TW201217352A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, manufacturing method for liquid crystal display element, and polymerisable compound - Google Patents

Abstract

A polymerisable compound having a terminal having an a-methylene-?-butyrolactone group and a terminal having a photopolymer or a photocrosslinking group; a polymer for forming a liquid crystal aligning agent capable of aligning liquid crystals; and a liquid crystal aligning agent containing a solvent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal alignment agent and a liquid crystal alignment which can be used for manufacturing a liquid crystal display element which is produced by irradiating ultraviolet rays in a state where a voltage is applied to liquid crystal molecules. A film, a liquid crystal display element, a method of producing a liquid crystal display element, and a polymerizable compound. [Prior Art] In a liquid crystal display device in which a liquid crystal molecule having a vertical alignment with respect to a substrate is responsive to an electric field (also referred to as a vertical alignment (VA) method), a voltage is applied to the liquid crystal molecule for the manufacturing process. The step of irradiating ultraviolet rays. In the liquid crystal display device of such a vertical alignment type, a photopolymerizable compound is added to the liquid crystal composition in advance, and a vertical alignment film such as polyimide or the like is used at the same time, and ultraviolet rays are applied to the liquid crystal cell to accelerate the liquid crystal. The technique of the response speed (for example, refer to Patent Document 1 and Non-Patent Document 1) (PSA (Polymer Sustained Alignment) type liquid crystal display). Generally, the tilt direction of the liquid crystal molecules responsive to the electric field is 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 is added to the liquid crystal cell. When the voltage 'is irradiated with ultraviolet rays and the polymer structure in which the liquid crystal molecules are tilted is formed on the liquid crystal alignment film, the liquid crystal display element can be accelerated compared with the method of controlling the tilt direction of the liquid crystal molecules only by the protrusions or slits. Response speed.

S-5-201217352 It has been reported that even if a photopolymerizable compound is added to a liquid crystal alignment film without being added to a liquid crystal alignment film, the response speed of the liquid crystal display element can be accelerated (SC-PVA liquid crystal display). (For example, refer to Non-Patent Document 2). [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2003-307720 [Non-Patent Document] [Non-Patent Document 1] K. Hanaoka, SID 04 DIGEST, P.1200-1202 [Non-Patent Document 2 KH Y.-J. Lee, SID 09 DIGEST, P.666-668 SUMMARY OF THE INVENTION Problems to be Solved by the Invention However, it is expected that the response speed of the liquid crystal display element can be further accelerated. In addition, it is considered that the increase in the amount of addition of the photopolymerizable compound can accelerate the response speed of the liquid crystal display device, and if the photopolymerizable compound remains directly in the liquid crystal without being reacted, it becomes an impurity (contamination) and becomes a liquid crystal. The reason for the reliability of the display component. At this time, a method of adding a polymerizable compound which accelerates the response speed to a small amount of liquid crystal is considered, but there is also a limit. In the above background, a liquid crystal alignment agent which accelerates the response speed even when the liquid crystal does not contain a polymerizable compound is desired. -6- 201217352 However, the liquid crystal alignment agent must be fired at a high temperature when the solvent is completely removed. Therefore, it is expected that the firing speed can be accelerated even at such a high temperature, and the requirement for accelerating the response speed is not limited to vertical. The alignment type liquid crystal display element also exists in other modes such as the Twisted Nematic TN method. In order to solve the problems of the prior art, the present invention provides a liquid crystal alignment agent which can improve the response speed of a liquid crystal display element even when the liquid crystal does not contain a polymerizable compound and is fired at a high temperature. A liquid crystal alignment film, a liquid crystal display element, a method for producing a liquid crystal display element, and a polymerizable compound. Means for Solving the Problem The liquid crystal alignment agent of the present invention which solves the above-mentioned problems is characterized by containing a polymerizable compound, a polymer, and a solvent, wherein the polymerizable compound is a terminal having an α-methyl-γ-butyrolactone group. A polymerizable compound having a terminal having a photopolymerization or photocrosslinking group, wherein the polymer is a polymer which forms a liquid crystal alignment film capable of aligning liquid crystals. The polymerizable compound may be at least one selected from the group consisting of the following formulas [1-1] to [1-4].

S 201217352 [化1]

I or minutes, W table Xiaoyuan base is 2~ I or selected (in the formula [1-1]~[1-4], 'V means single bond or -R310-, R31 is the direct abuse of the carbon number 1~1 The alkylene group of hydrazine, for example, v is -(CH2) ηι-〇-shows a single bond or -OR32-, and R32 is a straight or branched carbon number of 1 to 10, for example, w is -0-(CH2) nl -' nl is an integer of 1 to 10, preferably 10, X and y are each independently 1 or 2' Rl is hydrogen or methyl 'A21 is a single | from the group below) [Chemical 2]

(wherein, pi is an integer of 2 to 10, ql is an integer of 0 to 2, and z is 1 or 2) Further, the polymerizable compound may be selected from the following formulas [Π-1] to [η-3] At least one of 201217352. [Chemical 3]

[Π-3] ) ~1 1 of whole I hydrogen, -CN, CH3 (ml 6H4-C6H4-

(In the formula [II-1] to [II-3], n2 is an integer of 2 to 11, and ml is (number, X is 1 or 2, R2 is hydrogen, -OCH3 or a halogen atom, R3f, -0(CH2) ) mlCH3 or a halogen atom, R4 is -(CH2) m is an integer of 0 to 11), A22 is a single bond, -0-C6H4- or -OC) Further, the above polymerizable compound may be of the following formula [III-1] ]. ^Hch^Ou—o—[ΙΠ-1] (In the formula [ΙΙΙ-1], 11 is an integer of 2 to 9 and X1 is a group selected from the group Μ~[iii-3]) 5]

-9- 201217352 (in the formula [iii-2], m2 is an integer of 4 to 8, and in the formula [iii_3], 'r5 is a group selected from the following formula) [Chem. 6]

(wherein, X2 is hydrogen, a halogen atom, a cyano group or an alkoxy group; R1 is hydrogen or a methyl group, n3 is an integer of 2 to 1 Å, P2 is an integer of 3 to 10, and 01 is an integer of 0 to 6) The aforementioned polymerizable compound may be of the following formula [IV] ° X? X4

Xs X6 (wherein X3, X4, X5 and X6 are each independently hydrogen or a fluorine atom' R6 is hydrogen, a dentate atom, a cyano group, a hospital group, a hospitaloxy group, or an alkoxy group, and 0 is a _C (= 0) 0- or - OC (= 0) group, n4 is an integer of 4 to 10) Further, a polymer which forms a liquid crystal alignment film obtained by aligning the liquid crystal is preferable, and it is preferable that the liquid crystal is aligned in a vertical side chain. The liquid crystal alignment film of the present invention is preferably obtained by applying the above liquid crystal alignment agent to a substrate and firing it. In the liquid crystal display device of the present invention, a liquid crystal layer is provided on a liquid crystal alignment film obtained by applying the liquid crystal alignment agent onto a substrate and fired thereon, and a liquid crystal layer is applied thereto while applying a voltage to the liquid crystal layer. - The liquid crystal cell of 201217352 is characterized. Further, in the method for producing a liquid crystal display device of the present invention, the liquid crystal alignment agent is applied onto a substrate, and a liquid crystal layer is provided on the liquid crystal alignment film obtained by firing, and is brought into contact with the liquid crystal layer, and a voltage is applied while the liquid crystal layer is applied thereto. It is characterized by the production of liquid crystal cells by ultraviolet rays. Further, the polymerizable compound of the present invention is characterized by any one of the following formulae. [化8]

According to the present invention, it is possible to provide a liquid crystal alignment agent which can improve the response speed of the liquid crystal display element, in the case where the liquid crystal does not contain a polymerizable compound and is fired at a high temperature. Further, a liquid crystal display element of a vertical alignment type having a fast response speed by using the liquid crystal alignment agent can be provided. The invention will be described in detail below. The liquid crystal alignment agent of the present invention contains a polymerizable compound, a polymer, and a solvent, wherein the polymerizable compound has a terminal having an α-methyl-γ-butyrolactone group and a group having photopolymerization or photocrosslinking. The polymerizable compound at the end, the polymer is a polymer which forms a liquid crystal alignment film capable of aligning the liquid crystal. Further, the liquid crystal alignment agent is a solution when a liquid crystal alignment film is formed. The liquid crystal alignment film is a film in which the liquid crystal is aligned in a predetermined direction, for example, in a vertical direction. The components contained in the liquid crystal alignment agent of the present invention will be described in detail below. <Polymerizable Compound> The polymerizable compound containing the liquid crystal alignment agent of the present invention is one having a terminal having an α-methyl-γ-butyrolactone group and a group having photopolymerization or photocrosslinking. The end. The polymerizable compound contained in the liquid crystal alignment agent of the present invention is a terminal having a terminal having an α-methyl-γ-butyrolactone group and a terminal having photopolymerization or photocrosslinking. That is, at both ends (both ends), by having an α-methyl-γ-butyrolactone group and a photopolymerization or photocrosslinking group, by irradiating light, a liquid crystal alignment film -12 obtained by forming an alignment liquid crystal - The polymer of 201217352 or the polymer of the polymerizable compound is reacted and can be crosslinked with them. Of course, since the terminal having an α-methyl-γ-butyrolactone group and a terminal having a photopolymerization or photocrosslinking group are held, the polymerizable compounds can react with each other to form a polymer. Further, the photopolymerization base is a polymerizable functional group by irradiation of light, and the photocrosslinking group is a polymer or a polymerizable compound which forms a liquid crystal alignment film obtained by aligning liquid crystal by irradiation with light. The polymers are reacted to pass the functional groups to which they are crosslinked. Further, since at least one of the functional groups having both terminals is an α-methyl-γ-butyrolactone group, the obtained polymer has a rigid structure and has excellent alignment ability of liquid crystal alignment, so that it will be described later. As shown in the examples, by using a liquid crystal display element such as a vertical alignment method such as a PS 液晶 type liquid crystal display or an SC-PV Α type liquid crystal display, the response speed can be greatly increased even when fired at a high temperature. This is presumed to be a structure in which the polymerizable compound contained in the liquid crystal alignment agent of the present invention lacks thermal polymerization properties, and therefore, it can be sufficiently resistant to, for example, a firing temperature of 20 °C or higher. Of course, even if the liquid crystal does not contain a polymerizable compound, the response speed can be greatly increased. In the polymerizable compound to be used in the liquid crystal alignment agent of the present invention, at least one of the functional groups at both terminals must be an α-methyl-γ-butyrolactone group, and for example, only the acrylic acid described in Patent Document 1 is used. A compound having a functional group such as an ester group, a methacrylate group, a vinyl group, a vinyloxy group or an epoxy group lacks thermal stability and is difficult to withstand firing at a high temperature. Therefore, when it is added in a small amount and is fired at a high temperature, it cannot be baked. The response speed of the liquid crystal display element such as the vertical alignment mode is greatly increased. Examples of the group to carry out photopolymerization or photocrosslinking include the following formula.

S -13- 201217352 shows a price base. When a photopolymerizable group or a photocrosslinkable group is used as a methyl group-methyl group, the functional group having a polymerizable compound at both ends is only an α-methylbutyrolactone group. Therefore, it can withstand higher firing temperatures. [Chemistry 9]

(wherein R15 is hydrogen 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; , Ζ 2 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. Further, the 〇:-methyl-γ-butyrolactone group is bonded to The linking group for photopolymerization or photocrosslinking is a divalent organic group, and examples of the divalent organic group include a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, and a carbon number of 1 to 12. The divalent organic group having a divalent aromatic ring, a heterocyclic ring or a heterocyclic ring substituted by an alkoxy group or an alkoxycarbonyl group having 1 to 12 carbon atoms. The structural example of the polymerizable compound is at least one selected from the group consisting of the following formulas. Further, in the formula, R15 is hydrogen or a carbon number of 1 to 4, and Ζ1 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 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. Q1 is a divalent organic group. Q1 has a stretching phenyl group (-C6H4-) Preferably, a ring structure such as a phenyl (_C6H4-C6H4-) or a cyclohexyl group (-C6H1()-) is preferred. Because of the interaction with the liquid crystal -14- 201217352 the effect is easy to become larger. [化10]

Specific examples of the polymerizable compound include the above formulas [I-1] to [1-4], [II-1] to [II-3], [III-1], and [IV]. Specific examples of the above formula [^^] include a polymerizable compound represented by the following formula [1-1-a], and the polymerizable compound can be removed from the present invention by another application. [化11]

[1-1-a] (wherein, V represents a single bond or -R310-, R31 is a linear or branched alkyl group having 1 to 10 carbon atoms, W represents a single bond or -OR32-, and R3 2 is straight The alkylene group of the liquid crystal alignment agent of the present invention can be synthesized by a combination of organic synthetic chemistry, and the synthesis method is not particularly limited. For example, it can be manufactured according to the embodiment described later. For example, by means of the method proposed by Talaga et al., P. Talaga, M. S. Chaeffer, C. Benezra and JLStampf, Synthesis, 5 30 (1 990), the following reaction formula can be used to convert 2-(bromo) with SnCl2. Base) propylene acid (2- ( bromomethy)

S -15- 201217352 propenoic acid ) The aldehyde or ketone is synthesized by reaction. And,

Amberlyst 15 is a strong acid ion exchange resin manufactured by Rohm and Haas Company. [化 12]

COOH

R, a CHO

SnClj/Amberlyst 15 thf/h2o

R_ (wherein R' represents a monovalent organic group) Further, 2-(bromomethyl)acrylic acid can be represented by the following reaction formula by Ramarajan et al. in K, Ramarajan, K. Kamalingam, DJO'Donnell and K. D. B er 1 i η, O rg an ic S y nt hesis , vo 1.6 1 , 5 6 - 5 9 ( 1 983 ) The proposed method was synthesized. [Chem. 13]

COOEt Fonnaldehyde (solution

NaHCO. COOEt Further, in the reaction using 2-(bromomethyl)acrylic acid of SnCl2, the substituted aldehyde or ketone can be reacted with the corresponding acetal or ketal to obtain α-methyl-γ-butyl Lactone structure. Examples of the acetal or ketal include a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxanyl group, and a 1,3-pentane group. The synthesis method and protecting group are shown below. -16- 201217352 [Chem. 14]

(wherein R' represents a monovalent organic group) - The specific synthesis is explained, for example, as follows. Further, in the following reaction formula, Μ is a group selected from the group consisting of R1 being the same as R1 in the above formulas [1-1] to [1-4].

(Synthesis example of a polymerizable compound represented by the above formula [1-1] to [1-4]) Α21=single bond and W=-0-(CH2) nl-(nl is an integer of 1 to 10) The reaction of the following formula is carried out. OH + Br-CCH^-Μ 〇-(chAi-m A2 1 = single bond and W = single bond, which can be synthesized by the reaction of the following formula. -17- 201217352 [Chem. 17]

When A2 single bond and W = single bond, synthesis can be carried out by the reaction of the following formula. [Chem. 18]

HO

When SnCl2/THF HCl(aq) a21=-(ch2) ql-o-(c=o)-, it can be synthesized by the reaction of the following formula. [Chem. 19]

When a21=-(c=o) -o-(ch2) pl-o-(c=o)-, the synthesis can be carried out by the reaction of the following formula. [Chem. 20]

A21=-(C=0) -0-(CH2) ql-(C6H4) z-(CH2) ql- -18- 201217352 o-(c=o)-, which can be synthesized by a reaction of the following formula. [Chem. 21]

When money c->0irW-M A21 = - ( C = O ) -O- ( C6H4COC6H4) -Ο- ( C = O)-, it can be synthesized by the reaction of the following formula. [化22]

Α2,= . ( C= Ο) -O-( CH2) ρ,-Ο-( C6H4) z-O- ( CH2 )pl-o-(c=o)-, which can be synthesized by the reaction of the following formula.

