TW201213395A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Disclosed are: a material for a liquid crystal alignment film, which does not undergo film detachment or scratching during rubbing even when the material is burned at a temperature of 200 DEG C or lower and can achieve good liquid crystal alignment properties; and a novel diamine which is used in the material. Specifically disclosed is a liquid crystal aligning agent comprising at least one polymer selected from the group consisting of a polyamic acid and a polyimide produced by dehydrating and ring-closing the polyamic acid, wherein a diamine component comprises a diamine represented by formula [3]. (In the formula, R3 represents a group selected from the group consisting of -CH2-, -O-, -CONH-, -NHCO-, -COO-, -OCO- and -NH-; R4 represents a single bond or an alkylene group having 1-10 carbon atoms; R5 represents a single bond, -CH2-, -O- or -NH-; R6 represents a bivalent organic group which is composed of one or several rings, has at last one aromatic ring at an terminal thereof, and has 5-18 carbon atoms; and R7 represents a hydrogen atom, a methyl group or the like.)

Description

201213395 6. Technical Field [Technical Field] The present invention relates to a liquid crystal alignment agent used in the production of a liquid crystal alignment film, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film, And the novel diamines that apply to them. [Prior Art] A liquid crystal display element used for a liquid crystal display such as a liquid crystal display, a liquid crystal display, or a liquid crystal display is used. The polyimine-based liquid crystal alignment film is used at most for reasons of excellent productivity and excellent chemical and thermal durability. . The polyimine-based liquid crystal alignment film is applied to a substrate by a solution of a polyimine or a polyaminic acid of a polyimine precursor, and is usually baked at a temperature of about 200 to 25 ° C. Made into. The firing process in the production of a polyimine-based liquid crystal alignment film is particularly necessary in the process of producing a liquid crystal display device, and is preferably a high-temperature process, and has hitherto been used for the purpose of using a plastic substrate or for a color filter. A polyimide-based liquid crystal alignment film material which can be fired at a low temperature of 200 ° C or lower is proposed for the reason of the heat resistance and the reduction of the energy cost (see, for example, Patent Document 1). After the polyimine-based liquid crystal alignment film is fired, it is rubbed by a cloth such as cotton, nylon or crepe, and is subjected to an alignment treatment by a so-called rubbing method. In recent years, in place of this friction, an alignment treatment method for irradiating polarized ultraviolet rays or the like, or a liquid crystal display element having a vertical alignment mode which is not required to be aligned has been developed, and some of them have been put into practical use. However, the current alignment of -5-201213395 is also an important position in the process of manufacturing a liquid crystal alignment film by the rubbing alignment treatment. In recent years, when the polyimine-based liquid crystal alignment film is fired at a low temperature, the mechanical strength of the film subjected to the rubbing treatment is insufficient. That is, when the rubbing treatment is performed, a flaw is generated on the surface of the liquid crystal alignment film, or a part of the film is peeled off by the substrate or the like. In the case of low-temperature firing, the film strength is insufficient when compared with the general firing temperature, so that the improper situation caused by the rubbing treatment becomes a serious problem. For a liquid crystal alignment film which improves the friction resistance at the time of low-temperature baking, a method of using a specific tetracarboxylic dianhydride for a raw material of polyamic acid (for example, refer to Patent Document 2) and a method of using an additive have been proposed (for example, refer to the patent document) 3) A method of introducing a diamine having an acrylic residue at the end of a side chain (for example, refer to Patent Document 4), etc. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 5-15804 7 [Patent Literature [Patent Document 3] JP-A-2002-357831 [Patent Document 4] JP-A-2008-203332 SUMMARY OF INVENTION Problems to be Solved by the Invention The problem of the present invention is to provide at 20 (TC). The following materials for liquid crystal alignment film which do not cause film peeling or scratching during rubbing and which have good liquid crystal alignment properties can also be produced by firing at 200 ° C or less, and rubbing

-6- S 201213395, which does not cause film peeling or scratches, and can provide a liquid crystal alignment film with good liquid crystal alignment, and the energy cost during production is reduced, and even a substrate having low heat resistance such as a plastic substrate is used. Suitable liquid crystal display elements, as well as novel diamines suitable for use herein. Means for Solving the Problems The inventors of the present invention have made a detailed review of the above problems, and by using a diamine component having a specific structure of a diamine having a novel diamine compound before the application of the present invention, even at 200 ° C or lower, firing is performed. Further, the present invention can be obtained by obtaining a liquid crystal alignment film which is excellent in liquid crystal alignment and which does not cause film peeling or scratching when rubbing. That is, the present invention is intended to be as follows. 1. A liquid crystal alignment agent containing a polyfluorene obtained by polymerizing a diamine component represented by the following formula [1] and a tetracarboxylic dianhydride component represented by the following formula [2]; A liquid crystal alignment agent of at least one polymer of a group consisting of an amine acid and a polyamidene obtained by subjecting the polyamic acid to dehydration ring closure, wherein the diamine component contains a diamine represented by the following formula [3] [Chemical 1] H2N-Ri-NH2 [ 1 ] (L is a divalent organic group) 201213395

(R2 is a tetravalent organic group) [Chemical 3]

[3] wherein R3 represents a group selected from the group consisting of -CH2-, -0-, -CONH-, -NHCO-, -COO-, -OCO-, and -NH-; R4 represents a single bond or An alkylene group having 1 to 10 carbon atoms, 1 or a plurality of -CH 2 - of the alkylene group may be substituted by -CF 2 , and may be substituted for any of the groups exemplified below which are not adjacent to each other. These groups; _〇_, -NHC0-, -CONH·, -COO- '-OCO- '-NH-; R5 represents a single bond, -CH2-, -0- or NH-; R6 represents 1 or a complex number a bivalent organic group having at least one aromatic ring having 5 to 18 carbon atoms at the terminal, wherein the ring may be a carbocyclic ring or a heterocyclic ring, and 1 or a plurality of hydrogens of the ring may be substituted by a fluorine atom; R7 is The liquid crystal alignment agent according to the above 1, wherein R3 in the formula [3] is -0- or -C00-. The liquid crystal alignment agent according to the above 1 or 2, wherein R4 in the formula [3] is a mercapto group having 1 to 4 carbon atoms. 4. The liquid crystal alignment agent according to any one of the above 1 to 3, wherein R5 in the formula [3] is -0-. The liquid crystal alignment agent according to any one of the above 1 to 4, wherein R6 in the formula [3] is 1,4_phenylene. 6. The liquid crystal alignment agent according to any one of the above 1 to 5, wherein R7 in the formula [3] is a methyl group. 7. The liquid crystal alignment agent according to any one of the above-mentioned, wherein the diamine component represented by the formula [1] contains 30 mol% or more of the diamine represented by the above formula [3]. The liquid crystal alignment agent according to any one of the above-mentioned items 1 to 7, wherein the tetracarboxylic dianhydride component represented by the formula [2] contains a tetracarboxylic acid having an alicyclic structure in the formula (2). anhydride. A liquid crystal alignment film obtained by the liquid crystal alignment agent according to any one of the above 1 to 8. 10. A liquid crystal alignment film which is obtained by applying the liquid crystal alignment agent according to any one of the above 1 to 8 to a substrate, firing at a temperature of 200 ° C or lower, and then rubbing it. A liquid crystal display device comprising the liquid crystal alignment film according to the above 9 or 1 . 12. A diamine characterized by the following formula [3]; -9 - 201213395

Wherein R3 represents a group selected from the group consisting of -CH2-, -〇-, -CONH-, -NHCO-, -COO-, -oco..., and _NH_; R4 represents a single bond or a carbon number of 1~ The alkyl group of 10, the alkyl group of the alkyl group or the plurality of -CH2- may be substituted by -CF2-, and the case where any of the groups exemplified below are not adjacent to each other 'may be substituted for these groups;- 〇-, -NHCO-, -CONH-, -COO-, -oco-, -NH-; R5 represents a single bond, -CH2-, -0- or NH-; R6 represents 1 or a plurality of rings, a divalent organic group having at least one aromatic ring having 5 to 18 carbon atoms at the terminal, the ring may be a carbocyclic ring or a heterocyclic ring, and 1 or a plurality of hydrogens of the ring may be substituted by a fluorine atom; R7 is hydrogen or methyl Or trifluoromethyl). EFFECTS OF THE INVENTION The liquid crystal alignment agent of the present invention does not cause film peeling or scratching by rubbing treatment even at a firing temperature of 200 ° C or lower, and a liquid crystal alignment film having a good liquid crystal alignment can be obtained. Further, the liquid crystal alignment agent of the present invention can obtain high reliability even when a liquid crystal display element which is subjected to an alignment treatment method such as irradiation of polarized ultraviolet rays or an alignment treatment method in which ultraviolet rays or the like is applied while applying a voltage.

