TW201206994A - Liquid crystal alignment agent containing polyamic acid ester, and liquid crystal alignment film - Google Patents

Abstract

Disclosed is a liquid crystal alignment agent characterised by containing component (A) and component (B). Component (A): a polyamic acid ester which has a repeating group represented by general formula (1), and which fulfils the condition below. Component (B): a polyamic acid which has a repeating group represented by general formula (4). (Condition): In general formula (1), at least one among X1, Y1, A1, A2 has a substituent of at least one structure selected from a group comprising general formula (2) and general formula (3). (In general formula (1), X1 represents a tetravalent organic group, Y1 represents a divalent organic group, R1 represents a C1-5 alkyl group, A1 and A2 independently represent a hydrogen atom or an optionally substituted C1-20 alkyl group or alkenyl group.) (In general formulae (2, 3), D1 and D2 independently represent a protective group which is replaced by hydrogen by heat. B1 represents a single bond or a divalent organic group. In general formula (3), the ester group is bound to a carbon atom.) (In general formula (4), X2 represents a tetravalent organic group, Y2 represents a divalent organic group, and A1 and A2 have the same definition as in general formula (1).)

Description

201206994 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent obtained by a liquid crystal alignment agent containing a polylysine having a thermally dissociable protecting group and a polyphthalic acid, and a liquid crystal alignment film obtained by the liquid crystal alignment agent invention. [Prior Art] A liquid crystal display element used in a liquid crystal television, a liquid crystal display or the like is usually provided with a liquid crystal alignment film for controlling the liquid crystal alignment state inside the element. A liquid crystal alignment film has been mainly applied to a glass substrate by using a liquid crystal alignment agent containing a solution of a polyamidene precursor such as polyamido acid (poly ami do aci d) or a soluble polyimine as a main component. The polyimine-based liquid crystal alignment film obtained by calcination is mainly used. In addition to the high definition of the liquid crystal display element, in order to suppress the decrease in the contrast of the liquid crystal display element or to reduce the image sticking phenomenon, in addition to the excellent liquid crystal alignment property or the pretilt angle of the stability and stability of the liquid crystal alignment film, It is important for the high voltage holding rate to suppress the residual image generated by the AC drive, generate a small residual charge when a DC voltage is applied, and/or to moderate the characteristics of the residual charge accumulated by the DC voltage. Polyimide-based liquid crystal alignment films have been proposed in response to the above requirements. For example, a liquid crystal alignment film capable of shortening the time until the disappearance of a DC voltage to disappear is proposed, and a specific structure may be used in addition to a polyaminic acid or a polyamido acid containing a quinone imine group. -5-201206994 A liquid crystal alignment agent of a quaternary amine (for example, Patent Document 1), or a liquid crystal alignment agent containing a soluble polyimine having a specific diamine compound having a pyridine skeleton or the like as a raw material (for example, Patent Document 2) ) and other proposals. Further, the liquid crystal alignment film having a high voltage holding ratio and shortening the time from the occurrence of the residual voltage due to the DC voltage to the disappearance, for example, in the case of polylysine or a ruthenium iodide polymer thereof, may further contain a pole. a small amount of a liquid crystal alignment agent of a compound selected from the group consisting of a compound having one carboxylic acid group in the molecule, a compound having one carboxylic acid anhydride group in the molecule, and a compound having one tertiary amino group in the molecule (for example, Patent Document 3) Proposal. Further, a liquid crystal alignment film having excellent liquid crystal alignment, high voltage holding ratio, low image sticking, excellent signal reliability, and high pretilt angle is known, for example, using a tetracarboxylic dianhydride having a specific structure and A liquid crystal alignment agent of cyclobutane obtained from a tetracarboxylic dianhydride and a specific diamine compound, or a quinone imidized polymer thereof (for example, Patent Document 4). Further, in a liquid crystal display device of a lateral electric field driving method, a method of suppressing image sticking due to AC driving is known, and it is known to use a liquid crystal alignment property and have a large interaction with liquid crystal molecules. A method of a specific liquid crystal alignment film (for example, Patent Document 5). However, in recent years, LCD TVs with large screens and high definition have been the mainstays, and the requirements for image sticking have become increasingly stringent, and they are also required to withstand long-term use in harsh environments. At the same time, the liquid crystal alignment film used must have a higher