyclobutane tetracarboxylate Acid, I,2-dimethyl-I,2,3,4·cyclobutane tetracarboxylic acid, hydrazine, 3-dimethyl- 1,2,3,4-cyclobutane tetradecanoic acid, hydrazine, 2,3,4-cyclohine tetradecanoic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3,4·dicarboxy- 1-cyclohexyl crotonic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-12,3,4-tetrazo-indole-naphthyl succinic acid, bicyclo[3,3, 0〕Xinyuan-2,4,6,8-tetraresidic acid, bicyclo[4,3,0] brothel · 2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane -2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0 <2,6>] i-alkane-3,5,9,1-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-di-side oxytetrahydrofuran-3- -i,2,3,4-tetrahydronaphthyl-1,2-dicarboxylic acid, bicyclo[2,2,2]oct-7-thin-2,3,5,6-tetraresidic acid, 5-(2,5-di-side oxytetrahydrofuran)-3-methyl-3-cyclohexane-12-dicarboxylic acid 'tetracyclo[.] dodecane-4,5,9,10-tetracarboxylic acid '3,5,6·Tricarboxynorbornane_2 : 3,5 : 6 —decanoic acid, 1,2,4,5-cyclohexanyltetracarboxylic acid, and the like. Of course, it is possible to use one type or two or more types in combination with the characteristics of liquid crystal alignment, voltage retention characteristics, and storage charge when the tetracarboxylic dianhydride is used as the liquid crystal alignment film. -32- 201219379 A polyamic acid is obtained by a reaction of a diamine component and a tetracarboxylic dianhydride, and a well-known synthetic method can 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 has an advantage that no by-products are produced. The organic solvent to be used in the above reaction is not particularly limited as long as it is a polylysine which is produced by dissolution. Further, even if it is an organic solvent which does not dissolve polyamic acid, it can be used after being mixed with the above solvent in the range in which the produced polyamic acid is not precipitated. Further, the water in the organic solvent hinders the polymerization reaction and becomes a cause of further hydrolysis of the produced polyamic acid. Therefore, it is preferred that the organic solvent is dried by dehydration. Examples of the organic solvent used in the reaction include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, and N-methylmethyl. Indoleamine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, i,3-dimethyl-2-imidazolium, 3-methoxy-N,N-di Methylpropane decylamine, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, isopropanol, A Oxymethylpentanol, dipentene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, methyl sarsulu, ethyl 赛路Sue, methyl sarbuta acetate, ethylene glycol dibutyl ether acetate, ethylene glycol diethyl ether acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol Acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol 'propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tertiary butyl ether' Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol , diethylene glycol-33- 201219379 monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, : dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl B Acid ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, Butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, η-hexane, η-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, 3 Methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methyl Propyl oxypropionate, butyl 3-methoxypropionate, two Glyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, and the like. 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, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride component is directly dispersed or dissolved in the organic solvent. a method of adding a solvent afterwards, a method of adding a diamine component by dissolving a tetracarboxylic dianhydride component in a solution dissolved in an organic solvent, or a method of mutually adding a tetracarboxylic dianhydride component and a diamine component, etc. Use any of these methods. Further, when the diamine component or the tetracarboxylic dianhydride component is formed of a plurality of compounds, the reaction may be carried out in a mixed state in advance, or the reaction may be carried out in an individual order, and the low molecular weight body which is individually reacted may be further The mixed reaction -34 - 201219379 was carried out as a high molecular weight body. The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted may be any temperature, and is, for example, -20 ° C to 150 ° C', preferably -5 ° C to 100 ° C. Further, the reaction can be carried out at any concentration. For example, the total amount of the diamine component and the tetracarboxylic dianhydride component in the reaction liquid is 1 to 50% by mass, preferably 5 to 30% by mass. In the above polymerization reaction, the molar ratio of the total number of moles of the tetracarboxylic acid dianhydride component to the total number of moles of the diamine component can be selected in accordance with the molecular weight of the obtained polyamic acid. As in the case of the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyamine. To indicate the best range, it is 〇. 8~1. 2. The method for synthesizing the polyamic acid used in the present invention is not limited to the above method, and in the same manner as the general method for synthesizing poly-branched acid, a tetracarboxylic acid or a tetracarboxylic acid having a corresponding structure is used instead of the above tetracarboxylic dianhydride. A tetracarboxylic acid derivative such as a carboxylic acid dihalide can be reacted by a known method to obtain a corresponding polyamine. As a method of imidating the above polyamic acid with ruthenium as a polyimine, a hydrazine imidization in which a poly phthalic acid solution is directly heated and a catalyst in a solution of a poly phthalic acid are added Media imidization. Further, the imidization ratio of polyaminic acid to polyimine is not necessarily 100%. The temperature at which the polyaminic acid is thermally imidized in a solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 T: while the water formed by the hydrazine imidization reaction Excluded from the outside of the system, it is better to carry out. The catalyst of lysine is imidized to a solution of poly-proline. -35-201219379 plus alkaline catalyst and anhydride, at -20~25 0 ° C, preferably stirred in hydrazine get on. The amount of the basic catalyst is 醯·5~, preferably 2 to 20 moles of anhydride of the phthalic acid group, and the amount of the anhydride is 1 time, preferably 3 to 30 moles. The basic catalyst ′ may, for example, be triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, it is preferred to carry moderate alkalinity in the reaction. As the acid anhydride, anhydride, trimellitic anhydride, pyromellitic dianhydride or the like, it is preferred that the purification after completion of the reaction is facilitated. The imidization rate by thixotropic oxime can be controlled by adjusting the amount of catalyst and the reaction temperature. Further, the polyphthalamide may be obtained by reacting a tetracarboxylic acid diester dichloride with the same diamine synthesized by the above polyamic acid or by reacting the same with the same diamine synthesized with the above polyamic acid. The appropriate condensation is carried out after the reaction is carried out in the next step. Alternatively, the acid may be acidified in advance in the above method, and the carboxylic acid in the lysine may be esterified by a polymer reaction. Specifically, for example, in the presence of a tetracarboxylic acid diester dichloride and a diorganic solvent, at -20 ° C to 150 ° C, preferably in the middle, for 30 minutes to 24 hours, preferably 1 hour. Polyamine amide can be synthesized in ~4 hours. Polypyridamine is obtained by heating the polyglycolate at a high temperature to cause ring closure. The reaction is carried out by recovering the produced polyglycolic acid, polyfluorene polyimide precursor or polyamidiamine from a reaction solution of a polyamidamine precursor amine such as polylysine or polyphthalate. The solution is poured into it to precipitate. As a weak solvent used for precipitation, it can be exemplified by 30 moles of 〜50 〇C to 50 moles of pyridine, and pyridine, which is an acetic anhydride with an acetic anhydride, a reaction product, and a carboxylic acid. The diesterification of the diester agent or base can also be obtained by reacting the amine with the base at 0 eC ～50 〇C, promoting the de- or poly- imidate to be equal to the weak solvent to produce methanol, -36-201219379 acetone, Hexane, ethylene glycol dibutyl ether, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer which has been introduced into a weak solvent and precipitated is filtered and recovered, and then dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the polymer recovered by precipitation is redissolved in an organic solvent, and the operation of reprecipitation recovery is repeated 2 to 10 times to reduce impurities in the polymer. The weak solvent in this case may, for example, be an alcohol, a ketone or a hydrocarbon. When three or more kinds of weak solvents selected from the group are used, the purification efficiency can be further improved, which is preferable. The liquid crystal alignment agent of the present invention may be one having the following polymer, a polymerizable compound, and a solvent, and the polymer is selected from the group consisting of a side chain having a liquid crystal alignment direction and a methacryl group. At least one of a photoreactive side chain polyimine precursor of at least one of a propylene group, a vinyl group, and a cinnamyl group, and at least one of the polyimine obtained by imidating the polyimine precursor with a quinone The polymerizable compound is a polymerizable compound having a group which undergoes photopolymerization or photocrosslinking at each of two or more terminals, and the compounding ratio is not particularly limited, and is carried out at each of two or more ends. The content of the polymerizable compound of the photopolymerization or photocrosslinking group is selected from at least one selected from the group consisting of a side chain having a liquid crystal alignment direction and a methacryl group, a propylene group, a vinyl group, and a cinnamyl group. The polyimine precursor of the photoreactive side chain and the at least one polymer of the polyimine obtained by imidating the polyimine precursor with 100 parts by mass of the polymer of 1 to 50 The share is better, to 5~ 30 parts by mass is more preferred. Further, it is selected from the group consisting of light having at least one selected from the group consisting of a methacryl group, a propenyl group, a vinyl group and a cinnamyl group, which has a side chain which is perpendicular to the liquid crystal alignment agent contained in the liquid crystal alignment agent. The content of the polyimine precursor of the chain and the at least one polymer of the polyimine obtained by imidating the polyimine precursor is preferably 1% by mass to 20% by mass. Preferably, it is 3 mass% to 15 mass%, and particularly preferably 3 mass% to 10 mass%. Further, the liquid crystal alignment agent of the present invention may be another polymer which may be selected from the group consisting of having a side chain having a liquid crystal alignment direction and a methacryl group, a propylene group, a vinyl group and At least one of a photoreactive side chain polyimine precursor of cinnabarinyl group and at least one polymer of the polyimine obtained by imidizing the polyimine precursor. In this case, the content of the other polymer in the entire polymer component is preferably 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass. The molecular weight of the polymer having a liquid crystal alignment agent is considered. When the strength of the liquid crystal alignment film obtained by coating the liquid crystal alignment agent and the workability at the time of coating film formation and the uniformity of the coating film, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is 5,000 to 1,000,000. Preferably, it is 1 inch, 〇〇〇~150,000. The solvent to be contained in the liquid crystal alignment agent is not particularly limited, and may be a component containing a polymer or a polymerizable compound, which is selected from the group consisting of the above-mentioned side chain having a liquid crystal alignment direction and containing a polyimide intermediate precursor of a photoreactive side chain of at least one of a methacryl group, a propylene group, a vinyl group, and a cinnamyl group, and a polyfluorene obtained by subjecting the polyimine precursor to imidization At least one polymer of the imine or a polymerizable compound having a photopolymerization or photocrosslinking group at each of two or more terminals. For example, an organic solvent exemplified as the synthesis of the above polyamic acid can be mentioned. 38- 201219379 wherein N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3·methoxy- N,N-dimethylpropane decylamine is preferred from the viewpoint of solubility. Of course, it is also possible to use a mixed solvent of two or more types. Further, it is preferred to use a solvent which improves the uniformity or smoothness of the coating film and is mixed with a solvent having a high solubility in a component of the liquid crystal alignment agent. Examples of the solvent for improving the uniformity or smoothness of the coating film include isopropyl alcohol, methoxymethylpentanol, methyl sarbuta, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and methyl group.赛路苏acetate, ethylene glycol dibutyl ether acetate, ethylene glycol diethyl ether acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol , ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol - third Butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate Methyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetic acid Ester monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl Butyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, η-hexane, η-pentyl Alkane, η-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, Methyl 3-methoxypropionate, 3-ethoxy-39-201219379 methyl ethyl propionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropane Acid, propyl 3-methoxypropionate butyl 3-methoxypropanoate, 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, η-propyl lactate, n-butyl lactate, Isoamyl lactate, 2-ethyl-1-hexanol, and the like. These solvents can be mixed in a plurality of types. When these solvents are used, the total amount of the solvent contained in the liquid crystal alignment agent is preferably 5 to 80% by mass, more preferably 20 to 60% by mass. The liquid crystal alignment agent may contain components other than the above. As such an example, 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 can be mentioned. Examples of the compound for improving film thickness uniformity or surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. More specifically, for example, Eftop EF301, EF3 03, EF3 52 (manufactured by TOHKEM PRODUCTS CORP), Megafac F171, F173, R-30 (manufactured by Otsuka Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahiguard AG710, Surflon S-382, SC101, SC102 > SC103, SC 104 'SCI 05 'SC106 (made by Asahi Glass Co., Ltd.), and the like. When the surfactant is used, the use ratio is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total of the polymer of the liquid crystal alignment agent. Specific examples of the compound which adheres to the substrate are -40 to 201219379, and examples thereof include a compound containing a functional decane or a compound containing an epoxy group. Examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxydecane. N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-醯Ureapropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxymercaptopropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1, 4,7-triazadecane, 10-triethoxyindolyl-1,4,7-triazadecane, 9-trimethoxyindolyl-3,6-diazepine acetic acid Ester, 9-triethoxyindolyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-amine Propyl triethoxy decane, N-phenyl-3-aminopropyl trimethoxy decane, N-benzene g-3-aminopropyl triethoxy decane, N-bis (oxyethyl) )-3-aminopropyltrimethoxydecane, N- Bis(oxyethylidene)-3-aminopropyltriethoxydecane'ethylene glycol propylene oxide ether, polyethylene glycol propylene oxide ether, propylene glycol propylene oxide ether, tripropylene glycol propylene oxide ether, Polypropylene glycol propylene oxide ether, neopentyl glycol propylene oxide ether, 1,6-hexanediol propylene oxide ether, glycerin propylene oxide ether, 2,2-dibromoneopentyl glycol propylene oxide ether, I , 3,5,6·Tetrapropenyl-2,4-hexanediol, N,N,N',N'-tetrakis(oxypropylene)-m-xylenediamine, 1,3 -bis (N, N-dioxypropylene aminomethyl)cyclohexane, N,N,N,,N,-tetrapropenyl-4' 4'-diaminodiphenylmethane, 3-(N-N- Alkyl-N-oxidized propyl base) Aminopropyltrimethoxy sand, 3_ (• 41 - 201219379 N, N-propylene oxide) aminopropyltrimethoxydecane, and the like. Further, in order to further increase the film strength of the liquid crystal alignment film, 2,2'-bis(4-hydroxy-3,5-.dihydroxymethylphenyl)propane or tetrakis(methoxymethyl)bisphenol may be added. Phenolic compound. When the amount of the polymer contained in the liquid crystal alignment agent is 100 parts by mass, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. Further, in the range in which the liquid crystal alignment agent does not impair the effects of the present invention, the above-mentioned other dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film may be added. By applying the liquid crystal alignment agent onto the substrate and firing, a liquid crystal alignment film in which the liquid crystal alignment is perpendicular can be formed. Since the liquid crystal alignment agent of the present invention has the following polymer and polymerizable compound, the response speed of the liquid crystal display element using the obtained liquid crystal alignment film can be accelerated. The polymer is at least one selected from the group consisting of a side chain having a vertical alignment of liquid crystals and at least one photoreactive side chain containing a methacryl group, a propyl group, a propyl group, a cinnamyl group. An amine precursor and at least one polymer of the polyimine obtained by imidating the polyimine precursor with ruthenium, the polymerizable compound having photopolymerization or photocrossing at each of two or more ends The base of the alliance. For example, after the liquid crystal alignment agent of the present invention is applied onto a substrate, the cured film obtained by drying after drying and drying may be used as a liquid crystal alignment film. Further, the cured film may be rubbed, or irradiated with a polarized light or a light of a specific wavelength, or subjected to an ion beam or the like, or may be irradiated with UV in a state where a voltage is applied to the liquid crystal display element after liquid crystal charging by the alignment film for PS. It is especially useful as an alignment film for PSA. -42- 201219379 In this case, 'the substrate to be used' is a substrate having high transparency, and is not particularly limited. A glass plate, polycarbonate, poly(meth)acrylate, polyether oxime, or poly can be used. Aromatic esters, polyurethanes, polyethers, polyethers, polyetherketones, trimethylpentene, polyolefins, polyethylene terephthalate, (meth)acrylonitrile, cellulose triacetate, cellulose diacetate, A plastic substrate such as acetate butyrate cellulose. Further, when a substrate on which an ITO electrode or the like to be driven by liquid crystal is formed is used, it is preferable from the viewpoint of simplification of the process. Further, if the reflective liquid crystal display device is only a single-sided substrate, an opaque material such as a germanium wafer may be used. In this case, a material that reflects light such as aluminum may be used as the electrode, and the method of applying the liquid crystal alignment agent is not particularly limited. Examples thereof include a printing method such as screen printing, offset printing, and stencil printing, a spraying method, a spraying method, a roll coating method or dipping, a roll coating, a slit coating, a spin coater, and the like. From the perspective of productivity, the transfer printing method is widely used in industry. It is also applicable to the present invention. The coating film formed by coating the liquid crystal alignment agent by the above method can be fired to form a cured film. Although the drying step after the application of the liquid crystal alignment agent is not necessary, the drying step is preferably performed when the time from the application to the baking is not constant for each substrate or when the coating is not immediately performed after coating. This drying is not particularly limited as long as the drying means is such that the solvent is removed without deforming the shape of the coating film. For example, a method of drying at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C, for 5 minutes to 30 minutes, preferably 1 minute to 5 minutes . The baking temperature of the coating film formed by coating the liquid crystal alignment agent is indefinitely -43 to 201219379, and can be carried out, for example, at any temperature of 100 to 350 ° C, preferably 120 ° C to 300 t, more Good for 150 ° C ~ 250 ° C. The firing may be carried out at any time from 5 minutes to 240 minutes, preferably from 10 minutes to 90 minutes, more preferably from 20 minutes to 90 minutes. The heating can be carried out by a generally known method, for example, using a hot plate, a hot air circulating furnace, an infrared furnace or the like. Further, the thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 1 to 10 nm. On the other hand, in the liquid crystal display device of the present invention, the liquid crystal alignment film can be formed on the substrate by the above method, and the unit cell can be produced by a known method. Specific examples of the liquid crystal display device include the above-described liquid crystal alignment agent having the two substrates arranged in the opposite direction, the liquid crystal layer provided between the substrates, and the liquid crystal layer provided by the liquid crystal alignment agent of the present invention. A liquid crystal display element in a vertical alignment mode of a unit cell of a liquid crystal alignment film. Specifically, the liquid crystal alignment agent of the present invention is applied onto two substrates and fired to form a liquid crystal alignment film, and the two substrates are arranged such that the liquid crystal alignment film is in a relative direction, and the liquid crystal alignment film is held between the two substrates. In the liquid crystal layer, the liquid crystal layer is provided with a liquid crystal layer which is a vertical alignment type liquid crystal display element which is provided with a cell which is irradiated with ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. By using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, ultraviolet light is applied to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, and the polymerizable compound is polymerized, and the photoreactivity of the polymer is obtained. The side chain or the photoreactive side chain of the polymer reacts with the polymerizable compound, and the alignment of the liquid crystal can be more efficiently fixed, and the liquid crystal display element having a remarkable response speed is excellent. *44 - 201219379 The substrate of the liquid crystal display device of the present invention is not particularly limited as long as it has a high transparency, and is generally a substrate on which a transparent electrode to be driven by a liquid crystal is formed. As a specific example, the same substrate as described in the above liquid crystal alignment film can be mentioned. The liquid crystal display element of the present invention can be used as a liquid crystal alignment agent for forming a liquid crystal alignment film by using the liquid crystal alignment agent of the present invention, and can be formed on a single-sided substrate, although a substrate having an electrode pattern or a protrusion pattern can be used. For example, the line/slot electrode pattern of 1 to 1 Ομιη can also function for a structure in which a slit pattern or a protrusion pattern is not formed on the opposite direction substrate, and the liquid crystal display element of the structure can simplify the manufacturing process. Get high transmission. Further, for a high-function element such as a TFT type element, an element such as a transistor is formed between an electrode to be driven by a liquid crystal and a substrate. In the case of a transmissive liquid crystal display device, a substrate such as the above is generally used. In the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as the single-sided substrate. At this time, a material such as aluminum which can reflect light can be used in the electrode of the substrate. The liquid crystal alignment film is formed by applying the liquid crystal alignment agent of the present invention to the substrate and firing it, and the details are as described above. The liquid crystal material constituting the liquid crystal layer of the liquid crystal display device of the present invention is not particularly limited, and a liquid crystal material used in the past vertical alignment method can be used. For example, a negative liquid crystal such as MLC-6608 or MLC-6609 manufactured by Moker Corporation can be used. As a method of holding the liquid crystal layer between the two substrates, a known method can be mentioned. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a spacer such as beads is spread on a liquid crystal alignment film of one of -45 to 201219379 substrates, and the other substrate is bonded to the inside of the surface formed by the liquid crystal alignment film, and the liquid crystal is decompressed. The method of sealing after injection can be exemplified. Also, prepare the liquid crystal alignment film to form! On the substrate, a spacer such as a bead is spread on a liquid crystal alignment film of one of the substrates, and then A liquid crystal is dropped, and then the other substrate is bonded to the inner surface of the liquid crystal alignment film to be sealed, and a cell can be formed. The spacer thickness at this time is preferably from 1 to 30 μm, more preferably from 2 to ΙΟμπι. The step of producing a unit cell by applying a voltage to the liquid crystal alignment film and the liquid crystal layer while applying a voltage is, for example, an electric field applied to the liquid crystal alignment film and the liquid crystal layer after the input voltage between the electrodes provided on the substrate is applied, and the electric field is maintained. A method of irradiating ultraviolet rays. The voltage input between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of the ultraviolet ray is, for example, 1 to 60 J', preferably 40 J or less, and the lower the amount of ultraviolet ray irradiation, the lower the letter reliability caused by the breakage of the member constituting the liquid crystal display element, and the manufacturing efficiency can be improved by reducing the ultraviolet ray irradiation time. Therefore, it is better. When the ultraviolet ray is irradiated to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, the polymerizable compound reacts to form a polymer, and the polymer liquid crystal molecules are memorized in the oblique direction to accelerate the response of the obtained liquid crystal display element. speed. Further, when the ultraviolet ray is applied to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, it is selected from the group consisting of a side chain having a liquid crystal alignment direction and at least one selected from the group consisting of a methacryl group, a propylene group, a vinyl group, and a cinnamyl group. a photoreactive side chain of a polyreuterine precursor of the photoreactive side chain and at least one polymer of the polyimine imide obtained by imidating the polyiminoimine precursor with each other, or polymerized The photoreactivity of the substance -46-201219379 The reaction between the side chain and the polymerizable compound can accelerate the response speed of the obtained liquid crystal display element. Further, the liquid crystal alignment agent can be used not only as a liquid crystal alignment agent for a liquid crystal display element of a vertical alignment type such as a PSA liquid crystal display or an SC-PVA liquid crystal display, but also by rubbing treatment or photoalignment processing. Applicable to the use of liquid crystal alignment film. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples. However, the invention is not limited thereto. <Polymerizable compound> (Synthesis of polymerizable compound (RM 1 )) To a 300 ml eggplant-shaped flask equipped with a cooling tube, 5.0 g (23.8 mmol) of 2,4'-biphenyldicarboxyaldehyde was added, 2 - (bromomethyl)acrylic acid 7.9 g (47.6 mmol), 10% hydrochloric acid (aq) 3 3 ml, tetrahydrofuran (THF) 100 ml, tin chloride (II) 9.5 g (50 mmol) as a mixture at 7 Torr.搅拌 Stir for 20 hours to react. After the completion of the reaction, the reaction solution was poured into 300 ml of purified water to give a white solid. The obtained solid was separated and purified by recrystallization (hexane / chloroform = 2 / 1) to afford 3.5 g of white solid. The solid was measured by NMR, and it was confirmed that the white solid was the polymerizable compound (RM1) represented by the following reaction formula. The yield was 72%. 'H-NMR ( CDC13 ) δ : 2.99 ( m, 2H) , 3.42 ( m, 2H) -47 - 201219379 » 5.60 ( m, 2H ) * 5.74 (m, 2H) ' 6.36 ( m, 2H) 1 7.42 ( m, 4H ) > 7.60 ( m, 4H ). [化31]