-10-S 201213395 MODE FOR CARRYING OUT THE INVENTION The diamine used in the production of the liquid crystal alignment agent of the present invention contains a diamine represented by the following formula [3].

(wherein R3 represents a group selected from the group consisting of -CH2-, -0-, -CONH-, -NHCO-, -COO-, -OCO-, and -NH-; and R4 represents a single bond or a carbon number of 1 ～10 alkylene, 1 or a plurality of _CH 2 - of the alkylene group may be substituted by -CF 2 , and may be substituted for any of the groups exemplified below which are not adjacent to each other; -Ο-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-; [3] R5 represents a single bond, -CH2-, -0- or -NH-; R6 represents 1 or a plurality a ring having at least one aromatic ring having a carbon number of 5 to 18 at the terminal, the ring may be a carbocyclic ring or a heterocyclic ring, and the ring 1 or a plurality of hydrogens may be substituted by a fluorine atom; R7 represents hydrogen, methyl or trifluoromethyl) wherein R3-R4-R5-R6 in the formula [3] is a spacer moiety in the side chain, and R3 represents a bond to the diamine benzene skeleton in the spacer moiety. base. The bonding group is selected from the group consisting of -CH2- (ie, methyl group), -0- (ie, ether), -CONH- (ie, decylamine), -NHC0- (ie, decylamine), -C00- (ie, ester) ), -0C0- (ie, reverse ester), and -NH- (ie, an amine group) are grouped. These bond groups can be formed by general organic synthesis methods, and from the viewpoint of ease of synthesis, it is preferable to use -11 - 201213395 -CH2-, -0-, -COO-, -NHCO- or -NH-, -〇- Or -COO- is preferred. R4 in the formula [3] is a portion which becomes a center of the spacer portion, and is basically a single bond or an alkylene group having a carbon number of 1 to 10. However, any -CH2- of the alkylene group may be substituted by -CF2-. Further, the substituted -CH2- may have no more than one or plural. And 1 or a plurality of -CH2- of the alkylene group may be substituted for the same ϋIp S ϊ -〇- ' -NHCO- ' -CONH- in the case where any of the bonding groups mentioned next are not adjacent to each other. '-COO- ' -OCO- ' -NH-, -NHCONH-, -NH. This means that R4 may contain a structure of a so-called alkylene group - the bonding group - an alkylene group. Further, when R3 is -CH2-, it means that the terminal on the R3 side in R4 may be the bonding group. Similarly, when R5 is -CH2-, it means that the terminal on the R5 side in R4 may be the bonding group. Thus, when R3 is -CH2-, and R5 is -CH2-, it means that R4 is a structure of the bonding group - an alkyl group - the bonding group, or R4 is any of the so-called bonding groups. Further, -CH2- which is substituted by the bonding group may be one, and if the bonding groups are not adjacent to each other, they may be plural positions. R4 is preferably an alkylene group having 1 to 6 carbon atoms, and an alkylene group having 4 carbon atoms is particularly preferred. R5 in the formula [3] represents a bond group with R6 in the spacer moiety. The bonding group is selected from the group consisting of a single bond, -CH2-, -0-, and -NH-, but preferably -〇-. R6 in the formula [3] represents a divalent organic group having 5 or 18 carbon atoms which is composed of 1 or a plurality of rings and has at least one aromatic ring at the terminal. The ring may be a carbocyclic ring or a heterocyclic ring. Specific examples of the structure of such an organic group include the following structures, but are not limited thereto. Again, 1 or a plurality of hydrogens of the ring

-12- S 201213395 can also be replaced by a fluorine atom. [化6] 〇 〇-〇 00-0

Coco

Further, it is desired to increase the reaction of a propylene group and a methacryl group (i.e., a substituent represented by -〇_c (= 〇) _ CH=CH2 or - 0-C (= 0) -C (= CH2) -CH3) The propylene or methacryl group is bonded to the aromatic ring. From such a viewpoint, as R6, for example, a 1,4-phenylene group or the like is preferred. R7 in the formula [3] is hydrogen, methyl or trifluoromethyl, but a methyl group is preferred. With respect to the above formula [3], the bonding position of the two amine groups on the benzene ring is not particularly limited. The two amine groups may have a 2,3-position, a 2,4-position, a 2,5-position, a 2,6-position, and a 3,4-position for the substituent having an acrylate structure at the terminal. The position, 3,5-position, preferably 2,4-position or -13-201213395 3,5-position. <Synthesis method of diamine compound> The method of synthesizing the diamine compound represented by the above formula [3] is not limited, and for example, the nitro group of the dinitro compound represented by the following formula [4] can be used. After conversion to an amine group. [化8]

(R3, R4, R5, r6, & r7 in the formula [4] is synonymous with the formula [3].) When the dinitro compound is reduced, the terminal double bond is not removed, and the catalyst is used for reduction. The reduction reaction is preferably carried out using a solvent such as ethyl acetate, toluene hydrofuran, dioxane or an alcohol, such as zinc, tin or tin chloride, ammonium chloride or hydrogen chloride. The dinitro compound represented by the above formula [4] can be obtained by a method in which a dinitro compound containing -R6-R R3 is bonded to a methyl acid compound or an acrylic compound via an ester bond. As an example, a dinitrate containing R6-R5-R4-R4-R3 substituted with a hydroxyl group (-OH) and an acrylic compound or an acrylic compound, such as (N,N'-dicyclohexylcarbodiimide), may be mentioned. a condensing agent of an amine) or EDC (1-ethyl-3-(3-ylaminopropyl)carbodiimide hydrochloride), or a compound containing R6 substituted by a hydroxyl group (-OH) R6-R5-R4- defines hydrogenation, tetra-, iron-propylene 5-R4- out-of-group DCC dimethyl group R3-14-

S 201213395 A method of reacting a dinitro compound with an acrylic acid chloride compound or an acrylic acid chloride compound in the presence of a base. The dinitro compound containing -R6-R5-R4-R3 can be obtained by a method of binding a dinitrobenzene compound containing -R4-R3 to an alcohol compound containing -R6 via R5. For example, when R5 is a carbon bond (-CH2-), a dinitrobenzene compound containing -R4-R3 halogenated with R4 and an unsaturated bond having an oxidized terminal having an R5 side of R6-R5 may be mentioned. A method in which an alcohol compound is synthesized by a heck reaction or a Sonogashira coupling reaction. When R5 is an ether bond (-〇-), a dinitrobenzene compound containing -R4-R3 halogenated with R4 and a diol compound having two hydroxyl groups bonded to R6 may be reacted in the presence of a base. method. When R5 is an amine bond (-NH-), a method of reacting a dinitrobenzene compound containing -R4-R3 wherein R4 is halogenated with an alcohol compound having an amine group at R6 in the presence of a base can be mentioned. The dinitrobenzene compound containing -R4-R3 is available from a method in which R3 is bonded to -R4 with respect to dinitrobenzene. For example, when R3 is a guanamine bond (-C0NH-), a method of reacting a dinitrobenzoic acid chloride with an amine compound containing R4 in the presence of a base can be mentioned. Further, when R3 is a ruthenium bond (-HNC0-), a method of reacting an amine group-containing dinitrobenzene with an acid chloride containing R4 in the presence of a base can be mentioned. When R3 is an ester bond (-C00-), a method of reacting dinitrobenzoic acid chloride with an alcohol compound containing R4 in the presence of a base may be mentioned. -15- 201213395 Further, a reverse ester is present at R3. In the case of a bond (-OCO-), a method of reacting a dinitrobenzene containing a hydroxyl group with an acid chloride containing r4 in the presence of a base can be mentioned. When R3 is an ether bond (-〇-), a method of reacting a halogen group-containing dinitrobenzene with an R4-containing alcohol compound in the presence of a base can be mentioned. When R3 is an amine bond (-NH-), a method of reacting a halogen group-containing dinitrobenzene with an R4-containing amine compound in the presence of a base can be mentioned. When R 3 is a carbon bond (-CH 2 ), a compound in which a halogen group-containing dinitrobenzene and an unsaturated bond having an R 3 -terminal end having R 4 — R 3 are oxidized may be exemplified by a heck reaction or a head coupling reaction. (Sono Sash ira coup1 ing reaction ) method. Examples of the dinitrobenzoic acid chloride include 3,5-dinitrobenzoic acid chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, and 3,5. - Dinitrobenzyl chloride, 2,4-dinitrobenzyl chloride, and the like. Further, examples of the nitrobenzene containing an amine group include 2,4-dinitroaniline, 3,5-dinitroaniline, and 2,6-dinitroaniline. Examples of the nitrobenzene containing a hydroxyl group include 2,4-dinitrophenol, 3,5-dinitrophenol, and 2,6-dinitrophenol. Examples of the dinitrobenzene containing a halogen group include 2,4-dinitrofluorobenzene, 3,5-dinitrofluorobenzene, 2,6-dinitrofluorobenzene, and 2,4-dinitro group. Iodobenzene, 3,5-dinitroiodobenzene, 2,6-dinitroiodobenzene, and the like. The liquid crystal alignment agent of the present invention contains a polyamine acid obtained by polymerizing a diamine component represented by the above formula [1] and a tetracarboxylic dianhydride component represented by the above formula [2], And the polylysine is dehydrated and closed-16-