S -19- 201217352 [Chem. 23]

H0-(CH2)pi-O

CHa〇j

• (CH2)p 广 U a21=-o-(c=o) - (C6H4) z-(c=o) -0-, can be synthesized by the reaction of the following formula. [Chem. 24]

When A21 = -0 - (C = 0) - (C6H10) - (C = 0) - 0 -, the synthesis can be carried out by a reaction of the following formula. [Chem. 25]

〇 0 DCODMAP (ΠΙ^,,-ΟΗ + „

HO '-* OH

-20- 201217352 A21=-(C=0) -0-(CH2) qi-(C6H,〇) -(CH2) qi- 〇-(C=〇)-, can be synthesized by the reaction of the following formula. [Chem. 26]

Further, the polymerizable compounds represented by the above formulas [1-3] and [1-4] can be synthesized by a reaction of the following formula. [化27]

(Synthesis Example of Polymerizable Compound of the above formula [11-ι] to [II-3]) The polymerizable compound represented by the above formula [11-1] can be synthesized by a reaction of the following formula. -21 - 201217352 [Chem. 28]

When the polymerizable compound represented by the above formula [Π-2], A22 = a single bond, it can be synthesized by a reaction of the following formula. [化29]

When the polymerizable compound represented by the above formula [II-2], A22 = -0-(C6H4)-, -0-(C6H4)-(C6H4)-, it can be synthesized by a reaction of the following formula. [化30]

The polymerizable compound represented by the above formula [II-3] can be synthesized by a reaction of the following formula. -22- 201217352 HO-(CH2)-(CH2)n2-Br - X O-R4 K2C〇3 Acetone IIOe(CH2)*(CH2)n2*〇H〇-(CH2)-(CH2) N2' PCX7CHA 〇HC-(CH2)n2- OR^* 0ΤΗ 0_R4•〇I0rH O-R4 OHC—(Cll2)n2

-Br COOH

SnCVHCI(aq) O-R* THF X O-R4 Further, the starting material in the above reaction can be synthesized, for example, by the following reaction [Chem. 32]

OHC

COOH = C:

X

Br SnCI/IHF COOH

COOH

Br SnO/THF COOH HCI (4) [Chem. 33]

(CH2>i Guang Br + HO

Or K2C03 Acetone

-(CH^rO othp

COOH

SaCl^/HClCaq) tof/h2o

(CHg^^—O- where THP represents tetrahydropyran) K2C〇3 Ac cton 丨〆**〇, -(CH2)d, —Br ^ HO K\ in (CH2)p, -OH- -(CH2>r»i-〇*4vk y/rCCH^i- -0.

COOH _(CH plus-SnayHaM ° ' /K thf/b2o

Money (CHj)pi-OH

S -23- 201217352 [Chem. 35] COOCH3

KjCOyAcctooe H〇-(CH2)-(CH2)n, cooch3 ch2ci2 OHC-(CH2)n"丨 COOCH3

HO-Kv />f-COOCH3 (^3)"!^ HO-CCHj)-(CHiJn, - and the polymerizable compound represented by the above formula [ΠΙ-1] can be published by International Publication No. 2006Π15112, International Publication No. The method described in the handbook 2008/072652, International Publication No. 20 1 0/0443 84, or the following reaction. [Chem. 36]

Further, the polymerizable compound represented by the above formula [IV] can be obtained by the following reaction: 0 - 24 - 201217352 [Chem. 37] Ο

CH2)n4—Br + HO K2C〇3 COOCH^^C>(ch2)--〇-〇〇- COOCH3 OQr C00CH3

SnCl^Cliaq) F (CH2)n4—〇 OQr cooch^ work y(C〇{^M^-co〇CH3.

l) K8〇H(aq) EtOH 3 2) Hd(aq)rmF ^〇^(chj5--〇-〇-〇-c〇〇h

DCC/DMAP COOH + Η〇·^λ ff °X>~^〇^〇K X5 xe <Polymer for forming liquid crystal alignment film obtained by aligning liquid crystal> Formation of alignment liquid crystal contained in the liquid crystal alignment agent of the present invention The polymer of the crystal alignment film can be disposed only on the liquid crystal on the liquid crystal formed on the substrate, and is not particularly limited. For example, the liquid crystal alignment on the liquid crystal alignment film on the substrate can be vertically polymerized on the substrate. Things. As the polymer which is formed in the vertical direction of the substrate on the liquid crystal alignment film which can be formed on the substrate, a polymer having a side chain perpendicular to the liquid crystal is preferable, and a polyfluorene having a side chain which aligns the liquid crystal is exemplified. Polyimine precursors such as amidinoic acid or polyamidomate, such as proline or polylysine, which are obtained by ruthenium imidization or the like, are aligned in a vertical side chain. The structure which is in the vertical direction is not particularly limited, and examples thereof include a group having a ring structure or a branched structure in the middle of an alkyl group or a long-chain alkyl group.

The liquid alignment film is formed in the direction of the liquid crystal in a vertical direction, the polyamine. A hydrocarbon group such as a solid-chain S 201217352 alcohol group or a group in which one or all of hydrogen of these groups is replaced by a fluorine atom. Of course, there may be two or more types of side chains in which the liquid crystals are aligned vertically. The vertical side chain of the liquid crystal alignment can be directly bonded to the main chain of a polymer such as a polyimide or a polyamidomate such as a polyimide or a polyimide, that is, a polyamine skeleton or a polyfluorene. The imine 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. Other examples of the side chain in which the liquid crystal is aligned perpendicularly are exemplified by the following formula (a). (8) -R7-^-R8J-^-R9^-^R10J—R1 (In the formula (a), 1, m and η each independently represent an integer of 0 or 1, and R7 represents a carbon number of 2 to 6. Affiliation, -0-, -COO-, -OCO-, -NHCO-, -CONH- or an alkylene-ether group of R 1 , R 8 , R 9 and R 1 G each independently represent a phenyl group or a ring extension. Alkyl, R11 represents hydrogen, an alkyl group having 2 to 24 carbon atoms or an alkyl group containing fluorine, a monovalent aromatic ring 'monovalent aliphatic ring' monovalent heterocyclic ring or a monovalent large cyclic substituent thereof) Further, R7 in the above formula (a) is preferably an alkylene-ether group having -〇-, -COO-, -CONH-, or a carbon number of 1 to 3 from the viewpoint of easiness of synthesis. Further, R8, R9 and R10 in the formula (a) are a combination of 丨, m, n, R8, R9 and R1G shown in the following Table 1 from the viewpoints of easiness of synthesis and ability to align the liquid crystal. good. -26- 201217352 [Table l] 1 m η R8 R9 R1 0 1 1 1 Phenylphenylene phenyl ring hexyl 1 1 1 phenyl phenyl ring hexyl ring hexyl 1 1 0 phenyl phenyl - 1 1 0 Phenylene ring-extension hexyl- 1 1 1 ring-extension hexyl ring-extension hexyl ring-extension hexyl group 1 10 ring-extension hexyl ring-extension hexyl group, at least one of 1, m, η is 1, R11 in formula (a) is preferred It is hydrogen or an alkyl group having 2 to 14 carbon atoms or an alkyl group containing fluorine. More preferably, it is 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, R11 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 preferably an alkyl group having 12 to 20 carbon atoms or an alkyl group containing fluorine. The liquid crystal alignment direction is a vertical side chain, and the liquid crystal alignment film is not particularly limited as long as the liquid crystal alignment direction is vertical. However, in the liquid crystal display element including the liquid crystal alignment film, 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 retention ratio or the accumulation of the residual DC voltage. good. Moreover, the polymer having the side chain of the liquid crystal alignment perpendicularly has the ability to align the liquid crystal in a vertical direction, and is different according to the structure in which the liquid crystal is aligned in a vertical side chain. Generally, the liquid crystal is aligned in a vertical side chain. The greater the amount, the higher the ability to align the liquid crystal alignment, and the lower the capacity. Further, when it has a ring structure, it tends to have a liquid crystal alignment perpendicular to the tube as compared with the case where the ring structure is not provided.

S -27- 201217352 Further, it is preferred to form a liquid crystal alignment film in which the liquid crystal alignment is perpendicular, and it is preferable to form a photoreactive side chain. If there is a photoreactive side chain, the response speed is increased in one step. It is of course also possible to use a polymer which forms a liquid crystal alignment film in which a liquid crystal having no light side chain is aligned in a vertical direction. The photoreactive side chain is a side chain having a functional group (hereinafter also referred to as a photoreaction) which forms a covalent bond by a photoreaction reaction such as ultraviolet light (UV), and the structure can be obtained if it has such a capability. The photoreactive side chain is not limited, and examples thereof include a acryl group, a methacryl group, an allyl group, a styryl group, a cinnamyl chalconyl group, a coumarin group, and a malayan group. Examples of the side chain such as an amine, an epoxy group, and an ethylene propyleneoxy group include an alkyl group in which these photoreactive groups are free from these hydrogen-reactive groups. The substituted hydrogen is preferably one. The alkyl carbon which is substituted by the photoreactive group is preferably 1 to 30, and more preferably 1 to 5, from the viewpoint of the response speed and the perpendicular alignment. Of course, it is also possible to have two or more types of light side chains. The photoreactive side chain may be directly bonded to a main chain of a polymer such as a polyimide, such as a polyimide, or a reactive side chain may be bonded via a suitable bonding group, and for example, the following formula (b) may be mentioned. Shower. R12-R13-R14 (b) (In the formula (b), R12 represents a single bond or -CH2-COO-, -NHCO-, -CONH- '-NH-, -CH20-,- Any of N ( CH3 CON ( CH3 ) -, -N(CH3) CO-, R13 represents a monosubstituted or substituted alkyl group having 1 to 20 carbon atoms, which is substituted by a fluorine atom, and is capable of undergoing a reaction. In the nature, it is carried out as a reactive group. As a vinyl fluorenyl group, an oxy group, a body, or an I number, a carbamide is 1 reactive or polyfluorene as a photo-OCO- bond or a non- awning- -28- 201217352 CH2- may be replaced by -CF2- or -CH=CH-gamma/worker and /丨_, and may be substituted for these bases if any of the following groups are not adjacent to each other; _〇_ , _c〇〇_, OCO-, -NHCO- '-CONH-·ΝΗ·, divalent carbocyclic ring, divalent heterocyclic ring. R14 represents vinyl 'propenyl' methacryloyl, allyl, styryl , -Ν (CH2CH= CH2 ) 2 or the structure shown below) [40]

OH

And 'R12 in the above formula (b) can be formed by a general organic synthesis method', but from the viewpoint of ease of synthesis, -CH2-, -0-, -COO-, -NHC0--NH--CH2 〇 - is better. Further, the carbon ring or heterocyclic ring which is a divalent carbocyclic ring or a divalent heterocyclic ring of any -CH2- which is substituted for R13 is specifically exemplified as follows, but is not limited thereto.

S -29- 201217352 [化 41]

Ο Ο 0~0 ΟΌ 0~^KD

CO CO 03⁄4 CnP V ^ ^ 9^0 0 0 v 〇>〇>〇>a;>a> c〇co 〇p οςο R14 from the viewpoint of photoreactivity, with vinyl, propenyl A methacryl group, an allyl group, a styryl group -n(ch2chch2) 2 or a structure represented by the following formula is preferred. [化42]

Further, the above formula (b) is preferably the following structure. -30- 201217352 [Chem. 43]

The amount of the photoreactive side chain present, when the covalent bond is formed by irradiation of ultraviolet rays, accelerates the response speed of the liquid crystal in a range of one step to accelerate the response speed of the liquid crystal, so as not to affect other characteristics as much as possible. The method for producing a liquid crystal alignment material in which the liquid crystal alignment is perpendicular is not particularly limited. For example, when a polylysine having a side chain to which a liquid crystal is mixed is produced, a polyamine is used by a diamine and a tetracarboxylic dianhydride. In the acid method, the liquid crystal alignment is made vertical

The method of polymerization is simple. Further, when the polymer which forms the crystal alignment film in the liquid crystal contains a photoreactive side chain, only the diamine of the reactive side chain or the tetracarboxylic acid having a photoreactive side chain is copolymerized as having a liquid crystal alignment vertical. a diamine of a side chain having a long-chain alkyl group or a long-chain alkyl group having a ring structure or a branch group, a hydrocarbon group such as a steroid group, or a group of hydrogen atoms of these groups acting as a fluorine atom as a side The diamine of the chain, for example, may have a reaction with -31 -, and the polymerization of the film is carried out in a vertical reaction, and the anhydride of the side chain is subjected to a total vertical hydration with photo-dianhydride. The structure or all of the diamine of the side chain represented by the above formula s 201217352 (a) is taken. More specifically, for example, a diamine having a hydrocarbon group having a hydrogen number of 8 to 30 substituted with fluorine or a diamine represented by the following formulas (2), (3), (4), and (5) However, it is not limited to this. [化44]

| m η (1, m, n, R7 to R11 in the formula (2) have the same definition as the above formula (a)) [Chem. 45]

(In the formulas (3) and (4), A! means -COO-, -OCO-, -CONH-, -NHCO-, _ch2-, -0-, -CO- or ·ΝΗ·, Αιι a bond or a phenyl group, a represents the same structure as the side chain perpendicular to the liquid crystal alignment shown in the above formula (a), and a represents the same side chain which is perpendicular to the liquid crystal alignment shown in the above formula (a) The structure takes out a divalent group of a structure of an element such as hydrogen) -32- 201217352 [Chem. 46] H2Nnt^cH2)a1-A17^CH2)a2-A16-A15'<[340)irAl4 ^ (Formula (5) In the above, Al4 is a group having a carbon number of 3 to 2 Å which may be substituted by a fluorine atom, A15 is a 1,4-cyclohexyl group or i, and a phenyl group 'Al6 is an oxygen atom or _C〇〇-* (but A bond with "*" is combined with A3), VIII is an oxygen atom or _COO-* (but a bond with "*" is combined with (CH2) a2). And '31 is an integer of 0 or 1. , a2 is an integer of 2 to 10 'a3 is an integer of 0 or 1) The bonding position of the two amine groups (·ΝΗ2) in the formula (2) is defined. Specifically, the bonding group of the side chain may be exemplified by 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, 3,5 position. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, it is preferable to have a position of 2, 4, a position of 2, 5, or a position of 3, 5. When the ease of synthesizing the diamine is added, the position of 2, 4 or the position of 3, 5 is preferred. The specific structure of the formula (2) is exemplified by the following formula [Α-1] to the diamine represented by the formula [A - 2 4 ], but is not limited thereto. [化47]

[A-" [A_2J [Α·3] CA-43 [A,6] (In the formula [cardiac]~[A-5], A is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkane base)

S -33- 201217352 [Chem. 48]

(In the formula [A-6] and the formula [A-7], A2 represents -〇-, -OCH2-, COOCH2- or -CH2OCO-, and A3 is an alkyl group having a carbon number of 1 to 22 and contains a fluorine atom or contains Fluoroalkoxy) [Chem. 49] -CH2〇- ' -

[A-8] [A-9] [A-10]

(In the formula [A-8]~[A-10], A4 represents -COO-, -OCO. .-NHCO- '-COOCH2- '-CH2OCO- '-CH2O- 'CH2-, A5 represents carbon number 1 ～22 alkyl, alkoxy, narrow or fluorine-containing alkoxy) [50] nh2 [A-12] (In the formula [A-ll] and the formula [A-12], A6 represents -COO -, CONH-, -NHCO-, -COOCH2- '-CH2OCO- ' - OCH2-, -CH2_, or -NH-, A7 is a group, cyano group, nitro group, azo group, methyl group, B Sulfhydryl, acetamidine, /CONH--OCH2- or - fluoroalkyl-oxime C 0 ·, -CH20-, -trifluoromethane: or hydroxy) -34· 201217352

Nh2 h2NX^-〇-€K>^ [A-13] 1,4-ring (in the formula [A-13] and the formula [A_14], a8 is an alkyl group having a carbon number of 3 to 12) The cis-trans isotropic is a trans isomer) [化52] nh2