(Synthesis of polymerizable compound (RM2)) 4,4'-bisphenol 6.7 g (35.9 mmol), 2-(4-bromobutyl)-1,3 was added to a 300 ml eggplant-shaped flask equipped with a cooling tube. 15.0 g (71.7 mmol) of dioxolane, 19.8 g (143 mmol) of potassium carbonate, and 150 ml of acetone were mixed, and the reaction was carried out while stirring at 60 ° C for 48 hours. After the end of the reaction, the solvent was distilled off under reduced pressure to give a yellow, dry solid. Thereafter, the solid was mixed with 200 ml of water, and 80 ml of chloroform was added thereto and extracted. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer which was separated and dried, filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. The solid was purified by recrystallization (hexane / chloroform = 4 / 1 (vol.)) to yield 14.6 g of white solid. The results of measurement of the obtained white solid by NMR are shown below. Further, the obtained solid was dissolved in 氘-chloroform (CDC13), and measured by a nuclear magnetic resonance apparatus (manufactured by Di ο 1 Co., Ltd.) at 300 Μ Η z. From the results, it was confirmed that the white solid was a compound (RM2-A) represented by the following reaction formula. The yield is 92%. *H-NMR (CDC13) δ : 1.65 ( m, 4H ), 1.74 ( m, 4H) '1.87 ( m, 4H ) , 3.86 (m, 4H) - 3.97 ( m, 8H ) , 4.89 -48 - 201219379 ( t, 2H) > 6.92 ( m, 4H ) , 7.44 ( m, 4H ). [化32] K, CO,

(RM2-A) hcKI)~0"〇h + 0- Next, add the above-obtained compound (RM2-A) to a 50〇ml eggplant-shaped flask with a cooling tube, 13.3g (30mmol), 2-(bromo) Methyl)acrylic acid 1 1.6 g (70 mmol) '10% hydrochloric acid (aq) 50 ml, tetrahydrofuran (THF) 160 ml, tin chloride (II) 13.2 g (70 mmol) as a mixture, and stirred at 70 ° C for 20 hours Its reaction. After the completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 200 ml of purified water, and then 100 ml of dichloroform was added and extracted. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer which was separated and dried, and the solvent was distilled off from the filtered solution to give a white solid. The solid was purified by recrystallization (hexane / chloroform = 2 / 1) to yield 9.4 g of white solid. The white solid obtained was measured by NMR in the same manner as above to confirm the polymer compound (RM2) represented by the following reaction formula for the purpose of the white solid. The yield was 64%.