S201213395 A liquid crystal alignment agent of at least one type of polymer of a polyimine obtained by a ring, wherein the diamine component contains a diamine represented by the above formula [3]. The diamine component may have one type of diamine represented by the formula [3], or may be mixed in two or more types. The content ratio of the diamine represented by the formula [3] to the diamine component of the formula [1] used for the polymerization reaction of poly-proline is not particularly limited, but it is possible to suppress film peeling or frictional damage during rubbing. From the viewpoint, it is preferably 10 mol% or more, more preferably 3 mol% or more. The 100 mol% of the diamine component may be a diamine represented by the formula [3]. When the diamine content ratio of the formula [3] is less than 100 mol%, the structure and composition of the remaining monoamine component are not particularly limited. Specific examples of the diamine component other than the diamine represented by the formula [3] include a diamine of the formula [1], which is a divalent organic group represented by the following table, and these may be one type. Or use 2 or more types together. 201213395 [Table 1] Β·1 B.2 ;a B-3 xra Β·4 H3Xn〇C B-5 Η3χπχ3 B-6 -b Β·7 B-8 Group B-9 XT Β_10 o-ch3 Valley B- Ll B-12 h3c >-ch3 Β·13 ^s^COOH xc B14 v^^COOH xc B-15 COOH Β16 ch3 X5^CH3 B17 ;0C B-18 Cl Cl Β19 good cf CH3 B_20 B-21 f> -NH Β·22 B-23 xr B-24 -Qr^ Β·25 XT" B-26 % B-27 & Β-28 B-29 H3c ch3 B-30 ch3 ^p- h3c

-18" S 201213395 [Table 2]

B-31 f3c B-32 iXXX B-33 i7〇XX Β·34 B-35 B-36 Β·37 XiV B-38 B-39 Β·40 h3c ch3 xra B-41 F3C 〇f3 xra B-42 f3c Cf3 Β·43 B-44 ^〇r B-45 Β-46 B-47 B-48 Β_49 B-50 B-51 ^〇-=-〇- Β-52 V B-53 B-54 iX -19- 201213395 [Table 3]

Β·55 B-56 ~OOr<]r Β-57 Φο B-58 Β·59 B-60 Β·61 wxr B-62 Β·63 B-64 H3C CH3 XT person. XX Β*65 H3C CH3 B-66 Β-67 B-68 χτχα Β·69 —(CH2)n——n = 2~12 B-70 CH3 -(0^2-0-(0^)2- Ch3 Β·71 ch3 —(CH2)4-C-(CH2)3— ch3 Β·72 CH3 CH3 -(^2-6-(0-12)2-0-(0^2- Β.73 CH3 CH3 -OV卜-卜- B-74 9H3 -(0^2-0-(0^5- H -20- s 201213395 [Table 4] Β·75 <ρπ3 Η B-76 one (ch2)3-o —(ch2)2—o-(ch2)3· B..7.7 ch3 ch3 I(CH2h-S—0—Si—(CH2)3— ch3 ch3 B-78 n = 3~20 Β·79 n = 2 ~20 B-80 OXrwXXj〇T n = 2~20 Β·81 n = 2 〜20 B-82 n = 2 〜20 Β·83 XX. One (CH2)nCH3 η = 5~19 B-84 Double η = 5~19 Β·85 ^^-(CH2)nCH3 η = 0 〜21 B-86 (^)-(CH2)nCH3 η = 0~21 Β-87 η = 0~21 B*88 γγ _ (Z )~〇(cH2>ncH3 η = 0~21 Β·89 3_0_0~〇(cH2)nCH3 η = 0~21 B-90 η = 〇~21 Β-91 Q-〇(CH2)nCH3 η = 0~21 B-92 ""~{"^~〇(〇Η2)η〇Η3 η = 2~19 Β-93 0~(^_y—(^_)-〇(CH2)nCH3 n = 0~21 B-94 :>~ζ~Λ)~〇(CH2)nCH3 η = 0 〜21 Β-95 p^l^hD~cF3 B-96 -21 - 201213395 [Table 5]

When a diamine of B-83 to B-104 is used as a part of the diamine component, the tilt angle of the liquid crystal can be increased when it is used as a liquid crystal alignment film. The structure and composition of the tetracarboxylic dianhydride component represented by the formula [2] used in the polymerization reaction of poly-proline are not particularly limited, and may be one type of compound, or two or more types of compounds may be used in combination. Specific examples of the compound include R4 of the formula [2], which is a tetravalent organic carboxylic acid dianhydride represented by the following table.

-22- S 201213395 [Table 6] Al A-2 h3( , CH3 A-3 l-bc CH3 it A_4 H3C CH3 一^— ----^ h3c CH3 A-5 A-6 文Α·7 A -8 XX A-9 XX A-10 JDC A-ll M A-12 me A-13 Take A-14 ::(π A-15 A-16 ΑΊ7 A-18 V Cl-b A-19 A-20 A-21 V ch3 A-22 A-23 A-24 XX: Α·25 DX A-26 A-2'7 A-28 A*29 A.30 -23- 201213395 [Table 7] Α-31 A- 32 A-33 xnx Α-34 A-35 x/a: A-36 Α-37 A-38 f3cvcf3 )OXC A-39 Α-40 OX A-41 ox A-42 Α-43 A-44 CHj y〇 ?c H3C A-45 CH3 h3c When a tetracarboxylic dianhydride having an alicyclic structure of an organic group of R2 of the formula [2] is used as the tetracarboxylic dianhydride component, the friction resistance is further improved. The content of the tetracarboxylic dianhydride having an organic structure of R2 having an alicyclic structure of the formula [2] is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 50 mol%. The above-mentioned table A-1 to A-24 may be mentioned as R2 having an alicyclic structure. As R2 having an alicyclic structure, A-1 of the above table is preferable. Obtaining polymerization of polylysine The reaction can be carried out by mixing a diamine component and a tetracarboxylic dianhydride component in an organic solvent. The organic solvent in this case is not particularly limited as long as it can dissolve the produced polyamic acid, for example,