(In the formula [A-15] and the formula [A-16], 八9 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) 53]

S-35-201217352 A specific example of the diamine represented by the formula (3) is exemplified by the following formula [A-25] to the formula [A-30], but is not limited thereto. [化54]

(In the formula [A-25]~[A-30], 'Ai2 represents -COO-'-OCO-, -CONH-, -NHCO-, -CH2-, -〇-, -CO- or -NH- A13 represents a hospital base having a carbon number of 1 to 22 or a hospital base containing fluorine.) Specific examples of the diamine represented by the formula (4) include the following formula [A-31] to formula [A-32] The diamine shown is 'but is not limited thereto. [化55]

Among them, W[A-1], [A-2], [A-3], [A-4], [A-5], from the viewpoint of the ability to align the liquid crystal in a vertical direction and the response speed of the liquid crystal. [A-25], [A-26], [A-27], [A-28], [A-29] '[A-30] diamine is preferred. The diamine may be used in one type or in a mixture of two or more types in accordance with characteristics such as liquid crystal alignment property, tilt angle, voltage holding property, and storage charge when used as a liquid crystal alignment film. The diamine having such a side chain in which the liquid crystal is aligned in a vertical direction is preferably used in an amount of from 5 to 50 mol%, preferably a diamine component, of the diamine component used for the synthesis of polyamic acid. 10 to 40 mol% is a diamine having a side chain in which the liquid crystal is aligned vertically, and particularly preferably 15 to 30 mol%. When the diamine having a side chain in which the liquid crystal is aligned vertically is used in an amount of 5 to 50 mol% of the diamine component used in the synthesis of polylysine, the response speed is improved or the liquid crystal alignment is immobilized. The point of view is particularly good. Examples of the diamine having a photoreactive side chain include a vinyl group, a propenyl group, a methacryl group, an allyl group, a styryl group, a cinnamyl group, a chalcony coumarin group, and a malayan hydrazine. Examples of the diamine which is a side chain of a photoreactive group such as an amine, an epoxy group, a vinyloxy group or a propyleneoxy group include a diamine having a side chain represented by the above formula (b). More specifically, for example, the diamine represented by the following general formula (6) can be mentioned, but it is not limited thereto. H2N a

(The definitions of R12, R13 and R14 in the formula (6) are the same as those in the above formula (b)) The bonding positions of the two amine groups (-NH2) in the formula (6) are not limited. Specifically, the bonding group of the side chain may be a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, and a position of 2, 6 '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. In addition to the ease of synthesizing the diamine, it is preferred to have a position of 2, 4 or a position of 3, 5. Specific examples of the diamine having a photoreactive side chain include the following -37-201217352 compound', but are not limited thereto. [化57]

(wherein, X represents a single bond or a bond group selected from -0, -COO-, -NHCO., _NH_, 'Y represents a single bond or an unsubstituted or substituted carbon number of 1 to 20 Alkyl group) A diamine having the above-mentioned photoreactive side chain, which corresponds to liquid crystal alignment property, tilt angle, voltage holding property, and storage charge when used as a liquid crystal alignment film: stomach and stomach, and liquid crystal when it is used as a liquid crystal display element , answer speed, etc., can be used in 1 type or in a mixture of 2 or more types. Further, the diamine having such a photoreactive side chain is preferably used in an amount of 10 to 70 mol%, preferably 20 to 60 mol%, based on the diamine component of the synthesis of polyamic acid. Good for 30 to 50 moles. Further, the polyamine can be used as a diamine other than the diamine having the side chain perpendicular to the alignment of the liquid crystal or the diamine having a photoreactive side chain, without impairing the effects of the present invention. Use the ingredients together. Specific examples thereof include p-phenylenediamine, 2,3,5,6·tetramethyl-indole-phenylenediamine, and 2,5-dimethyl-?-phenylene Amine, 111-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, -38-201217352 2, 5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4 ,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-di Methoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-di Aminobiphenyl, 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'-diamine Diphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'- Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3 , 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether , 4,4'·sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-double (4-Aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diamine Diphenylamine, 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-methyl (3,4'-Diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl (2,3'-diaminodiphenyl) Amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene , 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthyl, 1,6-diaminonaphthyl, 1, 7-diaminonaphthyl 1,8-Diaminonaphthyl,

S -39- 201217352 2,5-Diaminonaphthyl, 2,6-diaminonaphthyl, 2,7-diaminonaphthyl, 2,8-diaminonaphthyl, 1,2-double ( 4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-amine Phenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-amine Phenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl) Benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methyl)diphenylamine, 4,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,4' -[1,4-phenylene bis(methyl)diphenylamine, 3,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,3'-[1, 4-phenylene bis(methyl)diphenylamine, 3,3'-[1,3-phenylenebis(methyl)diphenylamine, 1,4-phenylene bis[(4- Aminophenyl)methanone], 1,4-phenylene bis[(3-aminophenyl) Methyl ketone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4- Phenyl bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoic acid) Ester), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)-p-phenylene Formate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene) Bis(4-aminobenzamide), hydrazine, Ν'-(1,3-phenylene)bis(4-aminobenzamide), N,N'- (1,4-phenylene) Bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), hydrazine, Ν'-bis(4-amine Phenyl phenyl) terephthalamide, -40- 201217352 Ν, Ν'-bis(3-aminophenyl)terephthalamide, hydrazine, Ν'-bis(4-aminophenyl) Isophthalamide, hydrazine, Ν'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis ( 4-amine Phenoxy)diphenyl milling, 2,2'-bis[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-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis(4-aminobenzene) Oxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, I,4-bis(3-aminophenoxyl) Butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminobenzene Oxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminobenzene Oxy) heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-amine Phenoxy)decane, 1,9-bis (3- Phenoxy group) decane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,1 1-(4-amino group Phenoxy)undecane, 1,1 1-(3-aminophenoxy)undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-( 3- An aromatic diamine such as an aminophenoxy)dodecane or an alicyclic diamine such as bis(4-aminocyclohexyl)methane bis(4-amino-3-methylcyclohexyl)methane; 3-Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8 -diaminooctane, 1,9-

S-41 - 201217352 An aliphatic diamine such as diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane. The above-mentioned other diamines can be used in the form of a liquid crystal alignment film, a tilt angle, a voltage holding property, and a charge storage, and can be used in one type or in a mixture of two or more types. The tetracarboxylic dianhydride in which the diamine component is reacted is not particularly limited. Specific examples thereof include pyromellitic acid, 2,3,6,7-naphthyltetracarboxylic acid, 1,2,5,6-naphthyltetracarboxylic acid, and 1,4,5,8-naphthyltetracarboxylic acid. , 2,3,6,7-decanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3' , 4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxybenzene Base, bis(3,4-dicarboxyphenyl)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)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2, 3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4, 9,10-decanetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxydi-phthalic acid, 1,2,3,4 - cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl Base-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3,4-di Carboxy-1-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthyl succinic acid, bicyclo[3 ,3,0]octane-2,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]decane--42- 201217352 2,4,7,9-tetracarboxylic acid, bicyclo[4 ,4,0]decane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane-2,4,8,l-tetracarboxylic acid, tricyclo[6.3.0 ·0<2,6>] Eleventh Institute_3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-di-side oxytetrahydrofuran- 3-yl)-1,2,3,4-tetrahydronaphthyl-1,2-dicarboxylic acid, bicyclo[2 2 2]oct-7-discriminated-2,3,5,6-tetramic acid, 5-(2,5-di-side oxytetrahydrofuran)_3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,〇,2,7]12 _ 4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid Acid, etc. Of course, the tetracarboxylic dianhydride also has one type or two or more types in combination with the liquid crystal alignment property, the voltage holding property, and the storage charge when used as a liquid crystal alignment film. When a polyamine acid is obtained by a reaction of a diamine component and a tetracarboxylic dianhydride, a well-known synthesis method can be used. It is generally a method of reacting a diamine component with a tetracarboxylic dianhydride in an organic solvent. The reaction of the diamine component with the tetracarboxylic dianhydride is relatively easy to carry out in an organic solvent, and it is advantageous in that no by-product is produced. The organic solvent 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, since the water in the organic solvent does not inhibit the polymerization reaction and becomes a polylysine which is formed by hydrolysis, it is preferred that the organic solvent is dried by dehydration. Examples of the organic solvent used for the reaction include hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, hydrazine, hydrazine-diethylformamide, and hydrazine-methylmethyl. Indoleamine, Ν-methyl-2-pyrrolidone, Ν-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazole

S -43- 201217352 Alkanone, 3-methoxy-N,N-dimethylpropane decylamine, N-methylcaprolactam, dimethyl submilling, tetramethylurea, pyridine, dimethyl Bismuth, hexamethyl sulfoxide, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl Amyl ketone, methyl isopropanone, methyl sarbuta, ethyl celecoxib, methyl sarbuta acetate, ethylene glycol dibutyl ether acetate, ethylene glycol diethyl ether acetate, butyl Kikabi alcohol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol Methyl ether 'propylene glycol monobutyl ether, propylene glycol-tert-butyl acid, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethyl Glycol dimethyl acid, 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 acetate, tripropylene glycol methyl ether, 3-methyl-3.methoxybutanol, diiso Propyl ether, ethyl isobutyl acid, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, V hexyl ether, two Oxane, η-hexane, η-pentane, η-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, acetic acid Ethyl ester, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methyl Ethyl oxypropionate ' 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, and the like. This -44- 201217352 Some organic solvents can be used alone or in combination. When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred. 'The tetracarboxylic dianhydride is directly or dispersed or dissolved in an organic solvent, and then added. In the method, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, a method of mutually adding a tetracarboxylic dianhydride and a diamine component, and the like may be mentioned, and any of these methods may be used. Can be. Further, when the tetracarboxylic dianhydride or the diamine component is formed of a plurality of compounds, the reaction may be carried out in a state of being mixed in advance, or the reaction may be carried out in a separate order, and the low molecular weight bodies of the respective reactions may be subjected to a mixing reaction. After that, it is a high molecular weight body. The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted may be any temperature, for example, -2 0 ° C to 150 ° C, preferably -5 ° C to 1 ° C. range. Further, the reaction can be carried out at any concentration. For example, the total amount of the diamine component and the tetracarboxylic dianhydride component of the reaction liquid is preferably from 1 to 50% by mass, preferably from 5 to 30% by mass. In the above polymerization reaction, the total molar ratio of the tetracarboxylic dianhydride component to the total number of moles of the diamine component is such that the molecular weight of the obtained polyglycolic acid can be any desired. As in the case of the general polycondensation reaction, the molecular weight of the polyproline which is formed closer to the molar ratio of 1.0' becomes larger. A preferred range is from 0.8 to 1.2. The method for synthesizing the polyaminic acid used in the present invention is not limited to the above-mentioned method 'in the same manner as the general method for synthesizing poly-proline, and the tetracarboxylic or tetracarboxylic acid corresponding to the above-mentioned tetracarboxylic dianhydride is used. A tetracarboxylic acid derivative such as a dihalide can be obtained by a known method even if it is reacted by a known method.

S -45- 201217352 Amino acid. The polyamidene which is ruthenium imidized with the above polyamic acid may be a ruthenium imidization of a solution of a hot hydrazine imine acid which is directly heated by a solution of polyglycine. Further, the imidization ratio of the quinone to the polyimine is not necessarily 100%. When polylysine is thermally imidated in a solution, the temperature is from 100 ° C to 400 ° C, preferably from 12 (TC to 250 ° C, while the water formed by the borrowing reaction is excluded from the system. Preferably, the ruthenium amide of the poly-proline is obtained by adding a basic catalyst and an acid anhydride to the poly-proline, and the mixture can be stirred at -20 to 250 ° C, preferably under stirring. The amount of the medium is 0.5 times of the valeric acid group, preferably 2 to 20 moles, and the amount of the acid anhydride is two times the valeric acid group, preferably 3 to 3 moles. As the alkaline catalyst. , can be, triethylamine, trimethylamine, tributylamine, trioctylamine, etc., among which is also preferred for the reaction to moderate alkalinity. As an anhydride acetic anhydride, trimellitic anhydride, pyromellitic dianhydride When acetic anhydride is used, the purification after the end of the reaction becomes easy, so that the imidization ratio of the imidization of the medium can be controlled by adjusting the amount of the catalyst and the reaction time. The ester is a reaction of the same diamine as the synthesis of the tetracarboxylic acid diester dichloride and the valine acid, or the same diamine of the tetracarboxylic acid diester polyamic acid is properly condensed. Or the base can be produced by reaction, or can be obtained by pre-synthesizing a polyamine polymer reaction by the above method to esterify a carboxylic acid in valeric acid. The method of the amine is at a temperature of the poly-proline From the imine solution, add 0 ~ 1 80 ° C ~ 30 moles 1 ~ 50 pyridine to 卩 陡 陡 , , , , 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In combination with the above, the acid is used, specifically -46-201217352, for example, the tetracarboxylic acid diester dichloride and the diamine can be used in the presence of an alkali and an organic solvent at -2 ° C to 150 ° C. Preferably, it is carried out at 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably for 1 hour to 4 hours after the reaction to synthesize the polyphthalate. The polyglycolate is at a high temperature. By heating, even if it is closed by a dehydration, a polyimine can be obtained. The reaction solution is recovered from a reaction solution of a polyamidene precursor such as polyglycolic acid or polyamidomate or polyimine. When a polyimine precursor such as polyglycolic acid or polyamidomate or polyimine is formed, the reaction solution is put into a weak solvent to make it As a weak solvent used for precipitation, methanol, acetone, hexane, ethylene glycol dibutyl ether, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water may be mentioned. Etc. The polymer which has been precipitated in a weak solvent is recovered by filtration, and then dried under normal pressure or under reduced pressure at normal temperature or under heating. Further, the polymer recovered by precipitation is redissolved in an organic solvent, and then reprecipitated and recovered. When the operation is repeated 2 to 10 times, the impurities in the polymer can be reduced. Examples of the weak solvent at this time include alcohols, ketones, hydrocarbons, and the like, and when three or more types of weak solvents selected from the above are used. The liquid crystal alignment agent of the present invention may have a polymerizable compound, a polymer, and a solvent, and the polymerizable compound is a methyl-γ-butyrolactone having the above-mentioned stretched methyl-γ-butyrolactone. a polymerizable compound having a terminal having a photopolymerization or photocrosslinking group, and the polymer is a polymer which forms a liquid crystal alignment film obtained by aligning a liquid crystal, and the compounding ratio is not particularly limited, and it has α- Methyl group The end of the γ-butyrolactone group and the content of the polymerizable compound having a terminal for photopolymerization or photointerference, for forming an alignment liquid

The 100 parts by mass of the polymer of the liquid crystal alignment film obtained by S-47 to 201217352 is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass. Further, the content of the polymer of the liquid crystal alignment film obtained by forming the alignment liquid crystal contained in the liquid crystal alignment agent is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, particularly preferably 3 ~10% by mass. Further, the liquid crystal alignment agent of the present invention may contain a polymer other than the polymer which forms the liquid crystal alignment film obtained by aligning the liquid crystal. 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 measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained by coating the liquid crystal alignment agent, the workability at the time of coating film formation, and the uniformity of the coating film. The weight average molecular weight is preferably 5,000 to 1,000,000, preferably 1 Å, 〇〇〇 150,000. <Solvent> The solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited, and if it is soluble or dispersible, it has a terminal having an α-methyl-γ-butyrolactone group and has photopolymerization or photocrossing. The polymerizable compound at the terminal of the group or the polymer of the liquid crystal alignment film obtained by aligning the liquid crystal may contain a component. For example, an organic solvent exemplified as the synthesis of the above polyamic acid can be mentioned. Among them, Ν-methyl-2-pyrrolidone, γ-butyrolactone, Ν-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy- Niobium, Ν-dimethylpropane decylamine is preferred from the viewpoint of solubility. Of course, more than two types of mixed solvents of -48 to 201217352 can be used. Further, it is preferred to use a solvent which improves the uniformity or smoothness of the coating film in a solvent having a high solubility in the component contained in 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 acid 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, n-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, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3- Propyl methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol ,