!H-NMR ( CDC13 ) δ : 1.69 ( m, 12H) , 2.61 ( m, 2H )> 3.09 ( m, 2H ) - 4.00 ( t, 4H ) , 4.57 ( m, 2H) ' 5.64 ( m, 2H ), 6.24 (m, 2H), 6.92 (d, 4H), 7.45 (m, 4H). -49- 201219379 [Chem. 33]

Y)-(CH2)4-〇-QQ^〇-(ch (synthesis of polymerizable compound (RM3)) Add 4,4'-bisphenol 11.2g (60mmol) to a 500ml eggplant-shaped flask with a cooling tube 2-(2-Bromoethyl)·1,3 - — 25.0g (1 38mmol) of Chewing Institute, 35.9g (260mmol) of potassium carbonate, and 200ml of acetone as a mixture, stirred at 60°C for 48 hours After the reaction was completed, the solvent was distilled off under reduced pressure to give a yellow-wet solid. After that, the solid was mixed with water (200 ml), and 100 ml of chloroform was added and extracted. The extraction was carried out three times. The organic layer was dried over anhydrous magnesium sulfate, and filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. The solid was dissolved in chloroform and precipitated with hexane (hexane/chloroform = 2/1) to give white. The solid was 17.6 g, and the solid was measured by NMR. The results were as follows. From the results, it was confirmed that the white solid was the compound (RM3-A) of the following reaction formula. The yield was 76%. 'H-NMR ( CDClj) δ : 2.19 ( m, 4H ) , 3.89 ( m, 4H) , 4.01 (m, 4H) > 4.1 6 ( m, 4H ) > 5.11 ( m, 2 H ) , 6.9 5 (m, 4H ) , 7.45 ( m, 4H ). • 50· 201219379 [Chem. 34]

(CH^-Br + HO 〇, 广.ΌΌ*〇,) κ:] (RM3-A) Next, the above-obtained compound (RM3-A) lO is added to a 500 ml eggplant-shaped flask with a cooling tube. Og (26mmol), 2-(bromomethyl)propionic acid l〇.〇g (60.6mmol), 10%HC1 (aq) 32ml, tetrahydrofuran (THF) 140 ml, tin chloride (II) 11.4 g (60.6 mmol) was prepared as a mixture, and the mixture was stirred at 70 ° C for 20 hours to cause a reaction. After the completion of the reaction, the reaction mixture was filtered under reduced pressure and then mixed with 200 ml of purified water. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the extracted organic layer to dry it, and the solvent was distilled off from the filtered solution to obtain a white solid. This solid was dissolved in chloroform and precipitated with hexane (hexane/chloroform == 2 Π) to give a white solid. The solid was washed with methanol to give 4.7 g of a white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a polymerizable compound (RM3) represented by the following reaction formula, and the yield was 42%. ^-NMR (CDC13) δ · 2.18 (m, 4H), 2.76 (m, 2H), 3.16 (m, 2H), 4.18 (m, 4H), 4.84 (m, 2H) > 5.67 (m, 2H ) , 6.27 (m, 2H), 6.95 (d, 4H), 7.46 (m, 4H). -51 - 201219379 [化35] Q-(cH2)r*0^O~O" 〇-(cha〆.〕

Βγ SnClj ten=3⁄4 um 丨 lCKaqK

COOH THF (RM3-A)

(ch^〇O~^-0 - (ci^"CC (RM3) (synthesis of polymerizable compound (RM4)) In a 500 ml eggplant-shaped flask with a cooling tube, 14.9 g (80.0 mmol) of bisphenol was added, 35 g (167. 〇mm〇l) of 5-bromopentyl acetate, 41.5 g (300 mmol) of potassium carbonate, and 250 ml of acetone were used as a mixture, and the reaction was carried out while stirring at 60 ° C for 48 hours. After the completion of the reaction, the reaction mixture was poured into 600 ml of pure water to obtain 33.6 g of a white solid. The solid was measured by NMR, and the results are as follows. From the results, it was confirmed that the white solid was a compound represented by the following reaction formula ( RM4-A). Yield 95% »

1H NMR (CDC13) 5: 1.57 (m, 4H), 1.74 (m, 4H), 1.86 (m, 4H), 2.06 (s, 6H) > 4.02 ( t, 4H ) » 4.12 (t, 4H ) 6.95 ( d, 4H ) , 7.47 ( d, 4H). [Chem. 36] IC2CO, Acetone o (RM4-A)

-H5C^V〇-(CH2)5~Br O H3C 〇- (called 5-〇 added to the 11 eggplant-shaped flask with a cooling tube, 250 ml of ethanol, the compound obtained above (RM4_A) 18. 〇g (41mm 〇i), and 10% KOH-52-201219379 Aqueous solution of 100 ml was used as a mixture and stirred at a temperature of 8 5 for 5 hours. After the reaction was completed, 500 ml of water and a reaction solution were added to a 1 000 ml beaker. After stirring at room temperature for 30 minutes, 80 ml of a 10% HCl aqueous solution was added dropwise, and the mixture was filtered to give a white solid i2.2 g. The solid was measured by NMR. The results are shown below. The compound of the formula (RM4-B) is obtained. The yield is 83%. 1H NMR (DMS0-d6) δ: 1.46 (m, 8H), 1.71 (m, 4H) > 3.4 1 ( m, 4H ) , 3.98 (m, 4H), 4.39 (m, 2H), 6.96 (m, 4H), 7·51 (m, 4H).

H0-(CH2)5-0 I The above-obtained compound (RM4-B) 5.0 g (M.Ommol), triethylamine 3.2 g and a small amount of 2,6-di-t-butyl-p-cresol ( BHT) was simultaneously dissolved in THF3 Oml, and stirred at room temperature, and a solution of 3.3 g (32 mmol) of methacrylium chloride chloride dissolved in 20 ml of THF was added dropwise thereto over 15 minutes while cooling under a water bath. After the dropwise addition, the mixture was stirred for 30 minutes, and after the water bath was removed, the mixture was allowed to stand overnight while stirring to room temperature. After the completion of the reaction, the reaction solution was poured into 200 ml of pure water and filtered to give a white solid. This solid was dissolved in chloroform, and precipitated (hexane/chloroform = 2 /1) using hexane to afford 2.6 g of white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a polymerizable compound (RM4) represented by the following reaction formula. The yield was 38%. -53- 201219379 • H-NMR (CDClj) δ : 1.56 ( m, 4H ) ' 1.74 ( m, 4H ) , 1.82 (m, 4H) , 1.97 (s, 6H) > 4.03 ( m > 4H ) » 4.20 (m, 4H ) , 5.55 ( m, 2H) ' 6.10 ( m, 2H) - 6.94 ( d, 4H ) , 7.45 ( d, 4H ) 0 [Chem. 38]

(Polymerizable compound (RM5)) A polymerizable compound represented by the following formula is used as a polymerizable compound (RM5). [化39]

(RM5) (Synthesis of Polymerizable Compound (RM6)) To a 200 ml eggplant-shaped flask equipped with a cooling tube, 4.61 g (50.0 mmol) of 4-hydroxybenzoic acid methyl group and 9.1 g of 6-bromo-1-hexanol ( 50.0 mmol), potassium carbonate (13.8 g (100 mmol), and acetone 70 ml as a mixture were reacted at 64 ° C for 24 hours while stirring. After the completion of the reaction, the reaction mixture was filtered under reduced pressure, and the solvent was evaporated. The solid was obtained by gel column chromatography (column: silicone 60, 0.063-0.200111111, \^1'), the solution was dissolved: hexane/acetic acid vinegar = 1/1 201219379 color knot (v/v )) Purification. The solvent was distilled off from the obtained solution to give a white solid (11.3 g). The NMR measurement results of this solid are shown below. It was confirmed that the white solid was a compound (RM6_A) yield of the following reaction formula of 90%. m, 'H-NMR ( CDC13 ) δ : 1.3-1.7 ( m, 8H) ' 3.67 ( 2H ) , 3.88 ( s, 3H) , 4.03 ( t, 2H) > 6.91 ( d, 2H ) 7.99 ( d, 2H). [化40] η〇"Ό" HO—(CH2)6~*Br COOCH3 .. » HO—(CH2)6—0 COOCH3 K2C〇a/Acetone (RM6-A) This is attached to the cooling tube In a 〇〇ml three-necked flask, put chlorochromate pyridine salt (PCC) 2.2g (1 O.Ommol), and C H2 C12 1 5 · 0 m 1 and

In the mixed state, a solution obtained by dissolving the above-obtained compound (RM6-A 2.5 g (10.Ommol) in CH2Cl 215.0 ml was added dropwise, and stirred at room temperature for 6 hours. Thereafter, the adhesion to the wall of the flask was removed. To the oily liquid, 90 ml of diethyl ether was added and filtered under reduced pressure, and the solvent was evaporated under reduced pressure to give a concentrated green solid solid.矽 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 The results of the measurement by NMR are shown below. From the results, it was confirmed that the colorless solid was the compound shown in the following reaction (f. 16-8). The yield was 50%. 'H-NMR (CDClj) δ : 1.3-1.8 (m, 6H), 2.49 ( t, ), 3.88 (s, 3H), 3.99 (t, 2H), 6.87 (d, 2H), 7 - 55-