N,N-dimethylformamide, N,N-dimethylacetamide 'N-methyl-hydrazine-S 201213395 pyrrolidone, N-methyl caprolactam, dimethyl hydrazine, Tetramethylurea, pyridine, dimethyl hydrazine, hexamethyl argon, γ-butyrolactone and the like. These can be used singly or in combination. Further, even if it is a solvent which does not dissolve polylysine, it can be used after being mixed with the above solvent in the range in which the produced polyamic acid is not precipitated. The water in the organic solvent hinders the polymerization reaction of the poly-proline and becomes the cause of the poly-proline produced by the hydrolysis. Therefore, it is preferred that the organic solvent be dehydrated as much as possible. A method of mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent includes a solution in which a diamine component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component is directly added or dispersed or dissolved. A method of adding an organic solvent, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, a method of mutually adding a tetracarboxylic dianhydride component and a diamine component, and the like. Further, when the tetracarboxylic dianhydride component or the diamine component is formed of a plurality of types of compounds, the polymerization reaction may be carried out in a state in which the plurality of components are mixed in advance, or the polymerization reaction may be carried out in an individual order. The temperature at which the polymerization of polyamic acid is carried out is usually -20 to 150 ° C, preferably 0 to 100 ° C, more preferably 10 to 80 ° C. The higher the temperature, the earlier the polymerization reaction ends, but if it is too high, there is a case where a high molecular weight polyamic acid cannot be obtained. Further, the polymerization reaction can be carried out at any concentration. However, when the concentration is too low, it becomes difficult to obtain a high molecular weight polymer. When the concentration is too high, the viscosity of the reaction liquid becomes too high and it is difficult to uniformly stir. 1 to 50% by mass, preferably 5 to 30% by mass. The initial stage of the polymerization is carried out at a high concentration, and thereafter an organic solvent may be added. -25- 201213395 The molecular weight of the obtained polylysine can be controlled by the molar ratio of the tetracarboxylic dianhydride component to the diamine component used in the polymerization reaction, and the molar ratio is closer to 1:1, and the molecular weight is changed. The bigger. The molecular weight of the polyaminic acid used in the present invention or the polyimine obtained by subjecting the polyamic acid to dehydration ring closure is determined by the easiness of handling and the stability of properties when used as a liquid crystal alignment film, and the weight average molecular weight is 2,000 to 200,000 is preferred, preferably 5,000 to 100,000 « Dehydration ring closure reaction (醯imination reaction) when polyimine is to be obtained from polyglycine can be carried out in an organic solvent in an alkaline catalyst and an acid anhydride In the presence of a stirred polyamine acid. The basic catalyst at this time may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has moderate alkalinity for carrying out the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic dianhydride. Among them, since the acetic acid is finally aminated, the purification of the obtained polyimine is easy to be preferable. As the organic solvent, it can be used (i. The solvent used in the polymerization reaction of the polylysine. The imidization ratio of the polyimine can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. The amount of the catalyst is preferably from 0.5 to 30 times the molar amount of the prolyl group, preferably from 2 to 20 moles. Further, the amount of the acid anhydride is preferably from 1 to 50 moles of the proline group. Preferably, the reaction temperature is from 3 to 30 ° C., preferably from 0 to 180 ° C. The ruthenium imidization ratio of the polyimine used in the liquid crystal alignment agent of the present invention. It is not necessary to 100%, but it can also be a part of the ruthenium imidization. The polyamine or polyimine thus obtained can be weakened by stirring.

-26- S 201213395 The solvent is put into the reaction solution, precipitated, filtered and recovered. The weak solvent to be used at this time is not particularly limited, and examples thereof include methanol, acetone, hexane, ethylene glycol dibutyl ether, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. Wait. The liquid crystal alignment agent of the present invention can be obtained by dissolving at least one polymer of polyglycine as obtained above or polyimine which is subjected to dehydration ring closure of the polyamic acid in an organic solvent. Further, the reaction solution of polylysine or polyimine may be used as it is, or may be diluted with an organic solvent, as an organic solvent used for dissolution of a polymer or dilution of a reaction solution, if the polymerization is soluble. The component is not particularly limited. To cite such a specific example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam , 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sub-milling, tetramethylurea, shame, dimethyl maple, hexamethyl arsenide, γ-butyrolactone, etc. Use these 1 types or mix multiple types. Further, even in the case where the solvent of the polymer component cannot be dissolved alone, the liquid crystal alignment agent of the present invention can be mixed in the range in which the polymer component is not precipitated. It is particularly known that the uniformity of the coating film can be improved when the substrate is coated by moderately mixing a solvent having a low surface tension, and is also applicable to the liquid crystal alignment agent of the present invention. Specific examples of such a solvent include ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, and 1- Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol II Acetate, propylene glycol monomethyl ether-2-acetate, -27- 201213395 propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy) Propanol, methyl lactate, ethyl lactate, η-propyl lactate, η-butyl lactate, isoamyl lactate, and the like. The solid content concentration of the liquid crystal alignment agent of the present invention can be appropriately changed depending on the thickness of the film to be formed, and is preferably 1 to 1% by mass, and preferably 3 to 1% by weight. 8% by mass is preferred. The liquid crystal alignment agent of the present invention may contain other polylysine or polyimine which is additionally polymerized within a range not impairing the effects of the present invention. It may also contain a resin other than polyamine or polyimine. In order to further improve the adhesion of the coating film to the substrate, a known additive such as a decane coupling reaction agent may be added. In the present invention, the liquid crystal alignment agent of the present invention can be coated, dried, and fired to form a film, and the liquid crystal alignment film can be obtained by performing the alignment treatment of the film surface by rubbing. The substrate to which the liquid crystal alignment agent is applied is not particularly limited as long as it has high transparency, and a glass substrate or the like can be used. Further, in the reflective liquid crystal display device, if it is only a single-sided substrate, an opaque substance such as a germanium wafer may be used, and in this case, a material that reflects light such as aluminum may be used as the electrode. Examples of the coating method of the liquid crystal alignment agent include a spin coating method, a printing method, a spray method, and the like. From the viewpoint of productivity, industrially, a transfer printing method such as stencil printing is widely used, and the present invention is also applicable to the present invention. Liquid crystal alignment agent. Further, it is preferred that the liquid crystal alignment agent is filtered using a membrane filter having a pore diameter of 1 μηι to 1 μηη.

-28- S 201213395 The drying step after coating the liquid crystal alignment agent is not necessary, but the time from the application to the baking is not constant for each substrate, or when the baking is not performed immediately after coating, it is dried. The step is preferred. This drying is not intended to cause the shape of the coating film to be deformed by evaporation of the solvent when the substrate is conveyed or the like, and the drying means is not particularly limited. To cite a specific example, a method of drying on a hot plate of 50 to 150 ° C, preferably 80 to 120 ° C, for 5 to 30 minutes, preferably 1 to 5 minutes. The firing after application of the liquid crystal alignment agent is preferably carried out at any temperature of from 100 to 350 °C. Further, even if the liquid crystal alignment agent of the present invention is fired at 200 ° C or lower, a good liquid crystal alignment film can be obtained. For example, at 100 ° C to 200 ° C, a good liquid crystal alignment film can be obtained even at a firing temperature of 100 to 160 °C. This firing can be carried out in a hot plate, a hot air circulating furnace, an infrared furnace or the like. If the thickness of the film after firing is too thick, it is disadvantageous in terms of the power consumption level of the liquid crystal display element. When the film thickness is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5 to 300 nm, more preferably 10 to 10. 100nm. Examples of the material of the rubbing cloth used for the rubbing treatment include cotton, nylon, and enamel. In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can be obtained by the above-described method, and a cell is produced by a known method as a liquid crystal display element. An example of the production of the unit cell is a pair of substrates on which a liquid crystal alignment film is to be formed, and a spacer is spread on the liquid crystal alignment film of the single-sided substrate, and the other single surface is bonded to the inside of the liquid crystal alignment film surface. The method of sealing the liquid crystal by subtracting -29 - 201213395, or sealing the substrate after the liquid crystal is deposited on the liquid crystal alignment film surface of the spacer, and sealing is performed. The spacer thickness at this time is preferably from 1 to 30 μm, more preferably from 2 to ΙΟμηη. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail with reference to examples but the present invention is not limited thereto. Further, the abbreviation of tetracarboxylic dianhydride and diamine which are used in the synthesis examples and the structure are as follows. [Chemistry 9]

-30-

S 201213395 [化 10]

DA-2 DA-1

H2N λ DA-4

The abbreviations of the organic solvents used in the examples and the like are as follows. NMP : N -methyl-2-pyrrolidone BCS : ethylene glycol dibutyl ether THF : tetrahydrofuran DMF : hydrazine, hydrazine - dimethylformamide -31 - 201213395

PhMe · Toluene <Measurement of molecular weight of polymer> The molecular weight of the polyimine or polylysine in the synthesis example is a room temperature gel permeation chromatography (GPC) apparatus (GPC-iOl) manufactured by Shodex Co., Ltd., Shodex The company's pipe string (KD-803, KD-805) is measured as follows.