reliability than the conventional one, so that various characteristics of the liquid crystal alignment film, in addition to having good initial characteristics, such as -6-201206994, also seek a kind of Those who maintain good characteristics after prolonged exposure at high temperatures. Further, among the polymer components constituting the polyimine-based liquid crystal alignment agent, the polyglycolate is proposed to be subjected to heat treatment at the time of quinone imidization treatment, and does not cause a problem of molecular weight reduction, and is excellent. Liquid crystal alignment stability • Report of excellent reliability (for example, Patent Document 6). However, polyglycolate generally has problems such as high volume resistance and an increase in residual charge when a DC voltage is applied, so that there is still no improvement in the polyazide containing the polyphthalate. A method of characterizing an amine-based liquid crystal alignment agent. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei No. Hei No. Hei. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. 2003-269 No. [Problem to be Solved by the Invention] The present invention relates to a method for improving the properties of a liquid crystal alignment agent containing the above polyphthalate ester, and proceeds to investigate a polyglycolate having excellent properties from the viewpoint of electrical characteristics. Liquid crystal alignment agent obtained by doping polyacrylic acid 201206994. However, the liquid crystal alignment film obtained by the liquid crystal alignment agent obtained by mixing the polyphthalate with polyphthalic acid has not reached a satisfactory stage in terms of liquid crystal alignment and electrical properties. That is, the liquid crystal alignment film obtained by the liquid crystal alignment agent containing the polyphthalate and the poly-proline does not cause white turbidity, and the low voltage retention rate and DC voltage accumulation of the film under high temperature use are generated. The afterimage, and the situation of the afterimages caused by the AC drive. The present invention provides a liquid crystal alignment agent containing a polyphthalate and a poly-proline, which can have excellent liquid crystal alignment and electrical properties, and can also have transparency without white turbidity. The liquid crystal alignment agent of the liquid crystal alignment film is for the purpose. [Means for Solving the Problem] The liquid crystal alignment film formed of a liquid crystal alignment agent containing a polyphthalate and a polyglycolic acid was analyzed by the inventors of the present invention, and it was confirmed that fine irregularities were formed on the surface of the film. . However, it has been found that when a polyglycolate having a specific structure having a functional group which can be substituted by a hydrogen atom by heat treatment is used, the fine unevenness formed on the surface of the film can be remarkably suppressed, and In order to reduce the fine unevenness generated on the surface of the film, the above problem can be eliminated by using a liquid crystal alignment agent containing a polyphthalate and polylysine. Further, based on the results of the investigation by the present inventors, a polyphthalate having a specific structure having a functional group which can be substituted by a hydrogen atom via the above heat treatment is known, and even if it is a high molecular weight, the organic solvent is also It has good solubility, and the liquid crystal alignment agent containing the polyphthalate can form a liquid crystal alignment agent having a lower viscosity even when the organic solvent contains a high concentration. Thus, For example, it has become easier to produce a liquid crystal alignment film by an inkjet method, and it is also easy to manufacture a liquid crystal alignment film having a high thickness. That is, the present invention has been completed based on the above findings, and has the following main contents. 1. A liquid crystal alignment agent comprising the following (A) component and (B) component, (A) component: a polyphthalate having a repeating unit represented by the following formula (1), and A polyglycolate which satisfies the conditions of any one of the following (i) to (iii). [Chemical 1]

(wherein, 乂1 is a tetravalent organic group, ¥ is a divalent organic group, L is an alkyl group having 1 to 5 carbon atoms, and human and A2 each independently represent a hydrogen atom or a carbon which may have a substituent A number of 1 to 20 alkyl, alkenyl, alkyl). (i) X丨, Y丨 or both of the formula (1) is a monovalent or divalent substituent having a structure selected from at least one of the groups of the following formulas (2) and (3) . (ii) Α, Α2 or both of the formula (1) is a monovalent or divalent -9- of a structure having at least one selected from the group consisting of the following formulas (2) and (3) 201206994 Dai Ke. (iii) X!, Υ2 or both of the formula (1) are monovalent or divalent substituents having at least one structure selected from the group consisting of the following formulas (2) and (3), Further, Ai, Α2 or both are monovalent or divalent substituents having at least one structure selected from the group consisting of the following formulas (2) and (3). [Chemical 2]