Pyridine) Re-dissolve the column liquid 2H .99 201219379 (d, 2H ) , 9.78 ( s, 1 Η ). HO-(CH2)6-Ο 〇· cooch3 (RM6-A) PCC ch2ci2 ► OHC—(CH2)5-—o—^ cooch3 (RM6-B) Next, 50ml eggplant with cooling tube The above-obtained compound (RM6-B) 1.25 g (5.0 mmol), 2-(bromomethyl)propionic acid 0-83 g (5.0 mmol), Amberlyst (registered trademark) 15 (Rohm and Haas Company trade name) were added to the flask. 0.8 g, THF 8.0 ml, tin chloride (II) 0.95 g (5.0 mmol), and pure water 2.0 ml were used as a mixture, and the mixture was stirred at 7 ° C for 5 hours to cause a reaction. After the completion of the reaction, the reaction mixture was filtered under reduced pressure and mixed with 40 ml of purified water, and 50 ml of diethyl ether was added thereto and extracted. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was distilled off from the filtered solution to obtain 1.5 g of a colorless solid. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the colorless solid was a compound (RM6-C) represented by the following reaction formula. The yield was 94%. 'H-NMR ( DMSO-d6) 6 : 1.3-1.8 ( m, 8H) , 2.62 ( m, 1 Η ) « 3.04 ( s, 1 Η ) , 3.81 (s, 3H) , 4.05 (t, 2H) , 4.54 (m, lH) - 5.70 ( s, 1H ) , 6.01 (s, lH) · 7.03 (d, 2H ) > 7.89 ( d, 2H ). OHC-tCH^-O^Q-COOCHa °^(CH2)5-0^-C00CH3 (RM6-B) THF/H20 (RM6-C) -56- 201219379 attached to the cooling tube 35 ml of ethanol was added to the 〇ml-shaped flask, and the compound obtained above (6-(:) 1.58 (4.7111111〇1), and 1 〇/() aqueous solution of 5 ml as a mixture was carried out at 8 5 After the reaction was completed, the reaction was completed. After adding 300 ml of water and a reaction liquid in a 500 ml beaker, stirring at room temperature for 30 minutes, and then dropping 5 ml of a 10% aqueous solution of H c 1 and filtering to obtain white. Solid 1.3 g. Next, a white solid l.lg, Amberlyst (registered trademark) 15 (R〇hm and Haas Company trade name), 〇g, and THF 20_0ml were added as a mixture in a 50 ml eggplant-shaped flask equipped with a cooling tube. 'Agitated and reacted at 7 ° C for 5 hours. After the reaction was completed, the reaction solution was filtered under reduced pressure and the solvent was evaporated from the solvent to give a yellow solid. The yellow solid was recrystallized (hexane / ethyl acetate After purification of the ester = 1 /1 (v/v)), -9 g of a white solid was obtained. The NMR measurement results of the solid were as follows. The white solid was identified as the compound of the following formula (RM6-D). The yield was 7 1 % » 】H-NMR (DMSO-d6) δ: 1.2-1.8 (m,8H), 2.60 (m , 1Η ) > 3.09 ( m, 1Η ) > 4.04( m, 2H ) » 4.55 ( m, 1H )> 5.69 ( s, 1H ) > 6.02 ( s, 1H ) , 6.99 ( d,2H) &gt ; 7.88 (d, 2H ) , 12.5 ( s, broad, 1 H ). [化43] _5一. 伽.CH3 ^^(4) I. Public deletion (RM6-C) THF (RM6-D) The compound obtained above (RM6-D) 21.1 g (69.3 mmol), 1,4-cyclohexanedimethanol 5.0 g (34.7 mmol), N,N-dimethyl-4-amine-57-201219379-based pyridine (DMAP) 0.35g and a small amount of BHT were stirred in room temperature with stirring at room temperature, and then added to the cyclohexane carbodiimide (DCC) 15.5g (75.0) dissolved in dichloromethane 50 ml. Ment), stirring for 48 hours to carry out the reaction. After the reaction is finished, the precipitated DCC urea is separated by filtration. The filtrate is sequentially treated with 60 ml of 0.5 N-HC1 and saturated aqueous sodium hydrogencarbonate solution and saturated brine twice. After washing and drying with magnesium sulfate, the solvent was distilled off and then recrystallized from ethanol to give the following. The polymerizable compound (RM6) represented by the reaction formula was 20.1 g. The results of measurement by NMR are shown below. The yield was also 81%.

*H-NMR ( CDC13 ) δ : 1.15 ( m, 4H ) , 1.50 ( m,8H ), 1.66 ( m,2H) , 1.79 ( m,8H) , 1.92 ( m,4H), 2.60 ( m, 2H ) , 3.08 (m, 2H), 4.01 (m, 4H), 4.12 ( m, 4H ) > 4.53 ( m, 2H ) , 5.63 ( d, 2H ) > 6.24 ( d, 2H ) , 6.89 ( d, 4H ), 7.97 (d, 4H). [化44]

(Synthesis of Polymerizable Compound (RM7))

The compound obtained by the above method (RM6-D) 6.1 g (20.0 mmol), 4-[(6-propenyloxy)hexyloxy]phenol (SYNTHON)

Chemicals) 5.3g (20.0mmol), N,N-dimethyl-4-aminopyridine (DMAP) O.lg, and a small amount of BHT stirred at room temperature, suspension -58-201219379 in dichloromethane To 〇〇ml, a solution of 5.1 g (25.0 mmol) of dicyclohexylcarbodiimide (DCC) was added thereto and stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 0.5 N-HC1 100 ml, saturated sodium hydrogen carbonate aqueous solution 100 ml, and saturated brine (150 ml), dried over magnesium sulfate, and then reduced. The solvent was distilled off under reduced pressure to give a yellow solid. The solid was purified by column chromatography on silica gel column (column: yttrium 60 0.063-0.200 mm, Moker Co., Ltd., hexane/ethyl acetate = 1/1). The solvent of the solution thus obtained was distilled off to obtain 4.3 g of a polymerizable compound (RM7) represented by the following reaction formula. The results of measurement by NMR are shown below. The yield was also 39%.

1H NMR (CDC13) δ: 1.53 (m, 10H) > 1.72 ( m, 2H

[化45]

A 0 (CH2)5*~~〇~^r^'^ooH + HO Ο o - Yang 2)6_〇"^^ (RMG-D)

〇·—(CH^-O* (synthesis of polymerizable compound (RM8)) The compound represented by the following reaction formula (RM8-A) 2.1β(7·3ΐηΠ1 -59- 201219379 ), compound (RM8-B) 2.5 g (7.3 mmol), DMAP 0.015 g, and a small amount of BHT were stirred at room temperature, and suspended in 30 ml of dichloromethane. After adding 1.8 g (9.0 mmol) of DCC dissolved in 5 ml of dichloromethane and stirring for one night. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 ml of 0.5 N-HC1 and saturated aqueous sodium hydrogencarbonate solution and saturated brine twice, dried over magnesium sulfate, and then evaporated. The recrystallization operation was carried out to obtain 1.3 g of the polymerizable compound (RM8) represented by the following reaction formula. The results of measurement by NMR are shown below. The yield was 30% 〇1H NMR (CDC13)): δ 1.40-1.90 (m, 14H), 2.64

(m, 1H ) > 3.07 ( m, 1 H ) , 4.00 (t, 2H) > 4.05 ( t, 2H ), 4.18 ( t, 2H) « 4.54 ( m, 1H ) > 5.83 ( d, 1H ), 6.14 ( m, 1 H ) , 6.25 (d, lH) , 6.37 (d, lH) > 6.97 ( d, 2H ) ' 7.26 ( d, 2H ) , 7.50 ( d, 2H ) ' 7.57 ( d, 2H ), 8. 1 7 ( d, 2H ). [RM46-A) ° (RM8-B) 0 DCX/DMAP V V Tao π. Personnel (RM8) (synthesis of polymerizable compound (RM9)) Add 4-hydroxybenzamide to 6.1 g (50 mmol), 6, bromo-p-hexanol 9.1 in a l〇〇ml eggplant-shaped flask with a cooling tube. g (50 mmol), potassium carbonate-60-201219379 13.8 g (100 mmol), and acetone 100 ml as a mixture were reacted at 64 ° C for 24 hours while stirring. After the completion of the reaction, the solvent was distilled off under reduced pressure to give a yellow, wet solid. Thereafter, 70 ml of the solid and water were mixed, and 50 ml of diethyl ether was added and extracted. The extraction was carried out 3 times. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered, and then evaporated. The solid was dissolved in 5 ml of ethyl acetate, and purified by column chromatography (column: silica gel 0.0 0.063-0.200 mm Merck solvent: hexane / ethyl acetate = 2 / 1). The solvent was evaporated from the obtained solution to give 7.4 g of a white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a compound (RM9-A) represented by the following reaction formula. The yield was 67%. 1H NMR (DMSO-d6) δ: 1.55 (m, 4H), 1.62 (m, 2H), 1.84 (m, 2H >, 3.67 (t, 2H ) > 4.05 ( t, 2H ), 4.20 ( t, 2H ) , 7.00 ( d, 2H) , 7.84 ( d, 2H) , 9.88 ( s, 1H ). [Chem. 47] /=\ Br-(CH2)6-OH /==\

H〇l/-CH〇〇HC Human/〇-(CH2)6 - 0H (RM9.A) In a 50 ml three-necked flask, compound (RM9-A) 2·2g, triethylamine 1.71111, 8111'0.211^ And 7'1^1〇1111 and dissolved. Under stirring of the solution, a solution of 8 g of acryioy1 chloride dissolved in THF 10 ml was added dropwise over 15 minutes. At this time, the three-necked flask was cooled in a water bath (water temperature of 20 ° C). After the dropwise addition, the mixture was directly subjected to 30 minutes in this state. After stirring at 1919379, the flask was taken out from a water bath, replaced with nitrogen, and stirred at room temperature for further 3 hours to cause a reaction. The reaction solution was filtered. The filtrate was concentrated under reduced pressure to a volume of 3/4, and then 100 ml of dichloromethane was added. The solution was washed with a saturated sodium carbonate solution (1 ml), EtOAc (EtOAc) (EtOAc)EtOAc. The solid was dissolved in 3 ml of ethyl acetate, and purified by column chromatography (column: yttrium 60 0.063 - 0.200 mm Merck solvent: hexane / ethyl acetate = 2 / 1). Here, the solvent was distilled off from the obtained solution to obtain a white solid (2.0 g). The solid was measured by NMR. From the results, it was confirmed that the white solid was a compound (RM9-B) represented by the following reaction formula. The yield was 72%.

1H NMR (CDC13) δ: 1.48 (m, 4H), 1.75 (m, 2H), 1.85 (m, 2H), 4.05 (t, 2H) > 4.1 8 ( t, 2H ) - 5.81

(d, 1 H ) - 6. 1 4 ( m, 1 H ) > 6.3 7 ( d, 1 H ) , 6.99 (m, 2H ), 7.82 ( m, 2H ) , 9.88 ( s, 1H ). [化48] 〇hcO~( <CH2) wide oh

Acryloyl Chloride -> EljN, THF 〇hc-〇^ 0-(03⁄4广0. (RM9>A) (RM9-B)

Next, in the eggplant-shaped flask of 5 〇ml with a cooling tube, 'the intermediate compound (RM9-B) obtained in the same manner as above was added. 2_0g (7mmol) '2-(bromomethyl)acrylic acid 1.2g (7.0mmol) ), Amberl yst (registered trademark) 15 (Rohm and Haas trade name) 1.2g, THF 8.0ml, tin (II) chloride 1.4g (7mmol), pure water 2.0ml as a mixture, at -62-201219379 degrees 70 The mixture was stirred at ° C for 24 hours and allowed to react. After the completion of the reaction, the reaction solution was filtered under reduced pressure, and then mixed with 60 ml of purified water, and 50 ml of diethyl ether was added thereto and extracted. The extraction was carried out 3 times. To the organic layer after extraction, anhydrous magnesium sulfate was added to dryness, and the solvent was filtered off under reduced pressure to give a pale brown solid. This solid was dissolved in 3 ml of ethyl acetate, and purified by a column chromatography (column: silica gel 60 0.063-0-200 mm Merck solvent: hexane / ethyl acetate = 2 / 1). The resulting solution was distilled off to give a white solid. The solid was measured by N M R. The white solid was confirmed to be a polymerizable compound (RM9) represented by the following reaction formula. The yield was 40%.

1H NMR (CDC13) δ : 1.48 ( m, 4H) ' 1.75 ( m, 4H ), 2.94 ( m, 1H) - 3.39 ( m, 1H ) , 3.95 ( t, 2H), 4.17 (t, 2H) , 5.45 (t,lH) , 5.68 (m,lH) , 5.83 (m, 1 H ) > 6.13 ( m, 1H ) · 6.30 ( m, 1H ) > 6.40 ( d, 1H ) ' 6.88 ( d, 2H ) , 7.26 ( m, 2H ). [化49] O—(CH2)6—ο (RM9-B)

SnCl2 Amberlyst 15 THF/H20

(Synthesis of Polymerizable Compound (RM10)) -63- 201219379 The compound (RM6-D) obtained in the same manner as above was 22.0 g (7 2.4 mm ο 1 ), 1,4-phenyldimethanol 5.0 g (36.2 mmol) , N,N-dimethyl-4-amino group D (DMAP) 0.35g and a small amount of BHT were stirred at room temperature, suspended in 100ml of dichloromethane, and dissolved in 50ml of dichloromethane Cyclohexylcarbodiimide (DCC) 17.0 g (80. 〇mm〇l) was stirred for 48 hours to cause a reaction. After the completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 0.5 ml of 0.5 N-HC1 and a saturated aqueous solution of sodium hydrogencarbonate and brine, and dried over magnesium sulfate. After the solvent was recrystallized from ethanol, 16.6 g of a polymerizable compound (RM10) represented by the following reaction formula was obtained. The results of measurement by NMR are shown below. Also, the yield was 65%.