Column temperature: 50 ° C Dissolution: N,N-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr'H20) is 30 mmol/L, phosphoric acid. Anhydrous crystal (〇-phosphoric acid) is 30 mmol /L, tetrahydrofuran (THF) is 10 ml / L) Flow rate: 1.0 mL / minute calibration line Standard sample: TSK standard polyethylene oxide manufactured by Tosho Co., Ltd. (molecular weight about 900,000, 1 50,000, 1 〇〇, 〇 〇〇, 3 0,000), and polyethylene glycol (molecular weight of about 12,000, 4,000 '1,000) manufactured by Polymer Laboratories Ltd. Measurement of dHNMR> Apparatus: Fourier-transformed superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz Solvent: deuterated dimethyl hydrazine (DMSO-d6), hydrazine-chloroform (CDC13) Reference material: tetramethyl decane (TMS) (Example 1) Synthesis of DA-1 - 32-

S 201213395 [化11]

PhMe reflux M$0 (12m〇 B^I(Z5«q) , F EtaN(1^eq) 〇2N,v 'N〇2 I ¢.0 eq)

OjN N02 89% CHfJ Ο,Ν^ΝΟ,

OH (3j〇9硌KjCOa (1.5 eq) OMF 80-C 0 o2n, ^ 'no2 77% OH <Y^Cl(1*3eq) OT ^ EtsN (1.3 eq) THF rt XX; οΆ ---- --Into J1 〇O2N N〇2 84%

Synthesis of SnCl2 (7.0 eq) (synthesis example O DA-1 precursor DA-1-1 [Chemical 12] HO, '"OH (5.0 eq)

OjN^^'NO; F Et3N (1.2 eq)

PhMe reflux

〇2N IX: DA-1 - 1 In a 500 mL three-necked flask, 56.8 g of 2,4-dinitrofluorobenzene, 300 mL of toluene, 137.0 g of 1,4-butanediol, and 37.0 g of triethylamine were added to heat the system. Stir to 100 °C. After the end of the reaction, 1N hydrochloric acid was added to bring the pH to 6 to 7. The organic layer was extracted with ethyl acetate, and anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, and filtered, and the solvent was distilled off using a rotary distillation apparatus to obtain 69.9 g of the object (yellow-yield) (yield 89%) . The results of 1H-NMR measurement of the target product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-1-1. And 1H-NMR represents a nuclear magnetic resonance spectrum of intramolecular hydrogen. H NMR ( 400 MHz, [ D6 ]-DMSO ) : 58.75-8.76 (d, 1 Η ) , 8.48-8.5 1 ( d,2H ). , 7.57 ( s, 1H ) , 4.33-4.36 -33- 201213395 ( t,2H) , 3.44-3.47 ( t,2H ) , 1.76- 1.84 ( m,2H ), 1.43 - 1.60 ( m,2H ) (Synthesis Example 2) Synthesis of DA-1 precursor DA-1-2 [ 13] o2n

MsCI (1.2 eq) Et3N (2.5 eq) CH2CI2

OMs DA-1-2 To a 500 mL three-necked flask were placed 38.43 g of DA-1-1, methylene chloride (250 mL), methanesulfonyl chloride (20.6 g) and triethylamine (37.9 g), and stirred at room temperature. After the completion of the reaction, the organic layer was extracted with ethyl acetate, and then anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, and filtered, and then distilled with a rotary distillation apparatus to obtain 48.8 g of the object (orange viscous). The rate is 97%). The results of measurement by 1H-NMR of the objective product are shown below. DA- 1 -2 ° !H NMR (400 MHz, [D6]-DMSO): 58.75 -8.77 (d, 1H), 8.48- 8.52 (d, lH), 7.5 7- 7.60 ( d,lH), 4.25-4.40 ( m,4H ) , 3.18-3.19 ( t,3H ) , 1.84-1.89 (m,4H ) (Synthesis Example 3) DA-1 precursor DA-1-3 Synthesis-34- s 201213395 [Chemistry 14]

To a 50 mL three-necked flask, 20.Og of DA-1-2, 200 mL of dimethylformamide, 20.0 g of hydroquinone, and 2.4 g of potassium carbonate were placed, and the amine system was heated to 80 ° C and stirred. After the end of the reaction, 1N hydrochloric acid was added to bring the pH to 6 to 7. The organic layer was extracted with ethyl acetate. anhydrous magnesium sulfate was added to the organic layer and dried over anhydrous, and filtered, and then evaporated. The residue was washed with hot water and filtered, and the filtrate was dissolved in methanol, and the insoluble matter was filtered and removed. The solvent was distilled off again using a rotary distiller, and the residue was separated by silica gel column chromatography (ethyl acetate:hexane = 1: 3 volume ratio) to obtain the object (yellow solid) (yield 77). %). The results of measurement by 1 H-NMR of the target product are shown in the following. From the results, it was confirmed that the obtained solid was the intended DA-1-3. !H NMR ( 400 MHz, [ D6 ]-DMSO ) : δ 8 8§ (s,lH ) , 8.76 ( s,lH ) , 8.49-8.52 ( d, 1H ) , 7'5^'7.6q (d, lH) , 6.72-6.75 ( d,2H ) , 6.64-6.67 ( d,2H ) 4.38-4.41 ( t,2H ) , 3.90-3.93 ( t,2H ) , 1,79'1.93 (m,4H) (Synthesis Example 4) Synthesis of precursor DA-1 -4 of DA-1 -35- 201213395 [Chem. 15]

To a 500 mL three-necked flask were placed 〇g DA-1-3, triethylamine 3_8 g, and THF 200 mL. To the 0 ° C in the cooling system, 3.9 g of methyl propyl chloride chloride was added and stirred at room temperature. After the completion of the reaction, 50 mL of pure water was added and stirred, and ethyl acetate was added thereto, and the organic layer was extracted, and anhydrous magnesium sulfate was added to the organic layer, and dried over anhydrous, and filtered, and then distilled with a rotary distillation apparatus. The residue was recrystallized from ethyl acetate / hexane = 2 / 8 to give the desired product (yellow solid) (yield: 84%). The results of measurement by 1H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the purpose of DA-1-4. * NMR (400 MHz, [D6]-DMSO): δ 8.77 (s, lH), 8.49-8.52 (d, lH), 7.59-7.61 (d, lH), 7.05-7.07 (d, 2H), 6.94 -6.97 ( d,2H ) , 6.25 (s,lH) 5.87 ( s, 1H ) , 4.40-4.43 ( t,2H ) , 4.03-4.05 (t,2H), 1.89- 1.99 ( m,7H ) (synthesis example) 5) Synthesis of DA-1 -36- s 201213395 [Chem. 16]

DA-1 Into a 200 mL three-necked flask, 4.2 g of DA-1-4, tetrahydrofuran 40 mL, and 4 ml of pure water were placed, and the system was stirred, 13.2 g of tin chloride was added, and the system was heated to 70 ° C and stirred. After the completion of the reaction, 200 ml of a 5% aqueous sodium hydrogencarbonate solution was added to adjust the pH to 7 to 8. 80 ml of ethyl acetate was added, and the white precipitate was filtered and removed, and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer and dried over water, filtered, and then evaporated to the solvent using a rotary distillation apparatus. The residue was recrystallized using ethyl acetate / hexane = 3 / 7 to give the title compound (yield: 30%). The results of measurement by 1 H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-1. 'Η NMR (400 MHz, [D6]-DMSO): δ 7.56-7.08 (d, 2H), 6.95-6.97 (d, 2H), 6.47-6.50 (d, lH), 6.25 (s, lH), 5.95 (s, lH), 5.87 (s, lH), 5.73-5.76 (d, lH), 4.42 (s, 2H), 4.34 (s, 2H), 4.00-4.03 (t, 2H), 3.8 1-3.84 ( t, 2H ) , 1.99 ( S, 3H ) , 1.81-1.86 (m, 4H ) (Example 2) Synthesis of DA-2 -37- 201213395 [Chem. 17]

(Synthesis Example 6) Synthesis of DA-2 precursor DA-2-1 [Chem. 18]

To a 300 mL three-necked flask, 16.2 g of dihydrobenzhydryl chloride 16.2 g of tetrahydrofuran 15 〇 niL and 13.9 g of 4-bromo-1-butanol were placed, and the mixture was stirred at room temperature. After the completion of the reaction, the organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, and filtered, and the solvent was distilled off using a rotary distiller to obtain 23.0 g of the object (yellow-yield). Rate 95%). The results of measurement by 1 H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-2-1. NMR (400 MHz, [D6]-DMSO): δ9·04 (s, 1Η), 8.92 (s, 2H), 4.43-4.46 (t, 2H), 3.62-3.65 (t, 2H), 1.90- 1.99 (m, 4H) (Synthesis Example 7) Synthesis of DA-2 precursor DA-2-2 -38- s 201213395 [Chem. 19]