-N- (2) (Ports of formulas (2) and (3)! and 02 are each a protecting group which may be substituted by a hydrogen atom by heat treatment. 1 is a single bond or a divalent organic group. The atom to which the ester group in (3) is bonded is a carbon atom). (Β) component: a poly-proline which has a repeating unit represented by the following formula (4).

(wherein Χ2 is a tetravalent organic group, ¥2 is a divalent organic group, and humans 1 and 八2 have the same definitions as those of the formula (1)). 2. The liquid crystal alignment agent according to the above 1, wherein the content of the component (A) and the content of the component (B) are 1/9 to 9/1 by mass ratio (a/b). The liquid crystal alignment agent of the above-mentioned 1 or 2, wherein the total content of the component (A) and the component (B) is 丨~"% by mass -10- 201206994 4. The above 1 to 3 The liquid crystal alignment agent according to any one of the preceding claims, wherein the 'protecting group Di' is at least one selected from the group consisting of tert-butoxycarbonyl and 9-fluorenylmethoxycarbonyl. The liquid crystal alignment agent according to any one of the above 1 to 4, wherein the protective group 〇2 is tert-butyl. 6. The liquid crystal alignment agent according to the above-mentioned 1 to 5, wherein the component (A) is a substituent represented by a structure having at least one selected from the group consisting of the following formulas (5) and (6). Polyphthalate. [Chemical 4]

(In the formula (5), B2 is a single bond and a divalent organic group, and R2, R3 and R4 each independently represent a hydrogen atom or a monovalent organic group having a carbon number of 1 to 20. [化5] o ch3

II-b3』一〇---ch3 (6) ch3 (In the formula (6), B3 is a single bond or a divalent organic group. Among them, the t-butoxycarbonyl group disclosed by the formula (6) is bonded. The atom is a carbon atom). 7. The liquid crystal alignment agent according to any one of the above 1 to 6, wherein the component (A) is a formula (1)! The structure has a polyamine derivative having a substituent represented by at least one structure selected from the group consisting of the formulas (5) and (6). 8. The liquid crystal alignment agent according to any one of the above 1 to 7, wherein the component (A) is A, *A2 or both of the formula (1) or a formula (5 -11 - 201206994) And (6) a polyperurethane having a substituent represented by at least one of the selected ones selected from the group. The liquid crystal alignment agent of any one of the above-mentioned (1), wherein the component (A) is Y of the formula (1) and is a polyamine amide having a structure represented by the following formula (7). . [Chemical 6]

4 (5) and (6) The structure selected by at least one of the groups. a is an integer). The liquid crystal alignment agent according to any one of claims 1 to 9, wherein the component (A) is a formula (1) having at least one selected from the group represented by the following formula. Kind of construction. -12- 201206994 [化7] jCk jCu n=2^-6

1. The liquid crystal alignment agent according to any one of the above-mentioned formulas (1) and (4), wherein the structures of Xi&X2 are each independently represented by the following formula. Construct at least one of the selected groups. [化8]

HjC h3c ch3 h3c ch3

The liquid crystal alignment agent according to any one of the preceding claims, wherein, in the formula (4), Y2 is at least selected from the group represented by the following formula. 1 species. [Chemistry 9]