'H-NMR (CDC13) δ : 1.46 ( m, 12H) , 1.80 ( m, 4H ), 2.60 ( m, 2Η ) , 3.08 ( m, 2Η ) , 4.01 ( m, 4H ), 4.56 ( m, 2H ) , 5.34 ( s, 4H ) , 5.63 ( d, 2H ) , 6.23 ( d, 2H ) , 6.90 ( d, 4H ) , 7.46 ( s, 4H ), 8.00 ( d, 4H). [化 50]

/==\ /=rv DCC/DMAP + T^{CH2)s—〇-^\-c〇OH __gHA · (RM6-D) (RM10) (synthesis of polymerizable compound (RM 1 1 )) The compound obtained by the same method (RM6-D) 6.1g (20. Ommol), 4,4'-biphenyldimethanol 2.1g (10.Ommol), N,N-dimethyl-4-aminopyridine (DMAP) 0.15g and a small amount of BHT were carried out at room temperature-64-201219379 under stirring, suspended in 50 ml of dichloromethane, and then added to a solution of 25 ml of dicyclohexylcarbodiimide (DCC) 5.3 g (25). Ommol) and stirred for 48 hours to react. After the completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 0.5 ml of 0.5 N-HC1 and a saturated aqueous solution of sodium hydrogencarbonate and brine, and dried over magnesium sulfate. The solvent was then subjected to recrystallization operation in ethanol to obtain a polymerizable compound (RM 1 1 ) 6 · 4 g represented by the following reaction formula. The results of measurement by NMR are shown below. Also, the yield was 81%.

H-NMR (CDC13) δ: 1.48 (m, 12H), 1.75 (m, 4H )' 2.60 ( m, 2H ) , 3.08 ( m, 2H ) , 4.01 ( m, 4H ), 4.55 ( m, 2H ) , 5.38 ( s, 4H) , 5.63 ( d, 2H) , 6.23 ( d, 2H ) , 6.89 ( d, 4H ) , 7.51 ( d, 4H) , 7.62 ( d, 4H ) , 8.05 (d, 4H ). [化51] (CHJ-OH +

(CH2)5-〇 (RM6-D) DCC/DMAP COOH CH2Cl2 · HO-(CH2)

(CH2)5-

P :ch2)-0 -(CH2)j

(RM11) (Synthesis of Polymerizable Compound (RM12)) The compound (RM6-D) obtained in the same manner as above was 6.1 g (20 mmol), and 4,4'-dibenzobenzophenone 2.1 g (10) .Ommol), hydrazine, hydrazine-dimethyl-4-aminopyridine (DMAP) O.lg, and a small amount of BHT were stirred at room temperature and suspended in 80 ml of dichloromethane, and dissolved dicyclohexyl carbon was added thereto. A solution of imipenem (DCC) 5.2 g (24_0 mmol) was stirred at -65-201219379 overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 0.5 N-HC1 50 ml, 50 ml of a saturated aqueous sodium hydrogencarbonate solution and a saturated aqueous solution of sodium chloride, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to give a yellow solid. The solid was recrystallized from ethanol and purified to give 6.2 g of a white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a polymerizable compound (RM12) represented by the following reaction formula. The yield was 79%. 1H NMR (CDC13) δ: 1.45- 1.95 (m, 16H), 2.58 (m, 2H), 3.07 (m, 2H), 4.05 (t, 4H), 4.54 (m, 2H), 5.64 (s, 2H) , 6.24 ( s, 2H) , 6.98 ( d, 4H ) , 7.32 ( d, 4H) , 7.91 (d, 4H), 8.18 (d, 4H). [化52]

(RM12) (Synthesis of polymerizable compound (RM13)) Add 4-hydroxybenzoic acid to 12.2 g (100 mmol) and 1,6-dibromohexanol 12.2 liters in a 500 ml eggplant-shaped flask with a cooling tube. 5〇111111〇1), potassium carbonate 16.0 g (1 16 mmol) and acetone 150 ml were mixed as a mixture, and the mixture was stirred at a temperature of 64 ° C for 48 hours to cause a reaction. After the reaction solution was filtered, the solvent was evaporated to dryness, m. The results of measurement of the solid by NMR are shown below. From the result -66-201219379, it was confirmed that the solid was a compound (RM 1 3 - A ) represented by the following reaction formula. The yield is 94%. *H-NMR (CDC13) δ : 1.49 ( m, 4H ) , 1.77 ( m, 4H) , 4.12 ( t, 4H) « 7.10 ( d, 2H ) > 7.86 ( d, 2H ) > 9.87 ( s, 2H). H0-〇-0 士::, ohc^-o-cch^o^-cho (RM13-A) Next, in the eggplant-shaped flask with a cooling tube of l〇〇ml, the same as above The obtained compound (RM13-A) 3.3 g (10.0 mmol), 2-(bromomethyl)acrylic acid 3.3 g (20.0 mmol), Amberlyst (registered trademark) 15 (Rohm and Haas trade name) 3.0 g, THF 32.0 ml, Tin (II) chloride 3.8g (20.0mmol) and pure water 8.0ml were used as a mixture, and the mixture was stirred and reacted at a temperature of 7 (TC for 24 hours. After the reaction was completed, the reaction solution was filtered under reduced pressure with pure water. After mixing 60 ml, 70 ml of diethyl ether was added thereto and extracted. The extraction was carried out 3 times. The extracted organic layer was dried over anhydrous magnesium sulfate, and the solvent was filtered off under reduced pressure to give a pale brown color. The solid was dissolved in 100 ml of ethyl acetate and purified by column chromatography (column: silica gel 60 0.063-0.200 mm Merck solvent: hexane/ethyl acetate = 1 /1). The solvent obtained by distilling off the solvent was obtained, and 2.6 g of a white solid was obtained. The result of the measurement of the solid by NMR is shown below. The white solid is a poly-67-201219379 compound (RM 1 3 ) represented by the following reaction formula. The yield is 55 %. 1H-NMR (CDC13) δ : 1.54 ( m, 4H ) , 1.80 (m, 4H) , 2.94 ( m, 2H ) , 3.35 ( m, 2H ) , 3.97 ( t, 4H ) , 5.47 (m, 2H ) > 5.68 ( m, 2H ) , 6.30 ( m, 2H) - 6.88 ( d, 4H), 7.26 (d, 4H). [Chem. 54]

(Synthesis of polymerizable compound (RM14)) 7.5 g (SO.Ommol) of p-formaldehyde benzoic acid and 9.1 g of 2-(glymethyl)propionic acid (55.0 mmol) were added to a 300 ml eggplant-shaped flask equipped with a cooling tube. ), THF 80.0 ml, tin (II) chloride, 5 g (UO.Ommol), and aqueous hydrochloric acid (10%) 3 5.0 m 1 as a mixture, and stirred at 7 ° C for 24 hours. reaction. After the completion of the reaction, it was mixed with pure water of 200 m 1 , and thus diethyl ether l〇〇ml was added thereto and extracted. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was evaporated under reduced pressure to give 8.3 g of a colorless solid. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the colorless solid was a compound represented by the following reaction formula (foot 1^114-eight). The yield was 76%. 'H-NMR ( DMSO-d6 ) δ : 2.85 ( m, 1H) , 3.50 ( m, 1H) > 5.75 ( m, 1H ) 1 5.80 ( s, 1H) > 6.18 ( s, 1H), -68 - 201219379 7.45 ( d, 2H ) , 7.98 ( d, 2H) ' 13.08 ( s, 1H ). [化55]

The above-obtained compound (RM14-A) 2_4g (11.0mmol), 1,6-hexanediol 0.6g (5_0mmol), N,N-dimethyl-4-aminopyridine (•DMAP) 0.05g and a small amount BHT was suspended in 10 ml of dichloromethane under stirring at room temperature. 2.5 g (12.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 5 ml of dichloromethane was added thereto, and the mixture was stirred for 48 hours to react. . After the completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 60 ml of 0.5 N-HC1 and saturated aqueous sodium hydrogencarbonate solution and saturated brine twice. After the solvent was recrystallized from ethanol, 1.3 g of the polymerizable compound (RM14) represented by the following reaction formula was obtained. The results of measurement by NMR are shown below. The yield was also 50%.

'H-NMR ( CDC13 ) δ : 1.53 ( m, 4H ) , 1.80 ( m, 4H )> 2.85 ( m, 2H) ' 3.45 ( m, 2H) , 4.36 ( m, 4H), 5.60 ( t, 2H ), 6.72 (d, 2H), 6.34 (d, 2H), 7.40 (d, 4H), 8.06 (d, 4H). -69- 201219379 + HO—(CH2)6-OH DCC/DMAP CH2C12

X^〇-c〇〇h (RM14-A) (Synthesis of polymerizable compound (RM15)) PCC6_2g (28.7 mmol) and CH 2 C121 0 0.0 m were placed in a 300 ml three-necked flask equipped with a cooling tube. Under stirring and mixing, a solution of 8.0 g (28.7 mmol) of the compound (RM15-A) shown in the following reaction formula in CH2C12 (30.0 ml) was added dropwise thereto, and the mixture was further stirred at room temperature for 2 hours. Then, 150 ml of diethyl ether was added to the solution of the oily substance adhering to the wall of the flask, and the mixture was filtered under reduced pressure, and the solvent was evaporated under reduced pressure to give a concentrated green solid. i The solid was purified by ruthenium column chromatography (column: oxime 60, 0.063-0.20 mm, manufactured by Mock Corporation, eluent: hexane/ethyl acetate = 1/1). The solvent of the obtained solution was evaporated to give 5.7 g of colorless solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the colorless solid was a compound (RM15-B) represented by the following reaction formula. The yield was 72%.

1H NMR ( CDC13 ) δ : 1.50 ( m, 2H ) > 1.70( m, 2H )'1 .85 ( m, 2H ) , 2.45 ( m, 2H) , 3.80 ( s, 3H), 4.00 ( t, 2H ) - 6.25 ( d, 1H ) > 6.83 ( d, 2H ) , 7.45 ( d, 2H) > 7.84 ( d, 1 H ) > 9.80 ( s, 1 H ). -70- 201219379 [化57] H〇-(CH2)6-〇-/ ο (RM15-A) 0-CH3

PCC OHC—(CH2)5-〇(RM15-B) O-CHj Next, add the above-obtained compound (RM15-B) 5.7g (20.6mmol), 2-(bromine) to a 100ml eggplant-shaped flask with a cooling tube. Methyl)acrylic acid 3.4 g (20.6 mmol), 10% hydrochloric acid aqueous solution 16 m 1 , THF 5 0 m 1 , and tin chloride (Π) 3.9 g (20.6 mmol) as a mixture, and the temperature was 70 ° C for 20 hours. Stir and react. After the completion of the reaction, the reaction mixture was filtered under reduced pressure and mixed with 100 ml of purified water, and then 50 ml of diethyl ether was added and extracted. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after the extraction, and the mixture was dried. The solvent was evaporated to dryness (yield: hexane/ethyl acetate = 1/1) to afford 4.6 g of colorless solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the colorless solid was a polymerizable compound (RM15) represented by the following reaction formula. The yield was 65%. 1H NMR (CDC13) δ: 1.40-1.90 (m, 8H), 2.60 (m, 1H) - 3.05 ( m, 1H ) > 3.80( s, 3H ) , 4.02 (t, 2H), 4.55 (m, lH > 5.63 ( s, 1H ) * 6.25 ( s, 1H ) > 6.33 ( d, lH), 6.90 (d, 2H) , 7.45 (d, 2H), 7.65 (d, lH). -71 - 201219379 [化58]

(Synthesis of Polymerizable Compound (RM16)) To a 200 ml eggplant-shaped flask equipped with a cooling tube, 4-bromobutyl-1,3-dioxolane 5.0 g (24.0 mmol), 2-(bromomethyl) was added. 4.5 g (27.0 mmol) of acrylic acid, 10% hydrochloric acid aqueous solution 191111, 1'1^6〇1111, and tin (II) chloride 4.7 g (27.0 mmol) were mixed as a mixture, and the mixture was stirred at 70 ° C for 20 hours to react. . After the completion of the reaction, the reaction mixture was filtered under reduced pressure and mixed with 100 ml of purified water. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was distilled off from the filtered solution to obtain 5.2 g of a colorless liquid. The results of measurement of the liquid by NMR are shown below. From the results, it was confirmed that the colorless liquid was a compound (RM 16-A) represented by the following reaction formula. The yield is 93% 〇

1H NMR ( CDC13 ) δ : 1.64 ( m, 4H ) , 1.96 ( m, 2H ) * 2.06 ( m, 1H ) * 3.07 ( m, 1H ) , 3.44 ( t, 2H), 4.55 ( m, 1 H ) , 5.65(s,lH) > 6.25 ( s, 1 H ) » -72- 201219379 [化59]

SnCl2/10% HCl (aq) THF T^V-(CH2)4--Br (RM16-A) The above-obtained compound (RM16-A) was added to a l〇〇ml eggplant-shaped flask equipped with a cooling tube. g (20.0 mmol), 4-methoxycinnamic acid 3.6 g (20.0 mmol), cesium carbonate 5.1 g (40.0 mmol), and N,N-dimethylformamide (DMF) 50 ml as a mixture at 110° C - The reaction was carried out while stirring for 48 hours. After the completion of the reaction, it was mixed with 200 ml of pure water, and 50 ml of ethyl acetate was added thereto and extracted. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was filtered off under reduced pressure to give a solid. The solid was dissolved in 10 ml of ethyl acetate and purified by silica gel column chromatography (column: solvent 60 0.063-0.200 mm Merck solvent: hexane/ethyl acetate = 1/1). Since the solvent thus obtained was evaporated to give a white solid, 2.8 g. The NMR measurement results of this solid are shown below. From the results, it was confirmed that the solid was a polymerizable compound (RM 1 6 ) represented by the following reaction formula. The yield was 43%.