S -49- 201217352 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, preferably 20 to 60% by mass. The liquid crystal alignment agent may contain components other than the above. In this example, a compound which improves the film thickness uniformity or surface smoothness when a liquid crystal alignment agent is applied, a compound which improves the adhesion between the liquid crystal alignment film and the substrate, and the like can be used as the film thickness uniformity or surface smoothness. Examples of the compound include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. More specifically, Eftop EF301, EF303, EF352 (made by TOHKEM PRODUCTS C0RP), Megafac F171, FI73, R-30 (made by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (made by Sumitomo 3M Co., Ltd.), Asahiguard AG710, S ur f 1 ο n S - 3 8 2. SC101 'SC102 ' SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). 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, per 100 parts by mass of the total of the polymer of the liquid crystal alignment agent. Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include a compound containing a functional decane or a compound containing an epoxy group. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyl-50-201217352 triethoxydecane'2-aminopropyltrimethoxydecane, 2-aminopropyltriethyl Oxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane , 3-guanidinopropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3 -Aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxysulfonium Base-1,4,7-triazadecane, 10-triethoxyindolyl-1,4,7-triazadecane, 9-trimethoxyindolyl-3,6-diaza Mercaptoacetate, 9-triethoxyindolyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis ( Oxy-extension ethyl)-3-aminopropyl three Methoxydecane, N-bis(oxyethylidene)-3-aminopropyltriethoxydecane, ethylene glycol propylene oxide ether, polyethylene glycol propylene oxide ether, propylene glycol dioxy acrylate, three Propylene 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·dibromo neopentyl glycol Dipropylene oxide, 1,3,5,6-tetrapropenyl-2,4-hexanediol, N,N,N',N',-propionic tetramethyl-m-xylenediamine, 1 , 3-bis(N,N-dioxypropyleneaminomethyl)cyclohexane, N,N,N,,N,,-tetrapropene oxide, 4'-diaminodiphenylmethane, 3 - (N-allyl oxypropylene)aminopropyltrimethoxysilyl' 3-(N,N-dioxypropylene)aminopropyltrimethoxyanthracene. Also want to further increase the film strength of the liquid crystal alignment film. Add 2, 2'·double (4_

S-51 - 201217352 Phenolic compounds such as 3-,5-dihydroxymethylphenyl)propane and tetrakis(methoxymethyl)bisphenol. When these compounds are used, the epoxy group-containing compound is preferably used in an amount of 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the polymer contained in the liquid crystal alignment agent. . Further, in the liquid crystal alignment agent, the above-mentioned other components of the dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant or the electrical conductivity of the liquid crystal alignment film may be added to the extent that the effects of the present invention are not impaired. By applying the liquid crystal alignment agent to the substrate and baking it, a liquid crystal alignment film obtained by aligning liquid crystals such as a liquid crystal alignment film having a vertical alignment of the liquid crystal can be formed. Since the liquid crystal alignment agent of the present invention has a polymerizable compound having a terminal having an α-methyl-γ-butyrolactone group and a terminal having a photopolymerization or photocrosslinking group, it is not contained in the liquid crystal. When the polymerizable compound is fired at a high temperature, the response speed of the liquid crystal display element using the obtained liquid crystal alignment film can be made fast. Of course, when the liquid crystal contains a polymerizable compound or when it is fired at a low temperature (for example, 1 40 ° C or lower), the response speed of the liquid crystal display element can be made fast. For example, the liquid crystal alignment agent of the present invention is coated. After being deposited on the substrate, the cured film obtained 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 the like, or an ion beam or the like may be applied. Alternatively, the film may be irradiated with UV in a state in which a voltage is applied to the liquid crystal display element after liquid crystal charging by the alignment film for PSA. It is especially useful as an oriented film for PSA. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency. A glass plate, polycarbonate, poly(methyl)-52-201217352 acrylate, polyether oxime, poly Aromatic esters, polyurethanes, polybenzazoles, 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, in the case of the reflective liquid crystal display device, only a single-sided substrate can be used, and an opaque material such as a germanium wafer can also be used. In this case, an optical material such as aluminum or the like, cellulose diacetate or acetic acid butyric acid can be used as the electrode. A plastic substrate such as ester cellulose. The method of applying the liquid crystal alignment agent is particularly limited, and examples thereof include screen printing, offset printing, offset printing, roll coating, or dipping, roll coating, and slit coating. , spin coater, etc. From the standpoint of productivity, a transfer printing method widely used in the industry is also applicable to the present invention. Although the drying step after the application of the liquid crystal aligning agent is not necessary, the drying step is preferably carried out after the application to the firing time is not constant for each substrate or when it is not immediately baked after coating. This drying is a method of transferring the substrate or the like without removing the solvent to the extent that the shape of the coating film is deformed, and the drying means is not particularly limited. For example, a method of drying at a temperature of 40 ° C to 15 (TC, preferably 60 ° C to 100 ° C on a hot plate for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes) is mentioned. The coating film formed by coating the liquid crystal alignment agent can be fired to form a cured film. The firing temperature of the coating film formed by coating the liquid crystal aligning agent is not limited to, for example, 100 to 3 50 ° C. It is carried out at any temperature, preferably from 1 2 0 ° C to 300 ° C, more preferably from 150 ° C to 2 50 ° C. It can be used in the firing time.

S -53- 201217352 It is baked at any time from 5 minutes to 24 minutes. It is 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, by using a hot plate, a hot air circulating furnace, an infrared furnace or the like. The thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 10. L〇〇nm. On the other hand, in the liquid crystal display device of the present invention, the liquid crystal cell can be produced by a known method after the substrate is formed into a liquid crystal alignment film by the above 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 of a liquid crystal 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. A liquid crystal display element such as a vertical alignment method in which a liquid crystal layer is formed by bringing a liquid crystal layer into contact with a liquid crystal alignment film and a liquid crystal cell is irradiated with ultraviolet light 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 rays are applied to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, and the end having the α-extended methyl-γ-butyrolactone group is held. The polymerizable compound having a terminal for photopolymerization or photocrosslinking is polymerized, and a polymer or a polymerizable compound which forms a liquid crystal alignment film obtained by aligning the liquid crystal is reacted with a polymerizable compound, by which The cross-linking is performed to obtain a liquid crystal display element having excellent response speed. -54-201217352 The substrate using the liquid crystal display element 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 liquid crystal driven is formed on a substrate. As a specific example, the same substrate as described in the above liquid crystal alignment film can be mentioned. In the liquid crystal display device of the present invention, a liquid crystal alignment agent of the present invention is used as a liquid crystal alignment agent for forming a liquid crystal alignment film, and a liquid crystal alignment agent of the present invention having the following polymerizable compound is used. The compound is a polymerizable compound having a terminal having an α-methyl-γ-butyrolactone group and a terminal having a photopolymerization or photocrosslinking group; and a line of, for example, 1 to ΙΟμπι is formed on the one-sided substrate. The pattern of the slit electrode 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 to obtain a high transmittance. 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 a conventional vertical alignment method or the like, for example, a negative liquid crystal such as MLC-66〇8 or MLC_66〇9 manufactured by Moker Corporation can be used. . As a method of holding the liquid crystal layer between two substrates, a method can be mentioned

S -55- 201217352 Well-known method. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are spread on the liquid crystal alignment film of one substrate, and the other substrate is bonded to the inside of the surface formed by the liquid crystal alignment film, and the liquid crystal is injected under reduced pressure and then sealed. The method can be mentioned. In addition, a pair of substrates formed by the liquid crystal alignment film are prepared, and a spacer such as a bead is spread on the liquid crystal alignment film of one of the substrates, and then the liquid crystal is dropped, and then the other substrate is bonded to the inside of the liquid crystal alignment film. The method of sealing can also produce a liquid crystal cell. The thickness of the spacer at this time is preferably from 1 to 30 μm, more preferably from 2 to ΙΟμηη. The step of producing a liquid crystal cell by applying ultraviolet light to the liquid crystal alignment film and the liquid crystal layer while applying a voltage is, for example, a substrate. After the input voltage between the electrodes, an electric field is applied to the liquid crystal alignment film and the liquid crystal layer to maintain the ultraviolet light under the electric field. 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 members 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 applied to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, the polymer having the terminal having an α-methyl-γ-butyrolactone group and the terminal having a photopolymerization or photocrosslinking group is polymerized. The compound reacts to form a polymer, and by the polymer, the tilt direction of the liquid crystal molecules is memorized, and the response speed of the obtained liquid crystal display element can be accelerated. In the above, the liquid crystal display element produced by including the following polymerizable compound in the liquid crystal alignment agent for forming a liquid crystal alignment film in which the polymerizable compound is held has α-extended methyl-γ-butyrolactone The liquid crystal display element of the present invention may be produced by including the following polymerizable compound in a liquid crystal, wherein the polymerizable property is the same as the polymerizable compound having a terminal at the end of the photopolymerization or photocrosslinking. The compound is a polymerizable compound having a terminal having a fluorene-methyl-γ-butyrolactone group and a terminal having a group which undergoes photopolymerization or photocrosslinking. Further, the liquid crystal alignment agent is useful not only as a liquid crystal alignment agent for producing a liquid crystal display element such as a vertical alignment method such as a PS-type liquid crystal display or an SC-PV A-type liquid crystal display, but also as a rubbing treatment or a photo alignment treatment. The use of the liquid crystal alignment film produced. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples. However, the present invention is not limited thereto. The abbreviations used in the examples are as follows. (tetracarboxylic dianhydride) BODA : bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic acid Anhydride TCA: 2,3,5-tricarboxycyclopentyl acetic acid - oxime: 2,3 - dianhydride

S -57- 201217352 [化58] ο

TCA (diamine) m-PDA: m-phenylenediamine p-PDA : p-phenylenediamine PCH: 1,3-diamino-4-[4-(4-heptylcyclohexyl) Phenoxy]benzene DBA: 3, 5-diaminobenzoic acid 3 AMPDA : 3,5-diamino-N-(pyridin-3-ylmethyl)-benzamide 0.31: 2-(Methethyloxy)ethyl 3,5-diaminobenzoate 0-8-2: as shown in the following formula! ^1,1^1-dipropylbenzene-1,2,4-triamine DA-3: 3,5-diamino benzoic acid cholestyl ester as shown in the following formula -58- 201217352 [Chemical 59 ]

DA-1

(amine compound) 3-AMP: 3-aminomethylmethodamine (organic solvent) NMP: N-methyl-2-pyrrolidone BCS: ethylene glycol dibutyl ether <polymerizable compound> (polymerizable compound ( Synthesis of R Μ 1 )) Add 4,4'-bisphenol 6.7g (35.9mmol), 2-(4-bromobutyl)-1,3-dioxole to a 300ml eggplant-shaped flask with a cooling tube. Alkane 15.0 g (7 1.7 mm 〇l), potassium carbonate l9.8 g (143 mmol), and acetone 150 ml were used as a mixture at 6 Torr. (: The reaction was carried out while stirring for 48 hours. After the completion of the reaction, 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 chloroform (80 ml) was added and extracted. -59- 201217352 The extraction was carried out three times. After the organic layer was separated, anhydrous magnesium sulfate was added and dried, and filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. The solid was recrystallized (hexane/chloroform = 4/1 ( The volume ratio)) was purified to obtain 14.6 g of a white solid. The obtained white solid was measured by NMR. The obtained solid was dissolved in chloroform (CDC13), using a nuclear magnetic resonance apparatus (manufactured by Diol). The measurement was carried out at 300 MHz. From this result, it was confirmed that the white solid was the compound (RM1-A) represented by the following reaction formula. The yield was 92%. iH-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 ( t, 2H) , 6.92 ( m, 4H) , 7.44 (m, 4H) 〇 60] h〇~〇~〇-〇h +[> (CH2)4~Br AcGyme ^ (RMl-A) Next, in the shape of an eggplant with a cooling tube The above-obtained compound (RMl-A) 13_3g (30mmol), 2-(bromomethyl)acrylic acid 11.6g (70mmol), 10% hydrochloric acid (aq) 50ml, tetrahydrofuran (THF) 160ml, Tin (II) chloride I3.2g (70mmol) was mixed as a mixture at 70 ° C for 20 hours. After the reaction was completed, the reaction solution was filtered under reduced pressure and mixed with pure water 2 0 〇m 1 . 100 ml of dichloroform was added and extracted. The extraction was carried out three times. -60-201217352 Anhydrous magnesium sulfate was added to the organic layer which was separated and dried, and the solvent was filtered off under reduced pressure to give a white solid. After recrystallization (hexane/chloroform = 2/1), 9.4 g of a white solid was obtained. The obtained white solid was measured by NMR in the same manner as above, and the following reaction formula was confirmed for the purpose of the white solid. The polymerizable compound (RM1) is shown in a yield of 64%. ^-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 ) [Chem. 61] =c: (RMl-A)

SnClj/lOyoHC 丨(aq)] THF/H20

(RM1) O-iCH^·

(Synthesis of Polymerizable Compound (RM2)) To a 300 ml eggplant-shaped flask equipped with a cooling tube, 5.0 g (23.8 mmol) of 2,4'-biphenyldicarboxyaldehyde and 2-(bromomethyl)acrylic acid 7 were added. 9 g (47.6 mmol), 10% hydrochloric acid (&9) 33〇11, tetrahydrofuran (butyl 1^) 100 ml, tin chloride (II) 9.5 g (50 mmol) as a mixture, and stirred at 70 ° C for 20 hours. Its reaction. After the completion of the reaction, the reaction mixture was poured into 300 ml of pure water to give a white solid. The obtained solid was separated and purified by recrystallization (hexane/chloroform = 2/1) to afford white solid 3.5 g.

S -61 - 201217352. The solid was measured by NMR, and the polymerizable compound (RM2) represented by the following reaction formula was confirmed for the white solid. The yield was 72%. *H-NMR (CDCls) δ : 2.99 ( m, 2H) , 3.42 ( m, 2H ) , 5.60 ( m, 2H) , 5.74 ( m, 2H) , 6.36 ( m, 2H) , 7.42 ( m, 4H ) , 7.60 ( m, 4H ). [化 62]

(Synthesis of Polymerizable Compound (RM3)) In a 500 ml eggplant-shaped flask equipped with a cooling tube, 4, 4, -11.2 g (60 mmol), 2-(2-bromoethyl)-1,3-di 25.0 g (138 mmol) of pentane, 35.9 g of cesium carbonate (260 mmol), and 200 ml of acetone were mixed as a mixture, and the mixture was stirred 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 100 ml of chloroform was added thereto and extracted. The extraction was carried out 3 times. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered, and then evaporated. This solid was dissolved in chloroform and precipitated with hexane (hexane/chloroform = 2/1) to afford 17.6 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 (RM3-A) represented by the following reaction formula. The yield was 76%. ^-NMR (CDCI3) δ : 2.19 ( m, 4H) , 3.89 ( m, 4H ) -62- 201217352 , 4.01 (m, 4H), 4.16 (m, 4H), 5.11 (m, 2H), 6.95 (m , 4H ), 7.45 ( m, 4H ). [化63] _0

_(CH2)2—Br + HO k2c〇3 Acetone C )-(ch2)2-o 〇- (ch2)2 “〇, (RM3-A) Next, add to the 500ml eggplant-shaped flask with a cooling tube 10.0 g (26 mmol) of the compound (RM3-A) obtained above, 10.0 g (60.6 mmol) of 2-(bromomethyl)acrylic acid, 32 ml of 10% HCl (aq), 140 ml of tetrahydrofuran (THF), tin chloride (II) 11.4 g (60.6 mmol) was stirred as a mixture 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, and then 100 ml of chloroform was added and extracted. 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. The solid was dissolved in chloroform and purified (hexane/chloroform = 2/1) using hexane to afford 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 the polymerizable compound (RM3) represented by the following reaction formula. The yield was 42%. ^-NMRCCDCh) 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)

S -63- 201217352 [Chem. 64]

(ch2>2-

+ (Polymerizable compound (RM4))

SnCb l〇%Ha(aq>.