(13) A liquid crystal alignment film which is obtained by coating and baking the liquid crystal alignment agent described in any one of the above items ι to 12. A liquid crystal alignment film obtained by applying the liquid crystal alignment agent according to any one of the above items 1 to 12, baking, and irradiating the liquid crystal alignment film obtained by polarized ultraviolet light. [Effect of the Invention] The present invention provides an improvement in the interface characteristics of a liquid crystal and a liquid crystal alignment film by reducing the fine unevenness on the surface of the obtained liquid crystal alignment film, reducing the image sticking caused by the AC driving, and the like, and improving the voltage holding ratio and the ion. The liquid crystal alignment agent of the present invention, the liquid crystal alignment agent of the present invention has a low viscosity even when it contains a high concentration in an organic solvent, and has, for example, a liquid crystal alignment agent which improves the reliability of the liquid crystal alignment agent. The method of manufacturing a liquid crystal alignment film by an inkjet method can be made easier, and the advantage of a liquid crystal alignment film having a relatively high thickness can be easily obtained from -14 to 06,006. In the present invention, when a polyphthalate having a specific structure having a functional group substituted with a hydrogen atom via heat is used, why is it possible to reduce fine irregularities generated on the surface of the film, and to eliminate the conventional polyamine The disadvantages of the liquid crystal alignment agent of the acid ester and the poly-proline are still unclear, but it is presumed that the effect obtained by the following reason is almost the same. That is, in the liquid crystal alignment film formed by removing the solvent from the liquid crystal alignment agent in which the polyphthalate and the polyphthalic acid are dissolved in the organic solvent, the ester polyglycine having a lower surface free energy than the poly-proline is biased. If the polyglycolate is separated from the polylysine, agglomerates of polyglycine will form in the polyphthalate phase, or poly(phthalic acid) will form a polypeptone. The agglomerate of the amine ester forms a film having a large number of fine irregularities on the surface of the film. On the other hand, the liquid crystal alignment agent of the present invention is a polyphthalate having a specific structure having a functional group substituted with a hydrogen atom as described above by heat treatment, and the solvent is removed by the liquid crystal alignment agent to form a liquid crystal alignment film. In the meantime, the phase separation of the polyperurethane and the poly-proline can be promoted, so that the polyamine fatty acid ester does not exist in the manner of mixing with the poly-proline which is present near the surface of the membrane, and the poly-proline does not It exists in a manner of mixing with the polyamidolate at the inside of the film and at the interface of the substrate. That is, on the surface of the obtained liquid crystal alignment film, due to the phase separation state of the polyphthalate and the polyaminic acid, a rough surface can be formed without forming irregularities, and the film due to occurrence of irregularities can be reduced. White turbidity. Moreover, the liquid crystal alignment film having a smooth surface having no unevenness and the like has excellent alignment properties because of its alignment stability, and the inside of the film and the electrode boundary are useful for the purpose of use. Can not make the special good, the child is the same as the excellent base, the phase can have the hydrogen base can be formed by the official can be shaped and the official, the heat of the story is made, the structure of the former ester acid In the presence of an amine, the amine is described in the presence of an amine, and there is no polycondensation in the polycondensation of the sympathetic group. The membrane can be baked to the functional vinegar and burned with the official acid or crystalline amine. Chemical structure. The deuterated film of decylamine has. Polyimide has a specific film, and some of them are specially formulated to have a liquid crystal after being deposited, and the liquid surface is not accepted. [Inventive embodiment] <Polyurethane and polypeptone Amino acid> The polyphthalate and polylysine used in the present invention are polyimine precursors used in the production of polyimine, and the following oxime imidization can be carried out by heating. The polymer at the site of the reaction. [化10]

The polyphthalate and polyglycine-16·201206994 contained in the liquid crystal alignment agent of the present invention each have the following formula (1) and the following formula (4). [化 12]