DA-2-2 In a 30 mL three-necked flask, 10 mL of DA-2-1, dimethylformamide, 6.6 g of hydroquinone, 7.2 g of potassium iodide and 4.4 g of potassium carbonate were added to the 30 mL three-necked flask. Heat to 80 ° C and stir. After the end of the reaction, IN hydrochloric acid was added to bring the pH to 6 to 7. The organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and evaporated to dryness, and filtered, and then evaporated. The residue was washed with hot water and filtered, and the filtrate was dissolved in methanol, and the insoluble matter was filtered and removed. The solvent was distilled off again using a rotary distiller, and the residue was separated by silica gel column chromatography (ethyl acetate:hexane = 1: 3 volume ratio) to obtain 5.7 g of the object (yellow solid) (yield 53%) ). The results of measurement by 1H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the target D A-2-2. NMR (400 MHz, [D6]-DMSO): δ 9.03 (s, lH), 8.89 (s, 2H), 8.86 (s, lH), 6.69-6.67 (d, 2H), 6.59-6.63 (d, 2H) ), 4.45-4.49 ( t,2H ), 3.99-3.95 ( t,2H ) , 1.82- 1.97 ( m,4H ) (Synthesis Example 8) Synthesis of DA-2 precursor DA-2-3 -39 - 201213395 [Chemistry 20]

To a 300 mL three-necked flask was placed 5.7 g of DA-2-2, triethylamine 2. 〇g and tetrahydrofuran l〇〇mL. The system was cooled to the inside of the system, and methacrylium chloride 2.0 g was added thereto and stirred at room temperature. After the completion of the reaction, 5 mL of pure water was added and stirred, and then ethyl acetate was added and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer and dried under reduced pressure. After filtration, the solvent was distilled off using a rotary distillation apparatus. The residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1:1) to afford 3.6 g (yellow solid) (yield: 54%). The results of measurement by W-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-2-3. *H NMR (400 MHz, [D6]-DMSO): δ 9.03 (s, lH), 8.89 (s, 2H), 7.02-7.04 (d, 2H), 6.93-6.96 (d, 2H), 6.24 (s , lH ) , 5.87 ( s, lH ) , 4.47-4.50 (t, 2H ) , 4.04-4.07 ( t, 2H ) , 1.89-2.00 ( m, 7H ) (Synthesis Example 9) Synthesis of DA-2 -40 s 201213395 [化21]

DA-2 Into a 200 mL three-necked flask, 3.6 g of DA-2-3, tetrahydrofuran (30 mL) and pure water (30 ml) were added, and the mixture was stirred in the system, and tin chloride (1.6 g) was added thereto, and the system was heated to 70 ° C and stirred. After the completion of the reaction, 200 ml of a 5% aqueous sodium hydrogencarbonate solution was added to adjust the pH to 7 to 8. 80 ml of ethyl acetate was added, and the white precipitate was filtered and removed, and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer and dried over water, filtered, and then evaporated to the solvent using a rotary distillation apparatus. The residue was recrystallized using ethyl acetate / hexane = 3 / 7 to afford 2.8 g (yield of white solid) (yield: 93%). The results of measurement by 1H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the target DA-2. *H NMR (400 MHz, [D6]-DMSO): 57.05-7.08 (d, 2H), 6.95-6.98 (d, 2H), 6.44 (s, 2H), 6.25 (s, lH), 6.02 ( s,lH ) , 5.87 ( s,lH ) , 4.98-5.00 (t,2H ) , 4.23 ( s,2H ),4.01 ( s,2H ) , 2.00-2.08 (t,2H),1.99 ( s,3H) , 1.83- 1.84 (m, 4H) (Example 3) Synthesis of DA-5 201213395 [Chem. 22]

(Synthesis Example 10) Synthesis of DA-5 precursor DA-5-1 [Chem. 23]

To a 300 mL three-necked flask, 10.4 g of DA-2-1, acetone 16 0 mL, 4,4'-bisphenol 14.2 g, potassium iodide 6.0 g, and potassium carbonate 5.5 g were placed, and the mixture was stirred at 50 ° C in a heating system. After the end of the reaction, 1N hydrochloric acid was added to bring the pH to 6-7. The organic layer was extracted with ethyl acetate. Water-free magnesium sulfate was added to the organic layer and then dried and dried, filtered, and then evaporated. The residue was dissolved in isopropyl alcohol, and the insoluble matter was filtered and removed. The solvent was distilled off again using a rotary distiller, and the residue was recrystallized using isopropyl alcohol / hexane = 1/2 to give 6.2 g of the object (yellow brown solid) (yield 46%). The result of measurement by j-NMR of the target is as -42-

S 201213395 is shown below. The resulting solid was confirmed to be DA-5-1 for the purpose. *H NMR ( 400 MHz, C 〇6 ) -DMSO ) : δ 9.43 (s,lH ) , 8.99 ( s,lH ) , 8.88 ( s,2H ) , 7.41-7.43 (d,2H ) ,7.3 5-7.3 8 ( d,2H) , 6.92-6.94 ( d,2H ) , 6.78-6.80 ( d,2H ) , 4.47-4.50 ( t,2H ) , 4.06-4.09 ( t,2H ), 1.90- 1.95 ( m,4H (Synthesis Example 1 1) Synthesis of DA-5 precursor DA-5-2 [Chem. 24]

DA-5-2 Into a 300 mL three-necked flask were placed 6-0 g of DA-5-1, triethylamine 1-3 g, and tetrahydrofuran 120 mL. 2.7 g of methyl propyl hydrazine chloride was added to the 系统 ° C ' in the cooling system, and stirred at room temperature. After the completion of the reaction, after adding 5 mL of pure water and stirring, ethyl acetate was added and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer and dried under reduced pressure. After filtration, the solvent was distilled off using a rotary distillation apparatus, and the residue was subjected to acetic acid. Ethyl acetate/hexane = 1/9 was recrystallized to give 5.5 g of object (yellow solid) (yield: 79%). The results of measurement by 1 Η-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-5-2. 'H NMR (400 MHz, [D6]-DMSO): δ 9.07 (s, lH), 8.90 (s, 2H), 7.62-7.64 (d, 2 H ), 7 _ 5 5 - 7 · 5 8 -43 - 201213395 (d,2H) , 7.21-7.23 ( d,2H) , 7.00-7.02 ( d,2H ) , 6.30 (s,lH),5.92 ( s,1H ),4.49-4.52 ( t,2H ) , 4.01 -4.13 (t, 2H ) , 2.02 ( s, 3H) , 1.9 3 - 1.99 (m, 4H) (Synthesis Example 12) Synthesis of DA-5 [Chem. 25]

To a 200 mL three-necked flask, 5.2 g of DA-5-2, tetrahydrofuran (50 mL) and pure water (50 ml) were added, and the system was stirred, and 1 3.3 g of tin chloride was added thereto, and the system was heated to 70 ° C and stirred. After the completion of the reaction, a 5% aqueous sodium hydrogencarbonate solution was added to bring the pH to 7-8. After adding 80 ml of ethyl acetate, the white precipitate was filtered and removed, and the organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, and filtered, and then evaporated. The residue was recrystallized using ethyl acetate / hexane = 3 / 7 to afford 2.8 g of object (yellow white solid) (yield 8*7%). The results of measurement by 1 H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-5. *Η NMR (400 MHz, [D6]-DMSO): δ 7.65-7-67 (d, 2H), 7.5 9-7.65 (d, 2H), 7.21-7.24 (d, 2H), 7.02-7.04 (d , 2H), 6.45 (s, 2H), 6.30 (s, lH), 6.03 (s, lH), 5.91 (s, lH), 5.00 (s, 4H), 4.24 - 4.26 s -44 - 201213395 • 86 C t,2H) , 4.01-4.13 ( t,2H ) , 2.02 ( s,3H ) , 1.84-1 (m,4H ) (Example 4) Synthesis of DA-6 [Chem. 26]

(Synthesis Example 13) Synthesis of DA-6 precursor DA-6-1 [Chem. 27]

Add 11.2 g of DA-2-1, C-18〇1^, 4,4|-dihydroxybenzophenone 7.7^, potassium iodide 6.58 and potassium 4.6 g to a 300 mL three-necked flask, and heat the system to 5 (TC). After the reaction was completed, 1N hydrochloric acid was added to adjust the pH to 6-7. The organic layer was extracted with ethyl acetate, and then anhydrous sodium sulfate was added to the mixture, and dried, dried, and filtered, and then evaporated. The residue was dissolved in isopropanol, and the insoluble keto acid was filtered and evaporated to remove -45-201213395. The solvent was distilled off again using a rotary distiller, and the residue was recrystallized using isopropyl alcohol / hexane = 1 / 1. 6.2 g of the object (yellow solid) was obtained (yield: 50%). The results of the measurement by the W-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was for the purpose of DA - 6 -1 ° 1H NMR. (400 MHz, [ D6 ) -DMSO ) : δ 10.34 (s, 1 Η ) , 9.03 ( s, lH ), 8.90 ( s, 2 Η ), 7.5 9 - 7.6 5 (m, 4H ) , 7.04-7.06 ( d,2H) , 6.87-6.89 ( d,2H ), 4.48-4.51 ( t,2H ) , 4.16-4.19 ( t,2H ) , 1.94-1 .97 (m,4H ) (Synthesis Example 14) DA-6 Synthesis of the precursor DA-6-2 [28]