1H NMR (CDC13) δ : 1.50 ( m, 2H ) > 1.75 ( m, 4H )» 2.63 ( m, 1 η ) . 3.05 ( m, 1Η ) > 3.85 ( s, 3H ) , 4.20

(t,2H) ' 4.55 ( m,1H), 5.65 ( s,1H), 6.23 ( s,1H )> 6.50 ( d, ih ), 6.90 ( d, 2H), 7.45 ( d,2H) * 7.66 (d, 1H). -73- 201219379 [化60]

(Synthesis of polymerizable compound (RM 1 7)) 4-bromobutyl-1,3-dioxolane 9.4 g (45.0 mmol), trans-4-benzene was added to a 200 ml eggplant-shaped flask equipped with a cooling tube. The cinnamic acid 〇g (45. Ommol), potassium carbonate 12.0 g (90.0 mmol), and DMF 100 ml were mixed as a mixture, and the mixture was reacted at 110 ° C for 48 hours while stirring. After the completion of the reaction, it was mixed with 100 ml of pure water to obtain a solid. The solid was filtered, and 50 ml of ethanol was added as a mixture and filtered. The solvent was distilled off from the solution after reduced pressure to give 6.2 g of a solid. The NMR measurement results of this solid are shown below. From the results, it was confirmed that the solid was a compound (RM17-A) represented by the following reaction formula. The yield was 40%.

1H NMR (CDC13) δ: 1.55 (m, 2H), 1.75 (m, 4H), 3.83 (m, 2H), 3.98 (m, 2H), 4.24 (t, 2H), 4.85 (m, 1H) » 6.45 (d, 1H), 7.36 (m, 1H) > 7.46 (m, 2H), 7.60 (m, 6H), 7.75 (d, lH). -74· 201219379 [化61]

Next, the compound (RM17-A) obtained above (RM17-A) 6.2 g (18.0 mmol) and 2-(bromomethyl)acrylic acid 3.3 g (20.0 mmol), 1% by weight were placed in a l〇〇ml eggplant-shaped flask equipped with a cooling tube. Aqueous hydrochloric acid solution 101111, 1'1^321111, and tin chloride (Π) 3.8 g (20.0 mmol) were reacted as a mixture at a temperature of 70 ° C for 20 hours. After the completion of the reaction, the reaction mixture was mixed with 100 ml of pure water, and 50 ml of diethyl ether was added thereto and extracted. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after the extraction to dryness, and the solvent was evaporated from the filtrated residue, and then recrystallized (hexane/ethyl acetate = 2/1) to afford 3.6 g of solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the solid was a polymerizable compound (RM 1 7 ) represented by the following reaction formula. The yield was 53%. 1H NMR ( CDC13 ) δ : 1.68 ( m, 6H) > 2.63 ( m, 1Η ), 3.07 ( m, 1Η ) > 4.24 ( t, 2Η ) > 4.55 ( m, 1Η ) « 5.64 ( s, 1Η > 6.25 ( s, 1Η ) - 6.50 ( d, 1Η ) , 7.36 ( m, 1Η ) > 7.46( m, 2H ) , 7.65 (m, 6H) , 7.75 (d, lH). -75- 201219379 [化 62]

(Synthesis of Polymerizable Compound (RM 18)) The compound obtained by the above method (RM6-D) 7.6 g (25_0 mmol), ethyl 4-hydroxycinnamate 4.8 g (25.0 mmol) 'Ν,Ν-dimethyl 4-Aminopyridine (DMAP) O.lg, and a small amount of BHT were stirred at room temperature, and suspended in 1 ml of dichloromethane, and dissolved in dicyclohexylcarbodiimide (DCC) 6.7 g was added thereto. The solution (3 2 mmol) was stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 N of 0.5 N-HC1, 50 ml of a saturated aqueous sodium hydrogen carbonate solution and 100 ml of a saturated aqueous sodium chloride solution, and dried over magnesium sulfate. It was distilled off to give a yellow solid. The solid was purified by recrystallization using ethanol to give a white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a polymerizable compound (111^18) represented by the following reaction formula. The yield was 59%. 1H NMR (CDC13) δ : 1.35 ( t,3H),1·40-1·90 ( m,8H )* 2.60 ( m, 1H ) > 3.08 ( m, 1H ) , 4.05 ( t,2H), 4.25 ( m, 2H ) > 4.55 ( m, 1H ) » 5.64 ( s, 1H ) , 6.22 ( s, lH) > 6.40 ( d, 1 H ) > 6.97 ( d, 2H ) , 7.22 (d, 2H > 7.60 ( d, 2H ) - 7.70 ( d, 1H ) , 8.15 (d, 2H). -76- 201219379 [Chem. 63]

(Synthesis of Polymerizable Compound (RM19)) 7.3 g (24.0 mmol) of the compound (RM6-D) obtained in the above method, and 5.0 g (24.0 mmol) of methyl 4-carbyl-3-methoxycinnamic acid vinegar, N,N-Dimethyl-4-aminopyridine (DMAP) 0·1 g, and a small amount of BHT were stirred at room temperature under stirring, 1 00 ml of dichloromethane, and dissolved dicyclohexylcarbodiimide was added thereto. (DCC) A solution of 6.4 g (31_0 mmol) was stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 0.5 N-HC1 100 ml, saturated sodium hydrogen carbonate aqueous solution i00 ml, and saturated brine 150 ml, dried over magnesium sulfate, and then solvent was evaporated under reduced pressure. Distilled to give a yellow solid. This solid was purified by recrystallization (ethanol) to obtain a polymerizable compound (RM 1 9 ) 6 · 1 g represented by the following reaction formula. The results of measurement by NMR are shown below. The yield was 5 1 % 〇1H NMR (CDC13) δ: 1.40-1.90 (m, 8H) > 2.58 ( m, 1H) J 3.08 ( m, in ) , 3.80 (m, 6H) , 4.05 (t, 2H), 4.55 (m,lH) « 5.62 ( s, 1 H ) > 6.22 ( s, 1H ) - 6.42 ( d, 1H) > 6.97 ( d, 2H ) , 7.18 (m, 3H) > 7.65 ( d, 1H ), 8. 1 8 ( d, 2H ). -77- 201219379 [Chem. 64]

(Polymerizable Compound (RM20)) A polymerizable compound represented by the following formula is known as a polymerizable compound (RM20). [化65] Ο

(Polymerizable Compound (RM21)) A polymerizable compound represented by the following formula is known as a polymerizable compound (RM21). [化66]

(Polymerizable Compound (RM22)) A polymerizable compound represented by the following formula is known as a polymerizable compound (RM22). -78- 201219379 [Chem. 67]

(Polymerizable Compound (Reverse M23)) A polymerizable compound represented by the following formula is known as a polymerizable compound (RM23). [68]

<Preparation of Liquid Crystal Aligning Agent> The abbreviations used in the preparation of the liquid crystal alignment agent described below are as follows. BODA: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride TCA: the following formula 2,3,5-trisole cyclopentyl acetic acid-I,4: 2,3-di-anhydrous-79- 201219379 [Chem. 69]

TCA m-PDA: m-phenylenediamine P-PDA: p_phenylenediamine PCH: 1,3-diamino-4-[4-(4-heptylcyclohexyl)phenoxy] Benzene DA-1: 2-(methacryloxy)ethyl 3,5-diaminobenzoate represented by the following formula [Chem. 70]

DA-2: N^N1-diisopropyl phenyl-1,2,4-triamine represented by the following formula [Chem. 71]

-80- 201219379 DA-3: 3,5-diamino benzoic acid cholestyl ester shown in the following formula [Chem. 72]

NMP: N-methyl-2-pyrrolidone BCS: ethylene glycol dibutyl ether The molecular weight measurement conditions of the polyimine are shown below. Device: room temperature gel permeation chromatography (GPC) device manufactured by Senshu Scientific Co., Ltd. (SSC-7200) Column: Shodex column (KD-803, KD-805)

Column temperature: 5 (TC dissolving solution: N, N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr, H20) is 30 mmol/L, phosphoric acid. Anhydrous crystal (〇-phosphoric acid) is 30 mmol /L, tetrahydrofuran (THF) is 10 ml / L) Flow rate: 1.0 ml / minute calibration line Standard sample: Tosho company TSK standard polyethylene oxide (molecular weight of about 900,000, 150,000, 100,000, 30,000), and Polymer Polyethylene glycol manufactured by Laboratories Ltd. (molecular weight: about 12,000 ' 4,000 > 1,000 ) « In addition, the ruthenium imidization ratio of polyimine was measured as follows. 20 mg of polyimine powder was placed in an NMR sample tube (Grassino Scientific company NMR standard -81 · 201219379 quasi-sampling tube), add 0.53mL of deuterated dimethyl hydrazine (DMSO-d6, 0.05% TMS mixture), completely dissolve it in ultrasonic wave. 500MHz of this solution The proton NMR was measured by an NMR measuring instrument (JNW-ECA500) manufactured by JEOL DATUM Co., Ltd. The ruthenium imidization ratio was determined by using protons having a structure which did not change before and after the imidization as a reference proton, and the proton was used. The peak score 値, with from 9.5 10. The proton peak integral NH of the NH group of proline which appears near Oppm is obtained by the following formula. For the following formula, X represents the proton peak integral 値 from the NH group of proline, and y represents the reference proton. The peak integral 値, α represents the ratio of the number of reference protons corresponding to one ruthenium matrix of proline in the case of poly-proline (〇 胺 〇 %). 醯 imidization rate (%) = ( L-a_x/y) χΙΟΟ (Example 1) BODA (6 · 0 1 g, 2 4 · Ommol ) , p-PDA (2.6 0 g, 24. Ommo 1 ), PCH ( 6.85 g, 18. 8 mmol) , DA-1 (4.7 6 g '18.0 mmol) was dissolved in NMP (81.5 g), and after reacting at 80 ° C for 5 hours, CBDA ( 6.94 g, 35.4 mmol) and NMP ( 27.2 g) were added. After the reaction was carried out for 10 hours at 40 ° C, a polyaminic acid solution was obtained. After adding NMP to the polyamic acid solution (135 g) and diluting to 6 mass%, acetic anhydride was added as a ruthenium amide catalyst ( 18.3g) and pyridine (.23.6g) were reacted at 5 ° C for 3 hours. The reaction solution was poured into methanol (1 700 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol.The polyimine powder (A) was obtained by drying under reduced pressure at 100 °C. The polyazinium-82-201219379 amine has a sulfhydrylation ratio of 60%, a number average molecular weight of 12,000, and a weight average molecular weight of 39,000. NMP (74.0 g) was added to the obtained polyimine powder (A) (6.0 g), and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (B). In addition, 0.06 g (100% by mass of the solid content) of the polymerizable compound (RM1) obtained above was added to the above-mentioned liquid crystal alignment agent (B), and the mixture was stirred at room temperature for 3 hours, and then dissolved. The liquid crystal alignment agent (B 1 ) is obtained. (Example 2) 0.06 g (10% by mass of the solid content) of the polymerizable compound (RM2) obtained above was added to the liquid crystal alignment agent (B) 1 O.Og, and the mixture was stirred at room temperature for 3 hours and then dissolved. The liquid crystal alignment agent (B2) was prepared. (Example 3) To 0.00.0 g of the liquid crystal alignment agent (B), 0.06 g (10% by mass of the solid content) of the polymerizable compound (RM3) obtained above was added at room temperature. After stirring for 3 hours, it was dissolved to prepare a liquid crystal alignment agent (B3) (Example 4) -83 - 201219379 For the liquid crystal alignment agent (B) l〇. 〇g, the above-mentioned polymerizable compound (RM4) 0.06 was added. g (10 mass% of the solid content), which was stirred at room temperature for 3 hours, and dissolved to prepare a liquid crystal alignment agent (B4) (Example 5) For the liquid crystal alignment agent (B) 1 〇.〇g 0.06 g (solid content: 1% by mass) of the polymerizable compound (RM5) obtained above was added, and the mixture was stirred at room temperature for 3 hours, and then dissolved to prepare a liquid crystal alignment agent (B 5 ) (Comparative Example 1) BODA ( 4.38g, 1 7.5 mm ο 1 ), m-PDA ( 2.65g, 2 4.5 mm ο 1), PCH (4.00g, l〇.5mmol) was dissolved in NMP (42.8g), and reacted at 80 ° C for 5 hours, then added CBDA (3.22g, 16.5mmol) and NMP ( 14.2g), at 40 After a reaction of ° C for 1 hour, a polyaminic acid solution was obtained. After adding NMP to the polyamic acid solution (70.0 g) and diluting to 6 mass%, acetic anhydride (1.76 g) and pyridine (5.44 g) as a ruthenium amide catalyst were added, and the mixture was carried out at 100 ° C. Hour response. The reaction solution was poured into methanol (900 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (C). The polyimine had a ruthenium iodide ratio of 73%, a number average molecular weight of 15,000, and a weight average molecular weight of 47,000.