In the above formula (1), R! is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms. Polyurethane esters increase the temperature at which the imidization is carried out with an increase in the number of carbon atoms in the alkyl group. Therefore, R, it is easy to carry out the oxime imidization, and the methyl group is particularly preferable. In equations (1) and (4), eight! And Az each independently represents a hydrogen atom, or an alkyl group, an alkenyl group or an alkynyl group having 1 to 20 carbon atoms which may have a substituent. Specific examples of the above alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl 'octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, a dicyclohexyl group and the like. The alkenyl group, for example, one or more CHz-CH2 structures present in the above alkyl group are replaced by a CH=CH structure. More specifically, for example, vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, ring Propylene, cyclopentenyl, cyclohexenyl and the like. The above-mentioned alkynyl group, for example, one or more CHyCH2 structures present in the upper alkyl group are substituted by a C=C structure, more specifically, for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group or the like. When the alkyl group, the alkenyl group or the alkynyl group described above has a carbon number as a whole, it may have a substituent, and it may further form a ring structure via a substituent. Further, the formation of a ring structure via a substituent means that the substituents are bonded to each other or a part of the substituent is bonded to a part of the mother skeleton to form a ring structure. Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, and a sulfur-17-201206994 vine group or a phosphate group. a halogen group in a β substituent such as a decylamino group, an alkyl group, an alkenyl group or an alkynyl group, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like. The aryl group in the substituent is, for example, a phenyl group or the like. The aryl group may be further substituted with the other substituents described above. The organooxy group in the substituent is, for example, a structure represented by 〇_R. These R may be the same or different, such as the aforementioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted by the aforementioned substituents. Specific examples of the organooxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group and the like. The organic thio group in the substituent, such as the structure represented by _S-R. The R may be, for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group or the like. These R may be further substituted by the substituents described above. Specific examples of the organic sulfur group include a methylthio group, an ethylthio group, a propylthio group 'butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group and the like. An organic decyl group in the substituent, such as the structure represented by -Si-(R)3. The R may be the same or different, such as the aforementioned alkyl, alkenyl, alkynyl, aryl, and the like. These R may be further substituted by the aforementioned substituents. Specific examples of the organic decyl group are, for example, trimethyldecyl, triethyl decyl, tripropyl decyl, tributyl decyl, tripentyl decyl, trihexyl decyl, pentyl dimethyl decyl, Hexyl dimethyl decyl group and the like. The thiol group in the substituent, for example, the structure represented by -C(0)-R. This R is, for example, an alkyl group, an alkenyl group, an aryl group or the like as described above. These R may be further substituted by the aforementioned substituents. Specific examples of the sulfhydryl group include, for example, methyl ketone, ethyl ketone, propyl ketone, butyl -18-201206994 fluorenyl, isobutyl decyl, pentylene, isoamyl, hexyl, and the like. The ester group in the substituent is, for example, a structure represented by -C(0)0-R, or -0C(0)-R. The R may be, for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. The thioester group in the substituent, such as -C(S)0-R, or the structure represented by -OC(S)-R. The R may be, for example, the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group or the like. These R may be further substituted by the aforementioned substituents. The phosphate group in the substituent, for example, the structure represented by -OP(0)-(OR)2. These R may be the same or different, such as the aforementioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted by the aforementioned substituents. Amidino group in the substituent, such as -C(0)NH2, or -C(0)NHR, -NHC(0)R, -C(0)N(R)2'-NRC(0)R Indicates the construction. These R may be the same or different, such as the aforementioned alkyl, alkenyl, alkynyl, aryl, and the like. These R may be further substituted by the aforementioned substituents. The aryl group in the substituent is, for example, the same as the aforementioned aryl group. The aryl group may be further substituted with the other substituents described above. The alkyl group in the substituent is, for example, the same as the alkyl group described above. The alkyl group may be further substituted with the other substituents described above. The alkenyl group in the substituent is, for example, the same as the above-mentioned alkenyl group. The alkenyl group may be further substituted with the other substituents described above. The alkynyl group in the substituent is, for example, the same as the alkynyl group described above. This alkynyl group can be further substituted with the other substituents described above. In general, when a large volume structure is introduced, there is a possibility that the reactivity of the amine group or the liquid crystal alignment property is lowered, and A, and VIII are hydrogen atoms, or the carbon number of the substituent having -19-201206994 is 1 The alkyl group of ～5 is more preferably a hydrogen atom, a methyl group or an ethyl group. In the above formulas (1) and (4), 乂1 and 乂2 each independently represent a tetravalent organic group, and 丫1 and Y2 each independently represent a divalent organic group. When X and X2 are organic groups of 4 valences, there is no particular limitation. In the polyimine precursor, Χι and χ2 may be a mixture of two or more types. When specific examples of Χι and X2 are listed, for example, X-1 to X-46 and the like which are each independently shown below. In terms of the easiness of monomer acquisition, X, X2 are independent X-1, X-2, X-3, X-4, X-5, X-6, X-8, X- 16. X-19, X-21, X-25, X-26, X-27, X-28 or X-32 are preferred. [Chem. 13]