TI1F

(CH2)2-〇0—(CH2>2 (RM3) A polymerizable compound represented by the following formula is known as a polymerizable compound (RM4).

(Synthesis of polymerizable compound (RM5)) 4-hydroxybenzoic acid methyl 7.61 g (50.0 mmol), 6-bromo-1.hexanol 9_lg (50,0 mmol) was added to a 200 ml eggplant-shaped flask equipped with a cooling tube. Further, 13.8 g (100 mmol) of potassium carbonate and 70 ml of acetone were used as a mixture, and the mixture was reacted while stirring at 64 ° C for 24 hours. After the completion of the reaction, the reaction mixture was filtered under reduced pressure and the solvent was evaporated under reduced pressure to give a yellow wet solid. The solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane/ethyl acetate = 1/1 (v/v)). The solvent was distilled off from the obtained solution to give 11.3 g of a white solid. The NMR measurement results of this solid are shown below. From the results, it was confirmed that the white solid was a compound represented by the following reaction formula (ΚΜ5·Α). -64 - 201217352 The yield is 90%. 'H-NMR (CDCh) δ : 1.3-1.7 (m, 8Η), 3.67 (m, 2Η), 3.88 (s, 3Η), 4.03 (t, 2Η), 6.91 (d, 2Η), 7.99( d, 2Η). HO—(CH2)6—Br c〇〇ch3 HO—(v /V-COOCH3 -► HO—(CH2)6- «2C〇3/Acetone (RMS-A) Next, attached to the cooling tube Into a three-necked flask, 2.2 g of chlorochromic acid pyridinium salt (PCC) (1 〇.〇mmol) and 15.0 ml of CH2C12 were placed, and the compound (RM1-A) obtained by dissolving the above was added dropwise 2.5 g ( lO.Ommol) a solution of CH2Cl2150-1ml was stirred at room temperature for additional 6 hours. Thereafter, 90 ml of diethyl ether was added to the solution of the oil adhering to the wall of the flask, and the mixture was filtered under reduced pressure. The solvent was distilled off under reduced pressure to give a dark green solid. The solid was purified by column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane/ethyl acetate Purification was carried out, and the solvent of the obtained solution was distilled off to obtain 1.3 g of a colorless solid. The result of measurement of this solid by NMR was as follows. From this result, it was confirmed that the colorless solid was the lower The compound of the formula (RM5-B) is obtained in a yield of 50%. W-NMR (CDCI3) δ: 1.3-1.8 (m, 6H), 2.49 (t, 2H), 3.88 (s, 3H), 3.99 (t,2H),6 .87 ( d,2H), 7.99 ( d, 2H ) , 9.78 ( s, 1 H ). -65- 1 201217352 [Chem. 67]

PCC /=\ ch2ci2 /=\ HO—(CH2)6—0-^ λ—COOCH3--► OHC—(CH2)5—o—^ COOCH3 (RM5-A) {RM5-B} Secondly with cooling The 50 ml eggplant-shaped flask was charged with the above-obtained compound (RM5-B) 1.25 g (5.0 mmol), 2·(bromomethyl)acrylic acid 0.83 g (5.0 mmol), Amberlyst (registered trademark) 15 (Rohm and Haas) Company product) 0.8 g, THF 8.0 ml, tin (II) sulfide 0.95 g (5.0 mmol), and 2.0 ml of pure water were mixed as a mixture, and the mixture was stirred at 70 ° C for 5 hours to cause a reaction. After the completion of the reaction, the reaction solution was filtered under reduced pressure, and then 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 evaporated under reduced pressure to give a colorless solid of 1.5 g. The NMR measurement results of the solid are shown below. From the results, it was confirmed that the colorless solid was a compound (RM5-C) represented by the following reaction formula. The yield was 94%. *H-NMR ( DMSO-d6) δ : 1.3-1.8 ( m, 8H) , 2.62 ( m, 1H), 3.04 (s, 1H), 3.81 (s, 3H), 4.05 (t, 2H), 4.54 ( m, 1H), 5.70 (s, 1H), 6.01 (s, 1H), 7.03 (d, 2H), 7.89 (d5 2H). [化68] OHC-(CH2)5-ο Or COOCH3

, COOH (RM5-B)

SnC^/Amberlyst 15 thf/h2o

(CH2)5—0 "O' cooch3 (RM5-C) Add 35 ml of ethanol to the 100 ml eggplant-shaped flask with a cooling tube, and obtain the compound (RM5-C) 1.5 g (4.7 mmol) from -66-201217352 And 1 〇% aqueous hydrogen hydroxide solution 5 m 1 as a mixture, and reacted at 85 ° C for 3 hours while stirring. After the completion of the reaction, 300 ml of water and a reaction liquid were added to a 500 ml beaker, and the mixture was stirred at room temperature for 30 minutes, and then a 10% aqueous HCl solution 51111 was added thereto, followed by filtration to obtain a white solid 1.38. Next, a white solid l.lg, Amberlyst (registered trademark) 15 (Rohm and Haas Company trade name), 〇g, and THF 20.0 ml were added as a mixture in a 50 ml eggplant-shaped flask equipped with a cooling tube, and subjected to 7 CTC. Stir for 5 hours and allow to react. After the completion of the reaction, the reaction mixture was filtered under reduced pressure, and the solvent was evaporated from the solvent to give a yellow solid. The yellow solid was purified by recrystallization (hexane/ethyl acetate = 1/1 (v/v)) to give a white solid. The NMR measurement results of this solid are shown below. From the results, it was confirmed that the white solid was a compound (RM5-D) represented by the following reaction formula. The yield was 71%. 'H-NMR ( DMSO-d6) δ : 1.2-1.8 (m, 8H), 2.60 ( 1H), 3.09 (m, 1H), 4.04 (m, 2H), 4.55 (m, 1H), 5_69 (s, 1H), 6.02 (s, 1H), 6.99 (d, 2H), 7.88 (d, 2H), 12.5 (s, broad, 1 H). [化69]

工^~(ch2)5—〇-^^-cooch3 —·Ν9〇Η(3Ι,)/Ε{〇ί T\(CH2)5-O-^^-COOH w 2) Amberlyst 15 (RM5-C THF (RM5-D) The above-obtained compound (RM5-D) 21.1 g (69_3 mmol), 1,4-cyclohexanedimethanol 5.0 g (34.7 mmol), N,N-dimethyl-4-amino group Pyridine (DMAP) 0.35 g and a small amount of 2,6-di-t-butyl-p-cresol (

S-67-201217352 BHT) was suspended in dichloromethane i〇〇mi with stirring at room temperature, and added to the cyclohexane carbodiimide (DCC) 15_5 g (75.0 mmol) dissolved in 50 ml of dichloromethane. The mixture 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 60 ml of 0.5 N-HC1 and saturated aqueous sodium hydrogencarbonate solution and saturated brine twice, dried over magnesium sulfate, and evaporated. The solvent was then subjected to recrystallization operation in ethanol to obtain a polymerizable compound (RM5) 20. lg represented by the following reaction formula. The results of measurement by NMR are shown below. Also, the yield was 81%. ^-NMRCCDCIS) δ: 1.15 (m, 4Η), 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70]

(Synthesis of Polymerizable Compound (RM6)) 6.1 g (20.0 mmol) of compound (RM5-D) obtained by the above method, and 4-[(6-propenyloxy)hexyloxy]phenol (SYNTHON Chemicals Co., Ltd.) 5.3 g (20.0mmol), N,N-dimethyl-4-aminopyridine (DMAP) O.lg, and a small amount of BHT were stirred at room temperature, suspended -68- 201217352 floated in 100ml of dichloromethane, added here A solution of 5.1 g (25_0 mmol) of dicyclohexylcarbodiimide (DCC) was dissolved 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 aqueous sodium bicarbonate (100 ml) and saturated brine (150 ml), dried over magnesium sulfate, and then solvent was evaporated under reduced pressure. Distilled to give a yellow solid. The solid was purified by column chromatography on silica gel column (column: oxime 60 0.063-0.20 0 mol solvent: hexane/ethyl acetate = 1/1). The solvent of the solution obtained therefrom was distilled off to obtain 4.3 g of a polymerizable compound (RM6) represented by the following reaction formula. The results of measurement by NMR are shown below. Also, the yield was 3 9%.

1H NMR (CDC13) δ: 1.53 (m, 10H), 1-72 (m, 2H), 1.79 (m, 4H), 2.58 (m, 1H), 3.07 (m, 1H), 3.96 (t, 2H) , 4.05 (t, 2H), 4.18 (t, 2H), 4.54 (m, 1H) ' 5.64 (d, 1H), 5.81 (d, 1H), 6.14 (m, 1H), 6.24 (d' 1H), 6.40 ( d,1H),6·97 ( m,4H),7.09 ( d,2H) ' 8.14 ( d, 2H ). [化71]

(ch2>5°°~^r^~C00H + HO-^ .^-O—(CH2)6 one (RM5-D) DCC/DMAP CH2C!2

(CH2)5-〇

〇(CH2)6-〇· (Synthesis of polymerizable compound (RM7)) 1 ( 7 3 ° ^ The compound represented by the following reaction formula (RM7-A ) L /' s -69- 201217352 ), compound ( RM7-B) 2.5 g (7.3 mmol), DMAP 0.015 g and a small amount of BHT were stirred at room temperature under stirring, 30 ml of dichloromethane, and then added to a solution of 5 ml of DCC 1.8 g (9.0 mmol) dissolved in dichloromethane. After 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 evaporated. The solvent was then subjected to recrystallization operation in ethanol to obtain 1.3 g of a polymerizable compound (RM7) represented by the following reaction formula. The results of measurement by NMR are shown below. Also, the yield was 30%. 'H NMR ( CDC13 ) ) : δ 1.40-1.90 ( m, 14H), 2.64 (m, lH) , 3.07 ( m, 1H), 4. 〇〇 (t, 2H) , 4.05 ( t, 2H), 4.18 (t, 2H), 4.54 (m, 1H), 5.83 (d, 1H), 6.14 (m, 1H), 6.25 (d, 1H), 6.37 (d, 1H), 6.97 (d, 2H), 7.26 ( d, 2H ) , 7.50 ( d, 2H ), 7.57 ( d, 2H) , 8.17 ( d, 2H ) [72]

(CH2), -0 (RM7-A)

OH 0 〇一(CH2>6_(RM7-B) O—(CH2)6-〇' DCC/DMAP -► CH2C12 (RM7) (synthesis of polymerizable compound (RM8)) in eggplant-shaped flask with cooling tube Add 4-hydroxybenzole to 6.1g (50mmol), 6-bromo-1-hexanol 9_lg (50mmol), cesium carbonate-70-201217352 13.8g (100mmol), and acetone 100ml as a mixture at 64 ° C - After reacting for 24 hours, the reaction was carried out. After the completion of the reaction, the solvent was evaporated under reduced pressure to give a yellow wet solid. Then, 70 ml of the solid and water were mixed, and 50 ml of diethyl ether was added and extracted. The extraction was carried out three times. The organic layer was separated and dried over anhydrous magnesium sulfate, and filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. The purification was carried out by column chromatography (tank 60: 0.063 - 0.200 mm eluted by Merck: hexane / ethyl acetate = 2 / 1). The solvent was evaporated from the obtained solvent to give 7.4 g of a white solid. The results of measurement by NMR are shown below. From the results, it was confirmed that the white solid was a compound represented by the following reaction formula (RM8-A). 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) [化73]

HO

CHO

Br-(CH2)6-OH K2C03/Acetone 〇Hc-〇-

〇-(CH2)6-〇H (RM8-A) 2.2 g of a compound (RM8-A), 1.7 ml of triethylamine, 0.2 mg of BHT and THF 10 ml were mixed in a 50 ml three-necked flask and dissolved. Under stirring of the solution, 0.8 ml of acryloyl 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 dripping, directly in this state for 3 〇 minutes

After stirring at S-71 201217352, 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, and the filtrate was concentrated under reduced pressure to a volume of 3/4. This solution was washed with a saturated sodium carbonate solution (100 ml) of aq. This solid was dissolved in 3 ml of ethyl acetate, and purified by column chromatography (column: solvate 60 0.063 - 0.200 mm Merck solvent: hexane / ethyl acetate = 2 / 1). Og。 The solvent was evaporated 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 compound (RM8-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), 4.18 (t, 2H), 5.81 (d, 1H), 6.14 (m,1H), 6.37 (d, 1H), 6.99 (m, 2H), 7.82 (m, 2H), 9.88 ( s, 1 H ). [化74] OHC Ό-. . (ch2)6-〇h

Acryloyl Chloride· Et3N, THF 0HC^〇- (RM8-A) _(CH2)6· (RM8-B) Next, in the eggplant-shaped flask with 5 〇ml attached to the cooling tube, 'add the middle of the same as above. Compound (RM8-B) 2.0g (7mmol), 2-(bromomethyl)acrylic acid 1_2g (7.0mmol), Amberlyst (registered trademark) 15 (Rohm and Haas trade name) 1.2g, THF 8.0ml, tin chloride (II) 1.4 g (7 mmol) and 2.0 ml of pure water as a mixture were stirred and reacted at a temperature of -72 to 201217352 °C at 70 °C for 24 hours. 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. The solid was dissolved in 3 ml of ethyl acetate, and purified by a silica gel column chromatography (column gel: 60 0.063-0.200 mm Merck's solution: hexane/ethyl acetate = 2/1). Since the solvent thus obtained was evaporated to give a white solid. The solid was measured by NMR, and the white was confirmed.

OHC

THF/H20

The color solid is a polymerizable compound (RM8) represented by the following reaction formula. The yield was 40%. 1H NMR (CDC13) δ: 1.48 (m, 4Η), 1.75 (m, 4H), 2.94 (m, 1Η), 3.3 9 (m, 1H), 3.95 (t, 2H), 4.17 (t, 2H), 5 • 45 ( t, 1Η ), 5.68 ( m, 1H ), 5.83 ( m, 1H ), 6.13 ( m , 1Η ) , 6.30 ( m, 1H ) , 6.40 ( d, 1H) , 6.88 ( d, 2H) , 7.26 ( m, 2Η ) 〇 [Chem. 75] (Synthesis of a polymerizable compound (RM9)) 201217352 Compound (RM5-D) obtained by the same method as above, 22.0 g (72.4 mmol), 1,4-phenyl Dimethylmethanol 5.0g (36.2mmol), N,N-dimethyl-4-aminopyridine (DMAP) 0.35g and a small amount of BHT were stirred at room temperature and suspended in 100ml of dichloromethane. Methyl chloride 50 ml of one of cyclohexyl carbon-y-fe (DCC) i7.0 g (80.0 mmol) 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 60 ml of 0.5 N-HC1 and saturated aqueous sodium hydrogencarbonate solution and saturated brine twice, dried over magnesium sulfate and then evaporated. After the solvent was recrystallized from ethanol, 16.6 g of a polymerizable compound (RM9) 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, 2H), 3.08 ( m, 2H), 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76]

(CH2)-〇H

H〇-fCH2) (CH2)s-O (RM5-D) COOH DCC/DMAP CH2CI2

(Synthesis of Polymerizable Compound (RM 1 0 )) The compound (RM5-D) obtained in the same manner as above was 6.1 g (20. Ommol), and 4,4'-biphenyldimethanol 2.1 g (10.0 mmol). , N, N- -74- 201217352 Dimethyl-4-aminopyridine (DMAP) 0.15g and a small amount of BHT were stirred at room temperature under stirring, 50 ml of dichloromethane, dissolved in dichloromethane 25 ml Dicyclohexylcarbodiimide (DCC) 5.3 g (25.0 mmol) 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 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 6.4 g of a polymerizable compound (RM10) 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). -(CH2)-OH +

(CH2)5—. 〇· (RM5-D) DCC/DMAP COOH CH2Cl2 > HO-(CH2)

-(CH2)-0

(RM10) (Synthesis of Polymerizable Compound (RM 1 1 )) The compound (RM5-D) obtained in the same manner as above was 6.1 g (20.0 mmol), and 4,4'-dihydroxybenzophenone 2.1 g (10.0) Methyl), N,N-dimethyl-4-aminopyridine (DMAP) O.lg, and a small amount of BHT were stirred at room temperature under stirring, 80 ml of dichloromethane, dissolved in dicyclohexyl--75 - ^ 201217352 carbodiimide (DCC) 5.2g (24.0mmol) solution and stirred for one night. The precipitated DCC urea was separated by filtration, the filtrate was 0.5N-HC1 50ml, saturated sodium bicarbonate 50ml The mixture was washed twice with a saturated aqueous solution of sodium chloride, and dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give a yellow solid. The solid was purified by recrystallization from ethanol to afford 6.2 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 polymerizable compound (RM11) represented by the following reaction formula. Yield: 79°/p 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 ) , 8.1 8 ( d, 4H ).