5.8 g of DA-6-1, 1.6 g of triethylamine and 60 mL of tetrahydrofuran were placed in a 300 mL three-necked flask. In the cooling system, to 〇 ° C, 2.5 g of methyl propyl hydrazine chloride was added, and the mixture was stirred at room temperature. After the completion of the reaction, 5 mL of pure water was added and stirred, and then ethyl acetate was added and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer and dried under reduced pressure. After filtration, the solvent was distilled off using a rotary distiller, and the residue was dried. Purification by column chromatography (ethyl acetate:hexane = 1 : 4 by volume) gave 5.6 g of object (yellow white-46-

S 201213395 color solid) (yield 85%). The results of measurement by 1H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was for the purpose of DA-6-2 ° !H NMR (400 MHz, [D6]-DMSO): δ 9.03 (s, lH), 8.90 (s, 2H), 7.70-7.77 (m, 4H) , 7.36- 7.38 ( d,2H ) , 7.07-7.09 ( d,2H), 6.33 ( s,lH), 5.95 ( s,lH ) , 4.48-4.51 ( t,2H) , 4.17-4.20 ( t, 2H), 2.03 ( s, 3H ) , 1.96-1.99 ( m, 4H ) (Synthesis Example 15) Synthesis of DA-6 [Chem. 29]

To a 200 mL three-necked flask, 5.5 g of DA-6-2, tetrahydrofuran 50 mL, and 50 ml of pure water were placed, and the system was stirred, 13.3 g of tin chloride was added, and the system was heated to 70 t and stirred. After the end of the reaction, a 5% aqueous sodium hydrogencarbonate solution was added to bring the pH to 7-8. 80 ml of ethyl acetate was added, and the white precipitate was filtered and removed, and the organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, filtered, and the solvent was distilled off using a rotary distiller. The residue was recrystallized using ethyl acetate / hexane = 1 / 9 to give 2.8 g of object (yellow viscous solid) (yield 84%). The results of measurement by iH-NMR of the target are shown in the following -47-201213395. From the results, it was confirmed that the obtained solid was the intended DA-6. 1H NMR (400 MHz, [D6]-DMSO): δ 7.74-7.79 (m, 4H), 7.3 6-7.3 8 (d, 2H), 7.10-7.12 ( d, 2H ), 6.44 ( s, 2H ) , 6.33 ( s,lH ) , 6.02 ( s,lH ) , 5.95 (s,lH ) , 4.99 ( s,4H ) , 4.23-4.26 ( t,2H ) , 4.14-4.1 7 (t,2H ) , 2.02 ( s , 3H ) , 1.84-1.8 7 ( m, 4H ) (Example 5) Synthesis of DA-7 [Chemical 30] Ο ^γΑα(1.0θς) 72%

(1.0 eq) THF

(Synthesis Example 16) Synthesis of DA-7 precursor DA_7_1 [Chem. 31]

O (1_0eq)

HO

OH

DA-7-1

Et3N (1.0 eq)

-► HO THF rt s 201213395 To a 300 mL three-necked flask was added 7.7 g of p-(trans-4-hydroxycyclohexyl)phenol, 4.4 g of triethylamine, and 100 mL of tetrahydrofuran. The inside of the cooling system was cooled to 〇 ° C, and 4.4 g of methacrylic acid chloride was added, and the mixture was stirred at room temperature. After the reaction was completed, 50 mL of pure water was added and stirred, and then ethyl acetate was added and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer and dried under reduced pressure. After filtration, the solvent was distilled off using a rotary distiller, and the residue was used. The ester/hexane = 1/9 was recrystallized to give 7.5 g of the object (yield of white solid) (yield: 72%). The results of measurement by 1H-NMR of the objective product are shown below. For the purpose of confirming the solid obtained, DA·7·1 ° »H NMR (400 MHz, [D6]-DMSO): δ 7.25-7.27 (d, 2H), 7.04-7.06 (d, 2H), 6.25 ( s,lH) ,5.88 (s,lH ) , 4.58 ( s,lH ),3.41-3.50 (m,lH),2.44- 2.50 (m,lH),1.99 ( s,3H ) , 1.8 7- 1.93 (m , 2H), 1.75- 1.7 8 ( m, 2H ) , 1.41-1.51 ( m, 2H ) , 1.23-1.33 (m, 2H ) (Synthesis Example 17) Synthesis of DA-7 precursor DA-7-2 - 49- 201213395 [化32]

5.2 g of DA-7-1, triethylamine 2. 〇g and tetrahydrofuran 50 mL were placed in a 30 mL three-necked flask. 4.6 g of 3,5-dinitrobenzhydryl chloride was added to the inside of the cooling system to 〇 ° C, and stirred at room temperature. After the completion of the reaction, 50 mL of pure water was added and stirred, and ethyl acetate was added thereto, and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer and dried under reduced water, and then filtered, and then evaporated. The residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1:1) to give EtOAc (yield: 75%). The results of measurement by 1 H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-7-2. *H nmr ( 400 MHz, [ D6 ]-DMSO ) : δ 9.05 (s, 1 Η ) , 8.93 ( s, 2H ) , 7.32 - 7.37 ( d , 2H ) , 7.08-7.11 (d, 2H ) , 6.26 ( s,lH ) , 5.89 ( s,lH ) , 5.09-5. 10 (m, 1H ) , 2.66-2.67 ( m, 1H ) , 2.18-2.2 1 ( m,2H ), 1 ·" ( s,3H ) , 1.91-1.94 ( m,2H ) , 1.68-1.76 (m,5H ) -50- s 201213395 (Synthesis Example 18) Synthesis of DA-7 [Chem. 33]

6.8 g of DA-7-2, 60 mL of tetrahydrofuran and 60 ml of pure water were placed in a 200 mL three-necked flask, stirred in the system, and 19.9 g of tin chloride was added thereto, and the system was heated to 70 t and stirred. After the end of the reaction, a 5 % aqueous solution of sodium hydrogencarbonate was added to bring the pH to 7-8. After adding 80 ml of ethyl acetate, the white precipitate was filtered and removed, and the organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, and filtered, and then evaporated. The residue was recrystallized from ethyl acetate / hexane = 1 / 9 to give 5.8 g of object (yield white solid) (yield 98%). The results of measurement by 1 H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was DA-7. *H NMR (400 MHz, [D6]-DMSO): δ 7.33-7.35 (d, 2H), 7.07-7.10 (d, 2H), 6.43 (s, 2H), 6.26 (s, lH), 6.02 (s , lH), 5.89 ( s, lH), 5.02 ( s, 4H), 4.85-4.90 ( m, lH ) , 2.59-2.65 ( m, 1H ) , 2.07-2.10 -51 - 201213395 (m, 2H), 2.00 (s, 3H), 1.86- 1.89 (m, 2H), 1.69- 1.89 (m, 4H) (Example 6) Synthesis of liquid crystal alignment agent CBDA 1.94g ( 0.0099mol), and 3.84g (O.Olmol) DA-2, in NMP 23.14g, was reacted at room temperature for 16 hours to prepare a polyaminic acid solution (PAA-1). The polyamic acid had a number average molecular weight of about 5,000 and a weight average molecular weight of about 8,000. NMP and BCS were added to the polyglycine solution and stirred to prepare a polyamine (PAA-1) of 6% by mass, NMP of 74% by mass, and BCS of 20% by mass. A liquid crystal alignment agent was obtained by pressure filtration of a 1 μηι membrane filter. (Example 7) Synthesis of liquid crystal alignment agent: CBDA 1.76 g ( 0.009 mol) and 4.6 0 g (0.0 1 m ο 1 ) of DA-5 were reacted in NMP 3 6.10 g at room temperature for 16 hours. A polyaminic acid solution (PAA-4) was prepared. The polyamic acid has a number average molecular weight of about 1,000,000 and a weight average molecular weight of about 80,000. NMP and BCS were added to 10 g of the polyaminic acid solution, and the mixture was stirred to prepare a polyamic acid (PAA-4) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and the pore diameter was 1 The membrane filter of μηι was subjected to pressure filtration to obtain a liquid crystal alignment agent. (Example 8) Synthesis of liquid crystal alignment agent -52-