x鸯H3£ H:5=fMay female XX CH3 H3C CH3 (X-1) (X-2) (X-3) (X-4 丨(Χ·5> (X-6) <X- 7) (X-8) (X-9) (X-10) (X-11) (X-12) (X-13) (X-14) [Chem. 14]

-20- 201206994 [Chem. 15]

[Chemistry 16]

Further, in the formulas (1) and (4), when 'γι and γ2 are divalent organic groups', there is no particular limitation. In the polyimine precursor, γ 1 and υ 2 may be a mixture of two or more types of "Y i and Υ 2", for example, the following Υ-1 to Υ-1 03. In view of the fact that a good liquid crystal alignment property can be obtained, it is preferable to introduce a diamine having a high linearity into a polyphthalate, and Y 1 , γ-10 , Y-ll, Y-12, Y-13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y-45, Y- 46. Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, Y-98 diamine are more preferred. Further, in order to increase the pretilt angle, it is preferred to introduce a side chain having a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a diamine having a structure obtained by combining the polyamines. , Y ! Υ-76, Υ-77, Υ-78, Υ-79, Υ-80, Υ-81, Υ-82, Υ·83, Υ-84, Υ-85, Υ-86, Υ- 87, Υ-88, Υ-89, Υ-90, Υ-91 -21 - 201206994, Υ-92, Υ-93, Υ-94, Υ-95, Y-96, or Y-97 diamine is Better. When the diamine is added in an amount of from 1 to 50 mol% based on the total diamine, an arbitrary pretilt angle can be obtained. When the volume resistivity of the polyphthalate is lowered, the image sticking due to the accumulation of the DC voltage can be reduced, so that a structure having a hetero atom, a polycyclic aromatic structure, or a diamine having a biphenyl skeleton can be introduced into the poly It is preferred for proline, Υ2 to Υ-19, Υ-23, Υ·25, Υ-26, Υ-27, Υ-30, Υ-31, Υ-32, Υ-33, Υ-34, Υ -35, Υ-36, Υ-40, Υ-41Υ-42, Υ-44, Υ-45, Υ-49, Υ-50, Υ-51, or Υ-61, Υ-98, or Υ-99 More preferably, it is preferably Υ-31, Υ40, γ·98, or Υ-99. [Chem. 17]

[Chem. 18]

-22- 201206994 [Chem. 19]

Σ-47) (Υ-4β) (Υ-49) (Υ-5〇) (V-51) [Chem. 21] —(〇<2) η— η = 2-5 ch3 (? Η3 一(CH2)4-C-(CH2)3-ό Η3 Λ Γ4 οΓ厂ο·ρι 召X ο 广〇·〇工\ <Ν ο I 1 (Υ-52) (V-53) (V -54) (V-55) CH3 CH3 9H3 巧3 -CH2-^-(CH2)2-0-(CH2)3--(CH2)2-C-(CH2)5- -iCH2)4C-< CH2)s--

-〇^=-〇~ "XX (X (Y-56) (Y-57) ^*58) [化22] —(CH2J3-〇-(CHd2-0~(CH2)3~· (Y- 59) CH3 CH3 —(CH2)3- and HD (CH2)j-CH3 CH3 (Y-60)

[Chem. 23] jCT°ia〇Jir (Y-64) (Y-65) _

(V-70) (Y-71) (Y-72) -23- 201206994 [V.24] (V-73) n_2^ (Y-74) n=2~5 ~〇~Πη〇~ Women's material CH3 ( Υ-75) η = 2-5 (Υ-76> η = 5~19 (Υ-77) η = 5-19