(Synthesis of Polymerizable Compound (RM12)) To a 500 ml eggplant-shaped flask equipped with a cooling tube, 12.2 g (100 mmol) of 4-hydroxybenzaldehyde, 12.2 g (50 mmol) of 1,6-dibromohexane, and potassium carbonate were added. 16.0 g (1) and 150 ml of acetone were used as a mixture, and the mixture was reacted while stirring at a temperature of 64 ° C for 48 hours. After the reaction solution was filtered, the solvent was evaporated under reduced pressure to give 5.4 g of pale brown wet solid. The results of measurement of the solid by NMR are shown below. From the result -76-201217352, it was confirmed that the solid was a compound (RM12_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) . [化79] h〇hO~

Br-(CH2)6-Br cho -► one K2C〇3/Acetone 0—(CH2)6—O points H. • (ch2)6-o· (RM12-A) Next, add the same compound (RM12-A) 3.3g (10.Ommol), 2·() to the same eggplant-shaped flask with a cooling tube. Bromomethyl)propionic acid 3.3 g (20.0 mmol), Amberlyst (registered trademark) 15 (Rohm and Haas trade name) 3.0 g, THF 32.0 ml, tin oxide (II) 3.8 g (20.0 mmol), pure water 8 As a mixture, Oml was stirred at a temperature of 70 ° 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. 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. The solid was dissolved in ethyl acetate (1 ml), and purified by a column chromatography (column: yttrium 60 0.063 - 0.200 mm Merck solvent: hexane / ethyl acetate = 1 / 1). The solvent thus obtained was evaporated to give a white solid (2.6 g). 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 -77-201217352 compound (RM 1 2 ) represented by the following reaction formula. The yield was 5 5 %. lH-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). [化80] -Ο O—(CH2}6—ο -〇~ch〇 (RM12-A) =c

tOOH

Sn〇2 / Amberlyst 15 thf/h2o (RM12) (Synthesis of polymerizable compound (RM13)) 7.5 g (50.0 mmol) of p-formaldehyde benzoic acid and 2-(bromine) were added to a 300 ml eggplant-shaped flask with a cooling tube. Methyl)propionic acid 9.1 g (55.0 mmol), THF 80.0 ml, tin chloride (II) l〇.5 g (110.0 mmol), and aqueous hydrochloric acid (1%) 35.0 ml as a mixture 'at 70 ° C Stir for 24 hours and allow to react. After the completion of the reaction, it was mixed with 200 ml of pure water, and 100 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 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 (RM13-A) represented by the following reaction formula. The yield was 76%. 'H-NMR ( DMSO-d6) δ : 2.85 ( m, 1H) , 3.50 ( m, 1H) , 5.75 (m, 1H) , 5.80 (s, 1H) , 6.18 (s, 1H) , 7.45 (d, 2H), 7.98 (d, 2H), 13.08 (s, 1H). -78- 201217352 [化81]

OHC Ο COOH +

COOH

SnCJz/THF · HCl (aq)

COOH (RM13-A) The above-obtained compound (RM13-A) 2.4g (1 1 ·0ηηηο1 ), 1,6-hexanediol 0.6g (5.0mmol), N,N-dimethyl-4-amine Base [I-precipitate (DMAP) 0.05g and a small amount of BHT were stirred at room temperature, and suspended in 10 ml of dichloromethane, and dissolved in dichloromethane (5 ml of dicyclohexylcarbodiimide (DCC) 2.5). g (12.0 mmol) 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, the polymerizable compound (RM 1 3 ) represented by the following reaction formula was obtained in an amount of 1.3 g. The results of measurement by NMR are shown below. Also, the yield was 50%. ^-NMRCCDCn) 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 ). [化82]

S-79-201217352 (Synthesis of polymerizable compound (RMl4)) PCC 6.2g (28.7mmol) and CH2C12 1 00. 〇ml were added to a 300 ml three-necked flask equipped with a cooling tube and mixed with stirring. A solution of 8.0 g (28.7 mmol) of the compound (RM14-A) shown in the following reaction formula was dissolved in CH2C12 (30.0 ml), and the mixture was 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. 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 a 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 (RM14-B) represented by the following reaction formula. The yield is 7 2% 〇1H NMR (CDC13) δ: 1.50 (ms2H), 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 ). [化83]

-80-201217352 Next, the above-obtained compound (RM14-B) 5.7 g (20.6 mmol) and 2-(bromomethyl)acrylic acid 3.4 g (20.6 mmol), 10 were added to a 100 ml eggplant-shaped flask equipped with a cooling tube. 16 ml of a hydrochloric acid aqueous solution, THF 50 ml', and tin chloride (II) 3.9 g (20.6 mmol) were used as a mixture. The temperature 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 mixed with 1 ml of pure water, and then diethyl ether (15 ml) 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 (R Μ 1 4 ) represented by the following reaction formula. The yield was 65 %. 1Η 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, 1H) , 5.63 (s, 1H), 6.25 (s, 1H), 6.33 (d, 1H), 6.90 (d, 2H), 7.45 (d, 2H), 7.65 (d, 1H) » [84]

(JRM14-B)

^ SnClz/10°/〇HCI(aq) 0_CH3 THF/H2〇

(Synthesis of polymerizable compound (RM15))

S -81 - 201217352 Add 4-bromobutyl-l,3-diacetopentane 5.0g (24.0mmol) and 2-(bromomethyl)acrylic acid 4.5g (27.0) to a 200ml eggplant-shaped flask with a cooling tube. Methyl), 10% aqueous hydrochloric acid 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 cause a reaction. After the completion of the reaction, the reaction solution was filtered under reduced pressure, and then mixed with 100 ml of purified water, and then 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 to dryness, and the solvent was distilled off from the filtered solution to obtain a colorless liquid (5.2 g). 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 (RM15-A) represented by the following reaction formula. The yield was 93%. 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,1H) , 5.65 ( s, 1H ), 6.25 ( s, 1H ). [化85]

The above-obtained compound (RM15-A) 4.7 g (20.0 mmol), 4-methoxycinnamic acid 3.6 g (20. Ommol), and potassium carbonate 5.1 g were added to a l〇〇ml eggplant-shaped flask equipped with a cooling tube. 50 ml of (40.0 mmol) and N,N-dimethylformamide (DMF) were used 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 2 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 of -82-201217352 after extraction to dry, 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 column chromatography (column: silica gel 60 0.063-0.200 mm Merck solvent: hexane / ethyl acetate = 1 / 1). The solvent thus obtained was distilled off to give 2.8 g of a white solid. The NMR measurement results of this solid are shown below. From the results, it was confirmed that the solid was a polymerizable compound (foot 1415) 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, 1H), 3.05 (m, 1H), 3.85 (s, 3H), 4.20 (t, 2H), 4.55 (m, 1H), 5.65 (s, 1H), 6.23 (s, 1H), 6.50 (d, 1H), 6.90 (d, 2H), 7.45 (d, 2H), 7.66 (d, 1H) ]

(Synthesis of polymerizable compound (RM 1 6 )) 4-bromobutyl-1,3·dioxazone 9.4 g (45.0 mmol), trans-4 - was added to a 200 ml preshaped flask equipped with a cooling tube. Phenyl cinnamic acid 10.Og (45.0 mmol), potassium carbonate 12.0 g (90. mmol), and DMF 100 ml were mixed as a mixture at 110 ° C for 48 hours while allowing to react. After the completion of the reaction, it was mixed with pure water of 100 m 1 to obtain a solid. The solid was subtracted from -83 to 201217352, and 50 ml of ethanol was added as a mixture and filtered. The solvent was filtered off under reduced pressure to give 6.2 g. The NMR measurement results of this solid are shown below. From the results, it was confirmed that the solid was a compound (11)^16-eight) 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, 1H). [化87]

Next, the above-obtained compound (RM16-A) 6.2 g (18.0 mmol), 2-(bromomethyl)acrylic acid 3.3 g (20.0 mmol), 10% hydrochloric acid were added to a 10 0 ml eggplant-shaped flask equipped with a cooling tube. 16 ml of an aqueous solution, 2 ml of THF3, and 3.8 g (20 0 0 ο 1 ) of tin chloride (11) were mixed 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 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 extraction to dryness, and the solvent was distilled off from the solution after filtration under reduced pressure to carry out recrystallization (hexane/ethyl acetate, 2/1) to obtain 3.6 g of a solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the solid was a poly-84-.201217352 compound (RM 1 6 ) represented by the following reaction formula. The yield was 53%. 1H NMR (CDC13) δ: 1.68 (m,6H), 2.63 (m,1H), 3.07 (m,1H),4·24 (t,2H), 4.55 (m,1H), 5.64 (s, 1H) , 6.25 (s, 1H), 6.50 (d, 1H), 7.36 (m, 1H), 7.46 (m, 2H), 7.65 (m, 6H), 7.75 (d, 1H). [化88]

(Synthesis of Polymerizable Compound (RM17)) The compound obtained by the above method (RM5-D) 7.6 g (25.0 ramol), ethyl 4-hydroxycinnamate 4.8 g (25.0 mmol), N,N-dimethyl 4-aminopyridine (DMAP) O.lg, and a small amount of BHT were suspended in 100 ml of dichloromethane under stirring at room temperature, and dissolved in dicyclohexylcarbodiimide (DCC) 6.7 g (32 mmol) was added thereto. The solution 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 hydrogencarbonate 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 lg was obtained by recrystallization from 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 (RM 1 7 ) represented by the following reaction formula. The yield was 59%.

S -85- 201217352 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 C m, 1H) , 5.64 ( s, 1H) , 6.22 ( s, 1H) , 6.40 (d, 1H) , 6.97 (d, 2H) s 7.22 (d, 2H) , 7.60 ( d, 2H), 7.70 (d, 1H), 8.15 (d, 2H). [化89]

(Synthesis of Polymerizable Compound (RM18)) The compound obtained by the above method (RM5-D) 7.3 g (24.0 mmol), methyl 4-hydroxy-3-methoxycinnamate 5.0 g (24.0 mmol), N , N-dimethyl-4-aminopyridine (DMAP) O.lg, and a small amount of BHT were suspended in 10 ml of dichloromethane under stirring at room temperature, and dissolved dicyclohexylcarbodiimide (DCC) was added thereto. A solution of 6.4 g (31 • Ommol) was stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 0.5 N-HC1 1 〇〇 ml, saturated sodium hydrogen carbonate aqueous solution 1 〇〇mi, and saturated brine 150 ml, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to give a yellow solid. This solid was purified by recrystallization (ethanol) to obtain 6.1 g of a polymerizable compound (RM 18) represented by the following reaction formula. The results of measurement by NMR are shown below. Again, the yield was 51%. -86- 201217352 1H NMR(CDC13) δ: 1.40-1.90 (m,8H), 2.58( m, 1H) , 3.08 ( m, 1H) , 3.80 ( m? 6H ) , 4.05 ( t, 2H) 4.55 (m , 1H), 5.62 (s, 1H), 6.22 (s, 1H), 6.42 (d, 1H), 6.97 (d, 2H), 7.18 (m, 3H), 7.65 (d, 1H), 8.18 (d, 2H). [90]

<Measurement of molecular weight of polyimine] The molecular weight of the poly-branched limb was measured by a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd., and a column made by Shodex (KD-803, KD- 805) and measured as follows.

Column temperature: 50 ° C Dissolution: N, N ' - monomethylformamide (as an additive, lithium bromide _ hydrate (LiBr.H20) is 30 mmol / L, phosphoric acid. Anhydrous crystal (〇-phosphoric acid) is 30 mmol /L, tetramethane furan (THF) is i〇mi / L) Flow rate: 1.0ml / min. Measure the line to make a standard sample. Tosho company's TSK standard to take ethylene oxide (molecular weight of about 9000,0 0 0 , 1 500, 〇〇〇, 1 〇〇, 〇〇〇, 3 〇, 〇〇〇) ' and polyethylene glycol manufactured by Polymer Laboratories Ltd. (molecular weight about 12,000 '4,000 '1,000).

S-87-201217352 <Measurement of ruthenium amination rate> The ruthenium iodide ratio of polyimine was measured as follows. 20 mg of polyimine powder was placed in an NMR sample tube (NMR standard sampling tube manufactured by Kusano Scientific Co., Ltd.), and 0.53 mL of deuterated dimethyl hydrazine (DMSO-d6, 0.05% TMS mixture) was added to make it in ultrasonic waves. It is completely dissolved. The 500 MHz proton NMR of this solution was measured by a NMR measuring instrument (JNW-ECA5 00) manufactured by Sigma Electronics DATUM. The ruthenium imidization ratio is determined by a proton derived from a structure which does not change before and after the imidization, and the peak of the proton is used, and the proline which appears near 9.5 to 10.0 ppm is used. The proton peak integral NH of the NH group is obtained by the following formula. Ruthenium amination rate (%) = ( 1 - a . x / y ) X 1 00 For the following formula, x represents the proton peak integral 値 from the NH group of the proline, and y represents the peak integral 値 of the reference proton. α represents the ratio of the number of reference protons corresponding to one hydrazine proton of proline in the case of polyproline (0% imidization). (Example 1) BODA ( 28.1 5 g, 1 1 2.5 mmol), m-PDA (4_86 g, 45 mmol), PCH (11.42 g '30 mmol), and DBA (ll_41g, 75 mmol) were mixed in NMP (187.8 g). After reacting at 80 ° C for 5 hours, CBDA (6.77 g, 36 mmol) and NMP (62.6 g) were added, and -88-201217352 was reacted at 40 ° C for 1 hour to obtain a polyaminic acid solution. To the polyamic acid solution (3 1 3 g), hydrazine was added, and after diluting to 6% by mass, acetic anhydride (79.1 g) and pyridine (30.7 g) were added as a ruthenium catalyzed catalyst at 10 Torr. The reaction was carried out for 3 hours at °C. The reaction solution was poured into methanol (4000 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (A). The polyamidiamine had a ruthenium iodide ratio of 70%, a number average molecular weight of 18,000, and a weight average molecular weight of 5,9000. To the obtained polyimine powder (A) (6.0 g), hydrazine (40.2 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. 3-AMP 5.0 wt% NMP solution (6.0 g) (3-AMP 0.3 g), hydrazine (27.9 g), and BCS (20.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 5 hours. The liquid crystal alignment agent (A 1 ) was obtained. Further, RM1 of 0.06 g (10% by weight of the solid content) was added to the liquid crystal alignment agent (A1) 10 g., and the mixture was stirred and dissolved at room temperature for 3 hours. The liquid crystal alignment agent (A2) was prepared. In the same manner, 10.0 g of the liquid crystal alignment agent (A1) was added to 0.18 g (30 wt% of the solid content) of RM 1, and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (A 3 ). (Example 2) BODA (8'76 g, 35.0 mmol), p-PDA (3.78 g '35.0 mmol), PCH (5.33 g '14.0 mmol), DA-1 (5.55 g, 21.0 mmol) in NMP ( 90.0 g), mixed at 80 ° C for 5 hours ζ -89- 201217352 After the addition, add CBDA ( 6.59g, 33.6mmol) and NMP (30.0g), and react at 40 ° C for 1 〇 hours to obtain poly Proline solution. After the polyacrylic acid solution (140.0 g) was diluted with NMP to 6 mass%, acetic anhydride (20.0 g) and pyridine (25.8 g) were added as a ruthenium amide catalyst, and the mixture was subjected to 50 ° C for 3 hours. reaction. The reaction solution was poured into methanol (1 800 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (B). The polyamidiamine had a ruthenium iodide ratio of 50%, a number average molecular weight of 22,000, and a weight average molecular weight of 77,000. To the obtained polyimine powder (B) (6.0 g), NMP (74.0 g) was added, 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 1 ). Further, RM1 of 0.06 g (10% by weight of the solid content) was added to 10.0 g of the liquid crystal alignment agent (B1), and the mixture was stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (B2). (Example 3) BODA (3.13 g, 12.5 mmol), p-PDA (1.08 g '10 mmol), PCH (1.90 g, 5 mmol), DA-1 (2.64 g, 10 mmol) were mixed in NMP (33.3 g) After reacting at 80 ° C for 5 hours, CBDA (2.35 g, 12 mmo1) (ll.lg) was added, and the reaction was carried out at 40 ° C for 1 hour to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (55.5 g) and diluting to 6 mass%, acetic anhydride (7.7 g) and pyridine (9.9 g) were added as a amide-90-201217352 amination catalyst at 50 The reaction was carried out for 3 hours at °C. The reaction solution was poured into methanol (7 10 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 (C). The polyimine has a ruthenium iodide ratio of 48%, a number average molecular weight of 26,000, and a weight average molecular weight of 102000.