S 201213395 CBDA 1.94 g (0.099 mol) and 4.60 g (0.01 mol) of DA-6 were reacted in NMP 27.31 g at room temperature for 16 hours to prepare a polyaminic acid solution (PAA-5). The polyamic acid has an average molecular weight of about 20,000 and a weight average molecular weight of about 200,000. NMP and BCS were added to the polyglycine solution and stirred to prepare a polyamine (PAA-5) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, followed by pore diameter. A 1 μηη membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent. (Example 9) Synthesis of liquid crystal alignment agent CBDA 1.94 g (0.099 mol) and 3 · 9 4 g (0.0 1 m ο 1 ) of DA-7 were reacted in NMP 33.35 g at room temperature for 16 hours. A polyaminic acid solution (PAA-6) was prepared. The polyamine has a number average molecular weight of about 700 and a weight average molecular weight of about 300 00. Adding NMP and BCS· to the polyglycine solution l并g and stirring to prepare a polyamic acid (PAA-6) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, followed by fine A membrane filter having a pore size of 1 μm was subjected to pressure filtration to obtain a liquid crystal alignment agent. (Comparative Example 1) Synthesis of liquid crystal alignment agent: CBDA 1.94 g ( 0.0099 mol) and 2.64 g (O.Omol) of DA-3 were reacted in NMP 1 8.34 g at room temperature for 16 hours to prepare polyamine. Acid solution (PAA-2). The polyamine has a number average molecular weight of about 22,000 and a weight average molecular weight of about 62,000. After adding the NMP and BCS to the polyaminic acid solution 1 〇g -53 - 201213395 and stirring, the polyamine acid (PAA-2) was 6 mass%, the NMP was 74 mass%, and the BCS was 20 mass%. The liquid crystal alignment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm. (Comparative Example 2) Synthesis of liquid crystal alignment agent: CBDA 1.86 g (0.095 mol) and 1.08 g (0·0 1 m ο 1 ) of DA-4 were subjected to N6 1 6.68 g for 16 hours at room temperature. After the reaction, a polyaminic acid solution (PAA-3) was prepared. The polyamine has a number average molecular weight of about 8,000 and a weight average molecular weight of about 18,000. NMP and BCS were added to the polyglycine solution and stirred to prepare a polyamine (PAA-3) of 6% by mass, NMP of 74% by mass, and BCS of 20% by mass. A liquid crystal alignment agent was obtained by pressure filtration of a 1 μm thin film filter. With respect to the liquid crystal alignment agents prepared in the above Examples 6 to 9 and Comparative Examples 1 and 2, a substrate having a liquid crystal alignment film was produced as follows. <Evaluation of Friction Resistance> The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70 ° C for 70 seconds, and then dried on a hot plate at 120 ° C. The film was fired in a minute to form a coating film having a film thickness of 10 nm. The coating film surface was rubbed with a rubbing apparatus having a roll diameter of 120 mm at a roll rotation speed of 100 rpm, a roll speed of 50 mm/sec, and a pushing amount of 55 mm to obtain a substrate with a liquid crystal alignment film. The surface of the obtained liquid crystal alignment film was observed by a confocal laser microscope, and the following evaluation was performed. Following -54-

S 201213395 indicates the evaluation result of friction tolerance. 〇: No shavings or frictional injuries were observed. △: A shaving or a rubbing injury was observed. X: Film peeling was observed or a scratch was visually observed. [Table 8]

Liquid crystal alignment agent polymer component friction resistance Example 6 PAA-1 〇 Example 7 PAA-4 〇 Example 8 PAA-5 〇 Example 9 PAA-6 〇 Comparative Example 1 PAA-2 Δ Comparative Example 2 PAA-3 X INDUSTRIAL APPLICABILITY The liquid crystal alignment agent of the present invention can provide a liquid crystal alignment film having a uniform liquid crystal alignment and no misalignment, so that the cost of firing the alignment film can be reduced, and it can be applied to a glass substrate or a glass substrate. A liquid crystal display element or the like using a plastic substrate. The contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2010-148, filed on June 30, 2010 are hereby incorporated by reference. -55-

Claims (1)

201213395 VII. Patent Application No. 1 A liquid crystal alignment agent which is obtained by polymerizing a diamine component represented by the following formula [1] and a tetracarboxylic dianhydride component represented by the following formula [2] a polyamic acid and at least one polymer selected from the group consisting of polyimine obtained by dehydration ring-closure of the polyamic acid, wherein the diamine component comprises the following formula [3] Diamine; [Chemical 1] H2N-Rj-nh2 [ 1 ] (I is a divalent organic group) [Chemical 2] Ο 〇 [2] (R2 is a tetravalent organic group) [Chemical 3] [3] (wherein R3 represents a group selected from the group consisting of -CH2-, -0-, -CONH-, -NHCO-, -COO-, -OCO-, and -NH-; R4 represents a single bond or The exfoliation group having a carbon number of 1 to 10, the one or a plurality of -CH2 - of the stretching base may be replaced by -56-S 201213395 -CFy, and any of the groups exemplified below are not adjacent to each other. The case 'may be replaced by these groups; -〇-, -NHCO-, -CONH-, -C〇〇·, -OCO-, -NH-; R5 represents a single bond, -CH2-, -〇- or NH-; R6 represents a divalent organic group having 5 or 18 carbon atoms at least one aromatic ring at the terminal, and the ring may be a carbocyclic ring or a heterocyclic ring, and 1 or a plurality of hydrogens of the ring may also be formed. It may be substituted by a fluorine atom; R7 represents hydrogen, methyl or trifluoromethyl). 2. For the liquid crystal alignment agent of claim 1, wherein R3 in the formula [3] is _〇• or _C〇〇_. 3. The liquid crystal alignment agent of claim 1 or 2 wherein R4 in the formula [3] is an alkylene group having 1 to 4 carbon atoms. 4. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein R5 in the formula [3] is -〇-. The liquid crystal alignment agent according to any one of the items 1 to 4, wherein R6 in the formula [3] is an I,4-phenylene group. 6. The liquid crystal alignment agent according to any one of claims 1 to 5 wherein R7 in the formula [3] is a methyl group. The liquid crystal alignment agent of any one of the above-mentioned items of the formula [1], wherein the diamine component represented by the formula [3] contains 30 mol% or more of the diamine represented by the above formula [3]. The liquid crystal alignment agent according to any one of the items 1 to 7, wherein the tetracarboxylic dianhydride component represented by the formula [2] has an alicyclic structure of R2 of the formula [2]. Carboxylic dianhydride. -57-201213395 9. A liquid crystal alignment film characterized by being obtained by the liquid crystal alignment of any one of the first to eighth aspects of the patent application. A liquid crystal alignment film which is applied to a substrate by a liquid crystal alignment agent according to any one of claims 1 to 8 and is fired at a temperature of 200 ° C or lower. Get the friction. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 9 or item 10 of the patent application. 12. A diamine characterized by the following formula [3]; [Chemical 4] (wherein R3 represents a group selected from the group consisting of -CH2·, -〇-, -CONH-, -NHCO-, -COO-, -OCO-, and -NH-; R4 represents a single bond or a carbon number of 1 ～10 alkylene, 1 or a plurality of _CH 2 - of the alkylene group may be substituted by -CFZ-, and may be substituted for any of the groups exemplified below which are not adjacent to each other. ;-〇-, -NHCO-, -CONH-, -COO- '-OCO- '-NH-; R5 represents a single bond, -CH2-, -0 - or NH-: R6 represents 1 or a plurality of rings The divalent organic group 'having a carbon number of 5 to 18 at least one aromatic ring at the terminal may be a carbocyclic ring or a heterocyclic ring, and 1 or a plurality of hydrogens of the ring may be substituted by a fluorine atom; R 7 represents hydrogen. , methyl or trifluoromethyl). -58- S 201213395 D A5 13. A diamine characterized by a diamine represented by the following formula DAI, formula DA2, formula, formula DA6 or formula DA7; 59- 201213395 Four designated representative maps: (1) The designated representative circle of this case is: None (2) The symbol of the symbol of this representative figure is simple: No 201213395 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention: None -4- S