To the obtained polyimine powder (C) (6.0 g), NMP-84 - 201219379 (74.0 g) was added, and the mixture was stirred and dissolved in 5 (TC for 12 hours. BCS (20_0g) was added to the solution. The polyimine solution (D) was obtained by stirring at 50 ° C for 5 hours. Further, for the polyimine solution (D) 10. 〇g, the above-mentioned polymerizable compound (RM2) 0.06 g (for solid content) was added. In a mass ratio of 1% by mass), it was stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (D1). <Preparation of unit cell> (Example 6) The liquid crystal alignment agent obtained in Example 1 was used. (B 1 ), the formation of the unit cell was carried out in the order shown below. The liquid crystal alignment agent (B1) obtained in Example 1 was spin-coated on a tantalum electrode pattern having a pixel size of ΙΟΟμηηχΒΟΟμηι and a line/pitch of 5 μm each. Thereafter, the crucible surface of the electrode substrate was dried on a hot plate at 80 ° C for 90 seconds, and then fired in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 1 〇〇 nm. Further, the liquid crystal alignment agent (B 1 ) was spin-coated on the ITO in which the electrode pattern was not formed. The film was dried in a hot plate at 80 ° C for 90 seconds, and then fired in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of ηηιη. After 6 μm of the bead spacer was spread on the liquid crystal alignment film, a sealant (solvent type thermosetting epoxy resin) was applied from the upper surface. Next, the surface of the liquid crystal alignment film forming the other substrate was used as the inner side, and the previous After the substrate is bonded, the sealant is hardened to prepare a hollow cell of -85-201219379. The liquid crystal MLC-6608 (trade name of Mock Corporation) is injected into the oven at 120 ° C by a vacuum injection method. The isotropic treatment (re-alignment treatment by heated liquid crystal) produces a unit cell. The post-production response speed of the obtained unit cell is measured by the following method. Thereafter, 20 Vp-p is added to the unit cell. In the state of voltage, UV20J of a 313 nm band-pass filter was irradiated from the outside of the unit cell. Then, the response speed was measured again, and the response speed before and after UV irradiation was compared. The results of the response speed after the UV irradiation of 20J (after UV20J) are shown in Table 2. "Measurement method of response speed" First, a set of backlights and orthogonal polarization states are set with polarizing plates and light amount detection. The measuring device is composed of a sequence of cells, and a unit cell is disposed between a group of polarizing plates. At this time, the pattern of the IT0 electrode formed by the line/pitch is 45° to the orthogonal polarized light. The above-mentioned unit cell is applied with a rectangular wave of voltage 4V and a cycle number of 1 kHz. The change in brightness observed by the light quantity detector reaches saturation change is read by the oscilloscope, and the brightness when no voltage is applied is 〇%, plus A voltage of ±4 V, and the saturation luminance is taken as 100%, and the time when the luminance is changed from 10% to 90% is taken as the response speed. (Example 7) The same operation as in Example 6 was carried out except that the baking temperature was changed from 200 ° C to 140 ° C, and the response speed before and after UV irradiation was compared. -86-201219379 (Example 8) The same operation as in Example 6 was carried out except that the liquid crystal alignment agent (B1) was used instead of the liquid crystal alignment agent (B1), and the response speed before and after the UV irradiation was compared. (Example 9) The reaction rate before and after UV irradiation was compared with the same operation as in Example 8 except that the baking temperature was changed from 200 °C to 140 °C. (Example 1 0) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the UV irradiation was compared. (Example 1 1) The reaction rate before and after UV irradiation was compared with the same operation as in Example 10 except that the baking temperature was changed from 200 °C to 140 t. (Example 1 2) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B1) was used instead of the liquid crystal alignment agent (B1), and the response speed before and after Uv irradiation was compared. (Example 1 3) -87-201219379 The same operation as in Example 12 was carried out except that the baking temperature was changed from 200 °C to 14 °C, and the response speed before and after UV irradiation was compared. (Example 1 4) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B1) was used instead of the liquid crystal alignment agent (B1), and the response speed before and after the UV irradiation was compared. (Example 1 5) The same operation as in Example 14 was carried out except that the baking temperature was changed from 200 °C to 140 °C, and the response speed before and after UV irradiation was compared. (Comparative Example 2) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the UV irradiation was compared. (Comparative Example 3) The same operation as in Comparative Example 2 was carried out except that the baking temperature was changed from 200 ° C to 140 ° C, and the response speed before and after UV irradiation was compared. (Comparative Example 4) The same operation as in Example 以外 was carried out except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the UV irradiation was compared -88 to 201219379 degrees. (Comparative Example 5) The firing rate was changed from 20 (TC to 140 °C, and the same operation as in Comparative Example 4 was carried out, and the response speed before and after UV irradiation was compared. The results are shown in Table 2, and the content contained therein was contained. Examples 6 to 15 of a photopolymerizable side chain of a methacryl group and a polymer (polyimine) in which a liquid crystal is aligned in a vertical side chain and a liquid crystal alignment agent of a polymerizable compound, and polymerization properties are used. Comparative Examples 4 and 5 of a compound which does not contain a liquid crystal alignment agent of a polymer having a photoreactive side chain, or a side chain containing a photoreactive side chain having a methacryl group and a liquid crystal alignment direction In comparison with Comparative Examples 2 and 3 of the polymer (polyimine), the liquid crystal alignment agent B to which the polymerizable compound was not added, the rate of improvement of the response speed before and after the ultraviolet irradiation was remarkably improved. When the photoreactive side chain of the propylene group and the polymer having a vertical side chain of the liquid crystal alignment and the polymerizable compound are used as a liquid crystal alignment agent, the response speed can be further improved, even if it is less concentrated. In the case where the amount of the compound to be compounded is sufficient, the reaction speed can be sufficiently increased. Further, a liquid crystal alignment agent containing a polymerizable compound having a polymerizable group at both terminals and a polymerizable group is used. 1 1 or a liquid crystal alignment agent containing a polymerizable compound having a methacrylate group at both ends and having a methacrylate group bonded to a phenyl group to form a phenyl group, and a methacrylate group having a structure in which an oxyalkylene group is bonded to a phenyl group. In 3, when the firing temperature is low (-89-201219379 140 °C) or higher (200 °c), the response speed is greatly improved. On the other hand, the use contains a methacrylate group, and In Examples 14 to 15 of the liquid crystal alignment agent having a structure in which the methacrylate group was directly bonded to a phenylene group, the rate of improvement of the response speed at the time of firing at 200 ° C was more than that at the time of firing at 1 40 ° C. In Examples 6 to 7 in which only the polymerizable compound different from the polymerizable compound used in Examples 14 to 15 was used, the firing temperature dependency was hardly confirmed, so it was estimated that the methacryl group was The combined carbon atoms are sp3 mixed orbits, making The thermal stability of the conjugate compound is increased, and the dependence of the rate of increase of the response speed on the firing temperature becomes small. cm2) The firing temperature of the liquid crystal alignment agent CC) The response speed (mscc> Name polymerization 1 Biochemical decoration addition amount valence %) Example 6 after initial UV20J B1 RM1 10 200 779 62 Example 7 B! 140 891 55 0 Example 8 B2 RM2 10 200 821 35 K Example 9 B2 140 862 37 Example 10 B3 RM3 10 200 783 36 Example 11 B3 140 808 42 Example 12 B4 RM4 10 200 766 35 Example 13 B4 140 882 31 Example 14 B5 RM5 10 200 814 732 Example 15 B5 140 850 31 Comparative Example 2 B One - 200 823 809 Comparatively fine 3 B 140 816 793 Comparative Example 4 DI RM2 10 200 798 456 Comparative Example 5 D1 140 812 398 Comparative Example (Example 1 6) For the liquid crystal alignment agent (B) 1 O.Og, the polymerizable compound (RM6) 0.06 obtained above was added. g (1% by mass for solid content) 'Agitated and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (B6) -90 - 201219379 (Example 17) For liquid crystal alignment agent (B) 1 0 · 〇g, adding the above-mentioned polymerizable compound (RM7) 0.06 g (10% by mass of the solid content), which was stirred at room temperature for 3 hours, and then dissolved to prepare a liquid crystal alignment agent (B 7 ) (Example 18) For the liquid crystal alignment agent (B) 1 〇.〇g, 0.06 g (10% by mass of the solid content) of the polymerizable compound (RM8) obtained above was added, and the mixture was stirred at room temperature for 3 hours, and then dissolved to prepare a liquid crystal alignment agent (B8). 1 9 ) The liquid crystal alignment agent (B ) 1 O.Og was added to the above-mentioned polymerizable compound (11^19) 0.068 (10% by mass for the solid content), and the mixture was stirred at room temperature for 3 hours, and then dissolved. Preparation of liquid crystal alignment agent (B9) (Example 20) For the liquid crystal alignment agent (B) 1 O.Og, 0.06 g of the polymerizable compound (RM10) obtained above (10% by mass for solid content) was added at room temperature. After stirring for 3 hours, the solution was dissolved to prepare a liquid crystal alignment agent (B 1 0 -91 - 201219379 (Example 2 1 ). For the liquid crystal alignment agent (B) 10.0 g, a compound (RM11) was added to 0.06 g (for solids into a room) After stirring for 3 hours, the mixture was dissolved, and the polymerization fraction obtained above was adjusted. 1 〇质量%), in the liquid crystal alignment agent (B 1 1 (Example 22) For the liquid crystal alignment agent (B) lO.Og, the compound (RM12) 0.06g (after solidification at room temperature for 3 hours) To dissolve, adjust the polymerization obtained by adding the above into 1 〇 mass%), in the liquid crystal alignment agent (B 1 2 (Example 23) 10.0 g for the liquid crystal alignment agent (B), add the compound (RM13) 0.06 g (the solid is allowed to stand at room temperature for 3 hours, and then dissolved, and the polymerization obtained by the above-mentioned addition is divided into 1% by mass), and the liquid crystal alignment agent (B 1 3 (Example 24) is liquid crystal. The alignment agent (B) lO.Og, the addition compound (RM14) 0.06 g (the solid is allowed to stand at room temperature for 3 hours, and then dissolved, and the polymerization obtained by the above-mentioned addition is divided into 1 〇 mass%). Liquid crystal alignment agent (B 1 4 -92- 201219379