To the obtained polyimine powder (c) (6.0 g), NMP (74.0 g) was added, 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 (C 1 ). Further, RM1 of 〇·〇6 g (1 〇wt% for solid content) was added to 10.0 g of the liquid crystal alignment agent (C 1 ), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent. (C2). (Example 4) BOD A (3.33 g, 1 2 · 5 mmo 1 ), p-PD A (0 · 8 1 g, 7.5 mmo 1 ), PCH (1.90 g, 5 mmol), DA -1 (3,30 g, 12.5 mmol) was mixed in NMP (34.5 g), and after reacting at 80 ° C for 5 hours, CBDA ( 2.35 g, 12 mmol) and NMP (ll. 5 g) were added, and the reaction was carried out at 40 ° C. A polyamine acid solution was obtained after 0 hours of reaction. After adding NMP to the polyamic acid solution (57.5 g) and diluting it to 6 mass%, acetic anhydride (7.7 g) and pyridine (9-9 g) were added as a ruthenium-imiding catalyst, and the mixture was carried out at 50 ° C for 3 hours. reaction. The reaction solution was poured into methanol (730 ml), and the obtained precipitate was filtered. The precipitate is washed with methanol,

S-91 - 201217352 After drying under reduced pressure at 00 ° C, a polyimide pigment (D) was obtained. The polyamidiamine had a oxime imidization ratio of 50%, a number average molecular weight of 23,000, and a weight average molecular weight of 63,000. To the obtained polyimine powder (D) (6.0 g), NMP (74 · 0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the liquid crystal alignment agent (D1) was obtained after stirring for 5 hours at TC. Further, 0.06 g of the above liquid crystal alignment agent (D1) 10·Og was added (for the solid content, l〇wt) RM1 of %) was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (D2). (Example 5) BOD A (5.00 g, 20 mmol), p-PD A (0 · 8 7 g) , 8 mm o 1 ), PCH (3.05g, 8mmo 1 ), DA-1 ( 6.34g, 24mmo 1 ) were mixed in NMP ( 5 7.1g ), and after 5 hours of reaction at 80 ° C, CBDA ( 3.77 was added. g ' 19.2 mmol) and NMP (19.0 g) were reacted at 40 ° C for 1 hour to obtain a polyaminic acid solution. After the polyacrylic acid solution (95.5 g) was added to NMP and diluted to 6 mass%, The hydrazine imidization catalyst was added with acetic anhydride (1 2.3 g) and pyridine (1 5.9 g), and the reaction was carried out for 5 hours at 50. The reaction solution was poured into methanol (1 200 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol at 1 Torr. (: The polyimine powder (E) was obtained after drying under reduced pressure. The ruthenium imidation ratio of the polyimine was 51%' number average The amount is 31〇〇〇, and the weight average molecular weight is 111000 〇-92- 201217352. The obtained polyimine powder (E) (6_0g) is added to NMP (74.0g) and stirred at 50 ° C for 12 hours and made The solution was added to BCS (20.0 g), and stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (E1 ). Further, for the above liquid crystal alignment agent (El) 10 · Og, 〇.〇6g (for solid content) The RM1 of 100% by weight was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (E2). (Example 6) BODA (5.00 g, 2 0.0 mm ο 1 ), p - PDA (2_16g, 2 0 . Ommo 1 ), PCH (3.04g, 8. Ommo 1 ) ' DA-2 ( 2.44g, 12.0mmol) was mixed in NMP (49.2g), and reacted at 80 ° C for 5 hours. Thereafter, CBDA (3.77 g, 19.2 mmol) and NMP (16. 4 g) were added, and a polyamine acid solution was obtained after reacting at 40 ° C for 10 hours. The polyglycine solution (75.0 g) was diluted with NMP to After 6% by mass, acetic anhydride (9.33 g) and hydrazine D (14.6 g) were added as a ruthenium catalyst, and the reaction was carried out at 50 ° C for 3 hours. The reaction solution was poured into methanol (950 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (F). The polyamidimide has a ruthenium iodide ratio of 47%, a number average molecular weight of 20,100, and a weight average molecular weight of 106,000 ». The obtained polyimine powder (F) (6.0 g) is added to NMP (74.0 g). The mixture was stirred at 50 ° C for 12 hours and dissolved. After adding BCS (20.Og) to the solution, the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment of 201217352 (F 1 ). Further, 10.0 g of the above liquid crystal alignment agent (FI) was added with 〇.〇6 g (for a solid content of 10% by weight) RM1' was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (F2). (Example 7) BODA (5.00 g, 20.0 mmol), p-PDA (0.87 g, 8.0 mmol), PCH (3.04 g, 8.0 mmol), DA-2 (4.88 g, 24.0 mmol) in NMP (52.7 g) The mixture was mixed and reacted at 80 ° C for 5 hours. Then, CBDA (3.77 g, 19.2 mmol) and NMP (17-56 g) were added, and the reaction was carried out at 40 ° C for 1 hour to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (75 g) and diluting to 6 mass%, acetic anhydride (8.7 g) and pyridine (13.5 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (95 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (G). The polyimine has a ruthenium iodide ratio of 50%, a number average molecular weight of 20,000, and a weight average molecular weight of 86,000. To the obtained polyimine powder (G) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the liquid crystal alignment agent (G1) was obtained after stirring for 5 hours at TC. Further, 0.06 g of the above liquid crystal alignment agent (G1) 10·Og was added (for the solid content, l〇) RM1 of wt%) was stirred at room temperature for 3 hours and dissolved in -94-201217352 to prepare a liquid crystal alignment agent (G2). (Example 8) BODA (6.01 g '24.0 mmol), p-PDA ( 2.60g, 24.0mmol), PCH ( 6.85g, 1 8.0 mmo 1 ), DA-1 (4.7 6g '18.0mmol) were dissolved in NMP (81.5g), and reacted at 80 ° C for 5 hours, then added CBDA ( 6.94 g, 35.4 mmol) and NMP ( 27.2 g) were reacted at 40 ° C for 1 hour to obtain a polyaminic acid solution. NMP was added to the polyamic acid solution (1 3 5 g) and diluted to After 6 mass%, acetic anhydride (18_3g) and pyridine (23.6g) were added as a ruthenium catalyst, and the reaction was carried out at 50 ° C for 3 hours. The reaction solution was poured into methanol (1700 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (Η). The ruthenium imidization ratio of the polyimine was 60%. The average molecular weight was 12,000, and the weight average molecular weight was 3 9000. The obtained polythenimine powder (H) (6.0 g) was added to ΝΜΡ (74·0 g)' for stirring at 50 ° C for 12 hours and allowed to Dissolved. Add BCS (2 0.0 g) to the solution, and obtain a liquid crystal alignment agent (Η1) after stirring at 50 ° C for 5 hours. ' Add a polymerizable compound RM10_06g to the above liquid crystal alignment agent (Η 1 ) 1 0.0 g ( The solid content was 10% by mass), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (H2). (Example 9) -95-201217352 For liquid crystal alignment agent (HI) 10.0 g, 0.06 was added. The polymerizable compound RM2 (g is a solid content of 1% by mass) is stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (H3). (Example 1 〇) For a liquid crystal alignment agent (HI) The polymerizable compound RM3 of 0.06 g (1% by mass of the solid content) was added to the OO.Og, and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (H4). (Comparative Example 1) Liquid crystal alignment agent (HI) lO.Og added 0.06g (for solid content 10% by mass) of the polymerizable compound RM4, stirred for 3 hours at room temperature and dissolved to prepare a liquid crystal alignment agent (H5). (Example 1 1) The polymerizable compound RM5 was added to the liquid crystal alignment agent (HI) 10 g (0.06 g (solid content: 1% by mass)), and the mixture was stirred at room temperature for 3 hours to dissolve the liquid crystal. Orienting agent (H6). (Example 1 2) The polymerizable compound RM6 of 0.06 g (1% by mass based on the solid content) was added to the liquid crystal alignment agent (HI) 10 g. The solution was stirred at room temperature for 3 hours to dissolve the liquid crystal. Orienting agent (H7). -96-201217352 (Example 1 3) The polymerizable compound RM7 of 6 g (10% by mass of solid content) was added to the liquid crystal alignment agent (HI) 10 O.Og, and stirred at room temperature for 3 hours. Dissolved to prepare a liquid crystal alignment agent (H8). (Example 1 4) 0.06 g (10% by mass of the solid content) of the polymerizable compound RM8 was added to the liquid crystal alignment agent (HI) 10. Og was stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent. (H9). (Example 1 5) 0.06 g (100% by mass of solid content) of the polymerizable compound RM9 was added to the liquid crystal alignment agent (HI) 10 g. The solution was stirred at room temperature for 3 hours to dissolve the liquid crystal. Orienting agent (H10). (Example 1 6) The polymerizable compound RM 1 0 was added to the liquid crystal alignment agent (HI ) 10 · Og to a polymerizable compound RM 1 0 (for a solid content of 1 〇 mass %), and stirred at room temperature for 3 hours to dissolve. , a liquid crystal alignment agent (Η 1 1 ) is prepared. (Example 1 7) The polymerizable compound RM 1 1 ' of the liquid crystal alignment agent (HI) 10·Og was added to the polymerizable compound RM 1 1 ' at a room temperature for 3 hours. A liquid crystal alignment agent (H12) is prepared.

C-97-201217352 (Example 1 8) To the liquid crystal alignment agent (HI) 10.Og, 0.06 g (100% by mass of the solid content) of the polymerizable compound RM 1 2 was added, and the mixture was stirred at room temperature for 3 hours. This was dissolved to prepare a liquid crystal alignment agent (H13). (Example 1 9) The polymerizable compound RM13 containing 0.06 g (1% by mass of the solid content) of the liquid crystal alignment agent (HI) was added to the polymerizable compound RM13 at room temperature for 3 hours, and dissolved to prepare a liquid crystal. Orienting agent (H14). (Example 20) The polymerizable compound RM 1 4 ' of 0.06 g (100% by mass of the solid component) was added to the liquid crystal alignment agent (HI) 10 g. The mixture was stirred at room temperature for 3 hours to be dissolved. Liquid crystal alignment agent (Η 15). (Example 2 1) The polymerizable compound RM 1 5 ' was added to the liquid crystal alignment agent (HI) 10 g of 0.06 g (the solid content was 1% by mass), and the mixture was stirred at room temperature for 3 hours to be dissolved. Liquid crystal alignment agent (Η 16). (Example 22) 0.06 g (100% by mass of solid content) of the polymerizable compound RM16 was added to the liquid crystal alignment agent (HI) 10. Og, and stirred at room temperature for 3 hours - 98 to 201217352 to dissolve A liquid crystal alignment agent (H17) was prepared. (Example 23) 0.06 g (100% by mass of the solid content) of the polymerizable compound RM 17 was added to the liquid crystal alignment agent (HI) 10 g. The solution was stirred at room temperature for 3 hours to be dissolved. Liquid crystal alignment agent (Η 18). (Example 24) 0.06 g (100% by mass of solid content) of the polymerizable compound RM18 was added to the liquid crystal alignment agent (HI) 10. Og, and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment. Agent (H19). (Example 25) BODA ( 4.38 g, 1 7.5 mmol), m-PDA (2.65 g, 24.5 mmol), PCH (4·0 0 g, 1 0.5 mm o 1 ) were dissolved in N Μ P ( 42.8 g ) After reacting at 80 ° C for 5 hours, CBDA (3.22 g, 16.5 mmol) and NMP (14. 2 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (70.0 g) and diluting to 6 mass%, acetic anhydride (17.6 g) and pyridine (5.44 g) were added as a ruthenium catalyzed catalyst, and the mixture was carried out at 100 ° C for 3 hours. reaction. The reaction solution was poured into methanol (900 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 (I). 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.

S-99-201217352 To the obtained polyimine powder (1) (6.9 g), nmp (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. To the solution was added B C S (2 0.0 g), and the mixture was stirred at 50 ° C for 5 hours to obtain a polyimine solution (11 ). Further, for the polyimine solution (11), 10 g of a polymerizable compound RM1 (for a solid content of 1% by mass) was added, and the mixture was stirred at room temperature for 3 hours to be dissolved. Liquid crystal alignment agent (12). (Example 26) 3AMPDA (2.54 g, 1 0.5 mmol), PCH (4.00 g, 10.5 mmol), DA-1 (3.70 g, 1.4 mmol) were dissolved in NMP (34.1 g), and CBDA was added to a water bath ( 6.79 g, 35.0 mmol) and NMP (34.1 g) were reacted at 23 ° C for 10 hours to obtain a polyaminic acid solution. After the NMP was diluted to 6 mass% in the polyamidic acid solution (84.0 g), acetic anhydride (10.6 g) and pyridine (4.5 gg) were added as a ruthenium catalyzed catalyst, and the mixture was allowed to stand at 40 ° C for 3 hours. reaction. The reaction solution was poured into methanol (1 000 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 (J). The polyimine had a ruthenium iodide ratio of 41%, a number average molecular weight of 13,000, and a weight average molecular weight of 47,000. To the obtained polyimine powder (J) (6.0 g), NMP (54.0 g) was added and stirred at 40 ° C for 12 hours to dissolve. The solution of BCS (40_0g) was added to the solution at 40 ° C for 5 hours to obtain a polyimine solution (J1 ). -100-201217352 Further, for the polyimine solution (ji) i〇.〇g, a polymerizable compound RM1 of 6 g (10% by mass of the solid component) was added, and the mixture was stirred at room temperature for 3 hours. This was dissolved to prepare a liquid crystal alignment agent (J2). (Example 2 7 ) TCA ( 3.36 g, 15.0 mmol), p-PDA ( 1.30 g, 1 2. Ommo 1 ), DA-3 ( 3.14 g, 6.0 mmol), DA-1 ( 3.17 g, 12.0) Ment) 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 to the mixture, and the mixture was reacted at 40 ° C for 10 hours to obtain a poly Proline solution. After adding NMP to the polyamic acid solution (68 g) and diluting it to 6 mass%, acetic anhydride (6.0 g) and pyridine (11.7 g) were added as a ruthenium-imiding catalyst, and the mixture was carried out at 50 ° C for 3 hours. reaction. The reaction solution was poured into methanol (850 ml) to remove the resulting precipitate. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (κ). The polyamidiamine had a ruthenium iodide ratio of 50%, a number average molecular weight of 180 Å, and a weight average molecular weight of 58,000. To the obtained polyimine powder (K) (6.0 g), NMP (74·0 g) was added and stirred at 50 ° C for 12 hours and dissolved. Adding BCS (20 · 0 g ) to the solution, stirring at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (K1 ), and adding 0.06 g to the above liquid crystal alignment agent (K1 ) l〇.〇g (for The solid content of 10% by weight of RM1' was stirred and dissolved at room temperature for 3 hours to adjust the liquid crystal alignment agent (K2).

S-101 - 201217352 (Example 2 8) Using the liquid crystal alignment agent (A2) obtained in Example 1, the production of liquid crystal cells was carried out in the order shown below. [Production of Liquid Crystal Cell] The liquid crystal alignment agent (A2) was spin-coated on an ITO surface of an ITO electrode substrate having an ITO electrode pattern having a pixel size of 100 μm x 30 μm and a line/pitch of 5 m, at 80°. The hot plate of C was dried 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 100 nm. Further, the liquid crystal alignment agent (A2) was spin-coated on the ITO surface on which the electrode pattern was not formed, dried on a hot plate at 80 ° C for 90 seconds, and then dried in a hot air circulating oven at 200 ° C for 30 minutes. The film was fired to form a liquid crystal alignment film having a film thickness of 100 nm. On the two substrates described above, a 6/5 m bead spacer was spread on the liquid crystal alignment film of one of the substrates, and then 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 set to the inside, and after bonding to the previous substrate, the sealant was cured to produce a cell. MLC-6608 was injected into the cell by a reduced pressure injection method, and Isotropic treatment (re-alignment treatment by heated liquid crystal) was performed in an oven at 1200 ° C to prepare a liquid crystal cell. The post-production response speed of the obtained liquid crystal cell was measured by the following method. Thereafter, in a state where the liquid crystal cell was externally applied with a voltage of 20 Vp-p, -102-201217352 was irradiated by the outside of the liquid crystal cell through a 313 nm band-pass filter of UV20J. Thereafter, the response speed was measured again, and the response speed before and after the UV irradiation was compared. The results of the response speeds of the liquid crystal cells after the preparation (initial) and after the UV irradiation of 20 J (after UV20J) are shown in Tables 2 to 4. (Example 2 9) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (A3). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Comparative Example 2) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (a1). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 30) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (B2). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Comparative Example 3) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (b1). The liquid crystal cell was produced in the same manner as in Example 28, and the reaction was performed before and after U V irradiation.

S -103- 201217352 Answer speed. (Example 3 1) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (C2). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Comparative Example 4) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (C1). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 3 2) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (D2). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Comparative Example 5) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (D1). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 3 3) The liquid crystal alignment agent (A2) was changed to other than the liquid crystal alignment agent (E2). 104 - 201217352 The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Comparative Example 6) The liquid crystal alignment agent (A 2 ) was changed to the liquid crystal alignment agent (e 1 ). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 3 4) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (F2). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Comparative Example 7) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (F1). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 3 5) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (G2). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Comparative Example 8) -105-201217352 The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (G1). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 3 6) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H2). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 3 7) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H2), and the firing temperature was changed to 140 ° C. The liquid crystal cell was produced in the same manner as in Example 28, and the UV irradiation was performed. The response speed before and after. (Example 3 8) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H3). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 3 9 ) The liquid crystal alignment agent (A 2 ) was changed to a liquid crystal alignment agent (Η 3 ), and the firing temperature was changed to 140° C., and liquid crystal cells were produced in the same manner as in Example 28, and UV irradiation was performed. The response speed before and after. -106-201217352 (Example 40) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H4). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 4 1) The liquid crystal alignment agent (A2) was changed to a liquid crystal alignment agent (H4), and the firing temperature was changed to 14 (other than TC, the liquid crystal cell was produced in the same manner as in Example 28, and the response before and after UV irradiation was compared. (Comparative Example 9) The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H5), and the response speed before and after the UV irradiation was compared. (Comparative Example 1 0) The liquid crystal alignment agent (A 2 ) was changed to a liquid crystal alignment agent (Η 5 ), and the firing rate was changed to 140° C., and the liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. 1 1) The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (?1), and the response speed before and after the UV irradiation was compared.

S-107-201217352 (Comparative Example 1 2) The liquid crystal alignment agent (A2) was changed to a liquid crystal alignment agent (?1), and the firing temperature was changed to 140 °C, and the liquid crystal cell was produced in the same manner as in Example 28, and then compared. Response speed before and after UV irradiation. (Example 42) A liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (12), and the response speed before and after the UV irradiation was compared. (Example 43) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (12), and the firing temperature was changed to 140 °C. The liquid crystal cell was produced in the same manner as in Example 28, and the response before and after the UV irradiation was compared. speed. (Comparative Example 1 3) The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the polyimine solution (11), and the response speed before and after the UV irradiation was compared. (Comparative Example 1 4) The liquid crystal alignment agent (A2) was changed to a polyimine solution (11), and the liquid crystal cell was prepared in the same manner as in Example 28 except that the firing temperature was changed to 1 40 °C. Response speed before and after UV irradiation. (Example 44) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H6). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 4 5) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H7). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 46) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H8). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 47) The liquid crystal alignment agent (A 2 ) was changed to a liquid crystal alignment agent (Η 9 ). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after UV irradiation was compared. (Example 4 8) The liquid crystal alignment agent (Α2) was changed to a liquid crystal alignment agent (Η1 0 )

S-109-201217352 A liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after UV irradiation was compared. (Example 49) The liquid crystal cell was changed in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (?1). The response speed before and after the UV irradiation was compared. (Example 50) The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (?2) was changed to the liquid crystal alignment agent (?2). The response speed before and after the UV irradiation was compared. (Example 5 1) The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (?2) was changed to the liquid crystal alignment agent (?1). The response speed before and after the UV irradiation was compared. (Example 52) The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (?2) was changed to the liquid crystal alignment agent (?1). The response speed before and after the UV irradiation was compared. (Example 5 3) -110-201217352 The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (?1). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 54) A liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to a liquid crystal alignment agent (?16). The response speed before and after UV irradiation was compared. (Example 5 5) The liquid crystal alignment agent (?2) was changed to a liquid crystal alignment agent (?7). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 5 6) The liquid crystal alignment agent (?2) was changed to a liquid crystal alignment agent (?8). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Example 5 7) The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (?2) was changed to the liquid crystal alignment agent (?1). The response speed before and after the UV irradiation was compared.

S-111 - 201217352 (Example 5 8) The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (J2), and the response speed before and after the UV irradiation was compared. (Example 59) The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (K2). The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared. (Comparative Example 1 5) The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the polyimine solution (A2), and the response speed before and after the UV irradiation was compared. The "measurement method of the response speed" is a set of a measuring device in the order of a polarizing plate and a light amount detector in a backlight or a quadrature polarization state, and a liquid cell is placed between a group of polarizing plates. At this time, the pattern of the ITO electrode formed by the line/pitch is made to be an angle of 45° with respect to the orthogonal polarization. At this time, the pattern of the ITO electrode formed by the line/pitch is made to be an angle of 45° with respect to the orthogonal polarized light. The rectangular wave with the applied voltage of the liquid crystal cell: UV and the number of cycles of 1 kHz is read by the oscilloscope (-112-201217352 oscilloscope) by the brightness observed by the light quantity detector, and the brightness when the voltage is not applied is 〇 %, plus the voltage of 4V of the soil, and the saturation brightness is 1100°/. The time when the brightness is changed from 1% to 90% as the response speed β is shown in Tables 2 to 4. [Table 2] Liquid crystal alignment agent response speed (msec) Type of polymerizable compound surface addition amount (% by mass) Initial UV20J after Example 28 Α2 RM1 10 763 468 Example 29 A3 RM1 30 691 23 Comparative Example 2 Α1 A - 751 653 Example 30 Β2 RM1 10 787 46 Comparative Example 3 Β1 748 521 Example 31 C2 RM1 10 741 41 Comparative Example 4 C1 - 791 457 Example 32 D2 RM1 10 760 33 Comparative Example 5 D1 - One 708 438 Example 33 Ε2 RM1 10 749 31 Comparative Example 1 - 763 429 Example 34 F2 RM1 10 791 87 Comparative Example 7 F1 One 803 457 Example 3 5 G2 RM1 10 753 42 Comparative Example 8 G1 - One 774 326 From Table 2 As a result, it was confirmed that the addition of the polymerizable compound RM 1 having an α-methyl-γ-butyl lactone group at the end thereof significantly improved the response speed after UV irradiation. In addition, when the addition amount of the polymerizable compound is increased, the rate of improvement of the response rate tends to increase. However, when a polymer having a photoreactive side chain is used, the reaction rate is improved even when the amount of the polymerizable compound added is small. rate.

S 113-201217352 [Table 3] Liquid crystal alignment agent firing temperature (6) Response speed (msec) Type of polymerizable compound surface addition amount (% by mass) Initially after 11 Example 36 Η2 RM1 10 200 821 35 Example 37 Η2 RM1 10 140 862 37 Example 38 Η3 M2 10 200 779 62 Example 39 Η3 RM2 10 140 891 55 Example 40 Η4 RM3 10 200 783 36 Example 41. Η4 RM3 10 140 808 42 Comparative Example 9 Η5 RM4 10 200 814 732 Comparative Example 10 Η 5 RM4 10 140 _ 850 31 Comparative Example 11 Η 1 - 200 823 809 Comparative Example 12 Η 1 - 140 816 793 Example 42 12 RM1 10 200 798 '456 Example 43 12 RM1 10 140 812 398 Comparative Example 13 11 — A 200 768 745 Comparative Example 14 11 1-140 835 812 The results of Table 3 show that when calcined at a high temperature of 200 ° C, the use of α-extended methyl-γ-butyl lactone group at the end is used. When the liquid crystal alignment agent of the polymerizable compound of RM1 to RM3 is RM4 having a methacryl structure without an α-methyl-γ-butyl lactone group at the terminal end, the rate of improvement of the response speed is remarkably higher. The tendency. This indicates that the α-extended methyl-γ-butyl lactone structure is stable even at a high temperature, and the reactive group is a structure which is less likely to cause thermal polymerization than the methacryl group. -114-201217352 [Table 4] Liquid crystal alignment agent polymerizable compound baking dirty response rate (msec) Screen addition amount m (% by mass) Initial UV20J after Example 44 Η6 RM5 10 200 790 24 Example 45 Η7 RN6 10 200 792 22 Example 46 Η8 RM7 10 200 821 .32 Example 47 Η9 RM8 10 200 849 331 Example 48 Η10 RM9 10 200 815 41 Example 49 Η11 RM10 10 200 860 41 Example 50 ΗΪ2 RM11 10 200 802 403 Example 51 Η13 RM12 10 200 784 40 Example 52 Η14 RM13 10 200 808 33 Example 5 3 Η15 RM14 10 200 757 186 Example 54 Ηί6 RM15 10 200 798 219 Example 55 H17 RM16 10 200 774 236 Example 56 H18 RM17 10 200 817 17 Example 57 H19 RM18 10 200 754 12 Example 58 J2 RM1 10 200 786 27 Example 59 K2 RM1 10 20α 649 43 Comparative Example 15 J1 One - 200 769 755 It was confirmed by the results of Table 4 that it was used as a polymerizable compound. Even when it is used for a polymerizable compound having an α-methyl-γ-butyl lactone group at the end, the response speed is remarkably improved. In addition, as the polymerizable compound having an α-methyl-γ-butyl lactone group, which is required to increase the response speed, the same effect can be obtained by including only one such structure, and a polymerizable group such as a propylene group is contained as another structure. The light-crosslinking group or the like which is quantified by the light bismuth or the like may also increase the response speed.

S -115-

Claims (1)

201217352 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by containing the following polymerizable compound, polymer and solvent; wherein the polymerizable compound is held with α-extended methyl-γ-butyrolactone a polymerizable compound having a terminal end and a terminal having a photopolymerization or photocrosslinking group; the polymer is a polymer which forms a liquid crystal alignment film capable of aligning the liquid crystal. 2. The liquid crystal alignment agent of claim 1, wherein the polymerizable compound is at least one selected from the group consisting of the following formulas [1-1] to [1-4]; (In the formula [1-1] to [1-4], V represents a single bond or -R31〇-, R31 is a linear or branched alkyl group having 1 to 10 carbon atoms, and W represents a single bond or -OR32- , R32 is a linear or branched carbon number of 1 to 1 fluorene alkyl, nl is an integer of 1 to 10, 5 (and ^ are each independently 1 or 2, R1 is hydrogen or methyl, A21 is a single bond or Selected from the following bases -116- 201217352 [Chemical 2 Ο 〇ν —(CH^pj-O —(ΟΗ^,,-Ο .0 Ο· ◦-(CHW-O People eight y~ -O-(CH2)pl-O- (wherein pl is an integer of 2 to 10, ql is an integer of 0 to 2, and z is 1 or 2) 3. As the liquid crystal alignment agent of the first application of the patent scope, Wherein the polymerizable compound is at least one selected from the group consisting of the following formulas [Π-1] to [Π-3]; (In the formula [II-1] to [II-3], n2 is an integer of 2 to 11, ml is an integer of 0 to 11, X is 1 or 2, R2 is hydrogen, -OCH3 or a halogen atom, and R3 is hydrogen. , -CN, -0(CH2) mlCH3 or a halogen atom, R4 is - (CH2) nnCHdml S -117- 201217352 is an integer from 0 to 11), A22 is a single bond, -o-c6h4- or -〇-C6h4- C6h4.) 4. The liquid crystal alignment agent of claim 1, wherein the polymerizable compound is represented by the following formula [III-1]; [ΙΠ-1] (In the formula [III-1], 11 is an integer of 2 to 9, and X1 is a group selected from the following formulas [in] to [iii-3]), [Chemical 5] (In the formula [iii-2], m2 is an integer of 4 to 8, and in the formula [iii-3], R5 is a group selected from the following formula:) η Ο -. -(Qing Dian (wherein, X2 is hydrogen, a halogen atom, a cyano group or an alkoxy group, R1 is hydrogen or a methyl group, n3 is an integer of 2 to 10, p2 is an integer of 3 to 10, and 〇1 is an integer of 0 to 6) . 5. The liquid crystal alignment agent of claim 1, wherein the polymerizable compound is represented by the following formula [IV]; -118-201217352 [Chem. 7] (wherein, X3, X4, X1 and X6 are each independently hydrogen or a fluorine atom, R6 is hydrogen, a halogen atom, a cyano group, an alkyl group, an alkoxy group or an alkoxycarbonyl group, and 0 is -C (= 0) 0- or - OC(= 0)-base, n4 is an integer from 4 to 10.). 6. The liquid crystal alignment agent of claim 1, wherein the polymer forming the liquid crystal alignment film capable of aligning the liquid crystal has a side chain having a liquid crystal alignment. A liquid crystal alignment film which is obtained by applying a liquid crystal alignment agent according to any one of claims 1 to 6 to a substrate and firing it. 8. A liquid crystal display device characterized by having a liquid crystal cell coated on a substrate by a liquid crystal alignment agent according to any one of claims 1 to 6 A liquid crystal layer was placed on the obtained liquid crystal alignment film and brought into contact therewith, and a liquid crystal layer was applied while applying a voltage while irradiating ultraviolet rays. 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 6 is applied to a liquid crystal alignment film obtained by firing a substrate. In contact with this, a liquid crystal cell is produced by applying a voltage to the liquid crystal layer while irradiating ultraviolet rays. 10. A polymeric compound characterized by any one of the following formulae; -119- 1 201217352 -120- 201217352 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201217352 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: none