(Example 25) The liquid crystal alignment agent (B) 10.Og' was added. Compound (RM15) 0.06 g (The solid was dissolved at room temperature for 3 hours, and then dissolved, and the polymerization obtained above was divided into 1 〇质量%), in [liquid crystal alignment agent (B 1 5 (Example 26) for liquid crystal alignment agent (B) 1 0 · 0g, added compound (RM16) 0.06g (for solids to room temperature for 3 hours of stirring) Thereafter, it was dissolved, and the polymerization property obtained by the above addition was divided into 1 〇 mass%), and the liquid crystal alignment agent was extracted (B 1 6 (Example 27). For the liquid crystal alignment agent (B) 1 0. 〇g, Tim Compound (RM17) 0.06 g (The solid is allowed to stand at room temperature for 3 hours, and then dissolved, and the polymerization property obtained above is divided into 1% by mass), and the liquid crystal alignment agent is extracted (B 1 7 (Example) 2 8 ) For the liquid crystal alignment agent (B ) 1 〇. 〇g, Add: Compound (RM18) 0.06 g (For solids: Stir at room temperature for 3 hours, dissolve, and prepare the above-mentioned polymerizability) 1 〇质量%), in the liquid crystal alignment agent (B 1 8 -93 - 201219379 (Example 29) For the liquid crystal alignment agent (B) 1 0·Og, 0.06 g of the above-obtained poly compound (RM19) (1% by mass for solid content) was stirred at room temperature for 3 hours, and then dissolved to prepare a liquid crystal alignment agent, which was in B 1 9 ( Example 30) To the liquid crystal alignment agent (B) 1 0 · Og, 0.06 g of the poly compound (RM20) obtained above (1% by mass based on the solid content) was added, and the mixture was stirred at room temperature for 3 hours, and then dissolved. For the liquid crystal alignment agent (B) (Example 3 1 ), the liquid crystal alignment agent (B) 10% was added with 0.06 g of the poly compound (RM21) obtained above (1% by mass for the solid content) at room temperature. After stirring for 3 hours, the solution was dissolved to prepare a liquid crystal alignment agent. In B21 (Example 32), for the liquid crystal alignment agent (B) 10 g, 0.06 g of the above-obtained poly compound (RM22) was added (for solid content) 1% by mass), stirred at room temperature for 3 hours, and then dissolved to prepare a liquid crystal alignment agent, in B22-94-201219379 (Example 3 3) For the liquid crystal alignment agent (B) 10. 〇g, the above is added The obtained polymerizable compound (RM23) 0.06 g (for solid The component was 10% by mass), and the mixture was stirred at room temperature for 3 hours, and then dissolved to prepare a liquid crystal alignment agent (B23 (Example 34). In place of the liquid crystal alignment agent (B1), a liquid crystal alignment agent (B 6 ) was used. The same operation as in Example 6 was carried out, and the response speed before and after the UV irradiation was compared. (Example 3 5) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B1) was used instead of the liquid crystal alignment agent (B1), and the response speed before and after the UV irradiation was compared. (Example 36) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the UV irradiation was compared. (Example 3 7) The reaction speed before and after UV irradiation was compared with the liquid crystal alignment agent (B1), except that the liquid crystal alignment agent (B9) was used, and -95-201219379 was subjected to the same operation as in Example 6. (Example 3 8) The response speed before and after U V irradiation was compared with the liquid crystal alignment agent (B 1 ) except that the liquid crystal alignment agent (B 1 0) was used, and the same operation as in Example 6 was carried out. (Example 3 9) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the UV irradiation was compared. (Example 40) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the UV irradiation was compared. (Example 4 1) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the UV irradiation was compared. (Example 42) -96-201219379 The same operation as in Example 6 was carried out except that the liquid crystal alignment agent (B1) was used instead of the liquid crystal alignment agent (B1), and the response speed before and after the irradiation of uV was compared. (Example 43) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B1) was used instead of the liquid crystal alignment agent (B1), and the response speed before and after the UV irradiation was compared. (Example 44) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the UV irradiation was compared. (Example 45) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the UV irradiation was compared. (Example 46) The response speed before and after UV irradiation was compared with that of the liquid crystal alignment agent (B1) except that the liquid crystal alignment agent (B18) was used. -97-201219379 (Example 47) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the U V irradiation was compared. Example 48) The same operation as in Example 6 was carried out except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the UV irradiation was compared. (Example 49) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the UV irradiation was compared. (Example 50) The same operation as in Example 6 was carried out except that the liquid crystal alignment agent (B1) was used instead of the liquid crystal alignment agent (B1), and the response speed before and after the UV irradiation was compared. (Example 5 1) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (B 1 ) was used instead of the liquid crystal alignment agent (B 1 ), and the response speed before and after the UV irradiation was compared. -98 - 201219379 (Example 5 2 ) TCA ( 3.36 g , 15.0 mmol ) , p-PDA ( 1.30 g , 1 2.0 mm ο 1 ), DA - 3 (3 · 1 4 g, 6 · Ommo 1 ), DA-1 (3.17 g, 12.0 mmol) was mixed in NMP (41.6 g), and after reacting at 60 ° C for 5 hours, CBDA (2.88 g, 14.7 mmol) and NMP (13.9 g) were added at 40 ° C. A polyamine acid solution was obtained after 10 hours of reaction. After adding hydrazine to the polyamic acid solution (68 g) and diluting it to 6% by mass, acetic anhydride (6.0 g) and pyridine (1 1.7 g) were added as a ruthenium-imiding catalyst, and the mixture was carried out at 50 ° C. Hour response. The reaction solution was poured into methanol (8 50 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (E). The polyimine has a ruthenium iodide ratio of 50%, a number average molecular weight of 18,000, and a weight average molecular weight of 58,000. NMP (74.0 g) was added to the obtained polyimine powder (E) (6.0 g), and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.Og) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (F). In addition, RM2 of 液晶.〇6g (100% by weight of solid content) was added to the above-mentioned liquid crystal alignment agent (F)10.Og, and stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent ( Further, 0.06 g (100% by weight of solid content) of RM4 was added to the above liquid crystal alignment agent (F) 10 Og, and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (F2). -99-201219379 (Example 53) The same operation as in Example 6 was carried out except that the liquid crystal alignment agent (B1) was used instead of the liquid crystal alignment agent (B1), and the response speed before and after UV irradiation was compared. 54) The same operation as in Example 6 was carried out, except that the liquid crystal alignment agent (F1) was used instead of the liquid crystal alignment agent (F1), and the response speed before and after the UV irradiation was compared. (Example 5 5) BODA (5.00 g, 2 0.0mm ο 1 ) , p-PDA ( 0.87g, 8.0mm ο 1 ), PCH (3.04g, 8. Ommol ), DA-2 ( 4.88g, 24.0mmol) mixed in NMP ( 52.7g), After reacting at 80 °C for 5 hours, CBDA (3.77 g, 19.2 mmol) and NMP (17.56 g, reacted at 40 ° C for 10 hours to obtain polyfluorene. After the NMP was added to the polyamic acid solution (75 g) and diluted to 6% by mass, acetic anhydride (8.7 g) and pyridine (13.5 g) were added as a ruthenium catalyzed catalyst at 50 ° C. The reaction solution was poured into methanol (95 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder ( G). The polyimine has a oxime imidization ratio of 50%, a number average molecular weight of 20,000, and a weight average molecular weight of 8600 ° -100 - 201219379 in the obtained polyimine powder (G) (6.0 g). Into the NMP (74.0g), stir and dissolve at 50 ° C for 12 hours. Add BCS ( 20.0g ) to the solution. After stirring for 5 hours at 50 ° C, the liquid crystal alignment agent (G 1 ) is obtained. 'The liquid crystal alignment agent (G1) l〇.〇g was added to 0.06 g (1% by mass of the solid content) of the polymerizable compound RM2, and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent. (G2) (Example 5 6) In place of the liquid crystal alignment agent (B 1 ), the liquid crystal alignment agent (g 2 ) was used. The same operation as in Example 6 was carried out to compare the response speeds before and after UV irradiation. The results of Examples 34 to 51, 53, 54 and 56 are shown in Table 3. As shown in Table 3, Examples 34 to 51, 53, 54, and 56 using a liquid crystal alignment agent containing the following polymer (polyimine) and a polymerizable compound, although each polymerizable compound or polymer was different, In the same manner as in Examples 6 to 15, the rate of improvement of the response speed before and after the ultraviolet irradiation was remarkably high, and the polymer (polyimine) had a photoreactive side chain containing a methacryl group or the like and aligned the liquid crystal. Vertical side chain. -101 - 201219379 [Table 3] Liquid crystal alignment agent firing temperature α) Response speed (msec) Type of polymerizable compound type addition amount (% by mass) Initial UV20J after Example 34 B6 RM6 10 200 790 24 Example 35 B7 RM7 10 200 792 22 Embodiment 36 B8 RM8 10 200 821 32 Embodiment 37 69 RM9 10 200 849 331 Embodiment 38 BI0 RM10 10 200 815 41 Embodiment 39 B11 RMU 10 200 860 41 Embodiment 40 B12 RM12 10 200 802 403 Embodiment 41 613 RM13 10 200 784 40 Example 42 B14 RM14 10 200 808 33 Example 43 B15 RM15 10 200. 757 186 Example 44 B16 RM16 10 200 798 219 Example 45 B17 RM17 10 200 774 236 Example 46 B18 RM18 10 200 817 17 Example 47 619 RM19 10 200 754 12 Example 48 B20 RH20 10 200 782 19 Example 49 ΰ21 RM21 10 200 816 295 Example 50 Β22 RM22 10 200 830 190 Example 51 Β23 RM23 10 200 794 123 Example 53 F1 RM2 10 200 649 43 Example 54 F2 SM4 10 200 702 51 Example 56 G2 RM2 10 200 753 42 -102-

Claims (1)

201219379 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by having the following polymer, a polymerizable compound, and a solvent; the polymer is selected from the group consisting of a side chain having a liquid crystal alignment direction and a content selected from the group consisting of a polyimide-based precursor of a photoreactive side chain of at least one of a methacryl group, a propylene group, a vinyl group, and a cinnamyl group, and a polyazide obtained by imidating the polyimine precursor with a ruthenium At least one polymer of an amine; the polymerizable compound is a polymerizable compound having a group which undergoes photopolymerization or photocrosslinking at each of two or more terminals. 2. The liquid crystal alignment agent of claim 1, wherein the photoreactive side chain comprises a base selected from the following formula (I); [Chemical Formula 1] 0) 〇II H2 -〇-c- C=CH2 ——C——C=CH2 L Η —〇—c=ch2 —c=ch2 (wherein R11 is Η or methyl). 3. The liquid crystal alignment agent according to claim 1, wherein the aforementioned radical or photocrosslinking group is selected from the following formula (II); (II) wherein R12 is hydrazine or an alkyl group having 1 to 4 carbon atoms, and hydrazine 1 is substituted by an alkyl group having 1 to -103 to 201219379 12 or an alkoxy group having 1 to 12 carbon atoms. An aromatic ring or a heterocyclic ring, and Z2 is a monovalent aromatic ring or a heterocyclic ring which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. A liquid crystal alignment film which is obtained by applying a liquid crystal alignment agent according to any one of claims 1 to 3 to a substrate and firing it. 5. A liquid crystal display device comprising: a liquid crystal layer provided on a liquid crystal alignment film and brought into contact with a liquid crystal alignment film; and the liquid crystal layer is irradiated with ultraviolet rays while applying a voltage thereto The liquid crystal alignment film is obtained by coating a substrate with a liquid crystal alignment agent according to any one of claims 1 to 3 and baking it. 6. A method of producing a liquid crystal display device, characterized in that a liquid crystal alignment agent according to any one of claims 1 to 3 is applied onto a substrate and fired to obtain a liquid crystal alignment film. The liquid crystal layer is placed in contact with the liquid crystal alignment film. The liquid crystal layer is irradiated with ultraviolet rays to apply a voltage to the liquid crystal layer. -104- 201219379 IV Designated representative map: (1) The designated representative circle in this case is: None. (2) A brief description of the symbol of the representative :: None 201219379 V If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none