[化25]"€C 〇-〇-〇-(CH2)n-CH3 (V-78) η =0-21

η = 〇-21 (Υ-79)

(Y-84) (V-85) ~^~QrOr (CH2)n-CH3 η = 0*21 ~^~\)^Q-〇〇-(CH2)n-^3 η = 0 -21 . Ν〇_0~ (Υ-87) η = 0~21 (Υ-86) 24 201206994 [化27]

[化 28]

-25- 201206994 [化 29]

02H

(Y-99) (Y-98) (Υ-100)

Further, the Yi structure in the above formula (1) represented by the above formula (7) is preferable. [化30]

(7) In the formula (7), R5 is a single bond or a divalent organic group having a carbon number of 1 to 20, preferably 1 to 12. The divalent organic group ' is preferably an alkyl group, an extended aryl group, or a combination thereof which may contain an ether bond, a guanamine bond, an ester bond, a thioester bond or a thioether bond. R6 is a structure of at least one selected from the group consisting of the above formulas (5) and (6). a is an integer of 1 to 4, preferably 1 or 2. Further, the structure of the formula (1) in the above formula (1) is preferably one having at least one selected from the group represented by the following formula. -26- 201206994 [化31]

Further, Y2 in the above formula (4) is particularly preferable in that at least one selected from the structures represented by the following formulas. [化32]

<Production Method of Polyphthalate> The polyphthalate represented by the above formula (1) may be any of the tetracarboxylic acid derivatives represented by the following formulas (10) to (12). It can be obtained by subjecting a diamine compound represented by the formula (13-27-201206994) to a polycondensation reaction. [化33]

HN—Y^NH (13) (wherein X, Yi, Ri, VIII, and 2 are respectively the same as defined in the above formula (1)). The polyperurethane represented by the above formula (1) can be synthesized by the above methods (1) to (3) using the above monomers. (1) In the case of synthesis from poly-proline. The polyphthalate can be synthesized by esterifying a tetracarboxylic dianhydride with a polyamine obtained from a diamine. [化35] Ο Ο -Λχ>-〇ΗH〇-ffxrrYi-N· Ο Α Α*| Α2- ο Ο—I JJ-OR! XRl〇lf 1『¥一丫1,一Ο Ο Α! Α2" Specifically, the polyamic acid and the esterifying agent are allowed to be carried out in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours. It is preferably synthesized by a reaction of 1 to 4 hours. The esterifying agent is preferably one which can be easily removed by refining, for example, N,N--28-201206994 dimethylformamide dimethyl acetal, n,n-dimethylformamide diethyl, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide pentyl butyl acetal, N,N-dimethylformamide di-t-butyl condensate Aldehyde, -3-P-tolyltriazene, 1-ethyl-3-P-tolyltriazene, 1-propyltoluenetriazene, 4-(4,6-dimethoxy-i, 3,5-triazabenzene-2-ylmethylmorpholinium chloride, etc. The amount of the esterifying agent added is preferably 2 to 6 mole equivalents per 1 mole of the repeating unit of the polyacid. The solvent used in the above reaction, in terms of solubility of the polymer, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and γ-butyrolactone may be used alone or Two or more types are used in combination. The concentration at the time of synthesis is less likely to cause precipitation of the polymer, and it is preferable that the high molecular weight body is easily obtained in an amount of from 1 to 30% by mass, more preferably from 5 to 20% by mass. Synthesis of a carboxylic acid diester dichloride and a diamine to form a tetracarboxylic acid diester dichloride The diamine is synthesized and synthesized. [Chemical 36] Acetalic new 1 - methyl-3-p-)-4-decylamine, preferably, in point, shape polycondensation

Ru〇\ %ci

Chi r O Ri + HN-YrNH Ai A2 O O-^X^~〇Rl Ri〇lf W丫1吖_ - Ο O Ai A2- Specifically, tetracarboxylic acid diester dichloride The diamine can be synthesized by reacting in the presence of a base and a solvent at -20 ° C to 150 ° C, preferably at ot 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours. As the base, pyridine, triethylamine, 4-dimethylamino group, pyridine 29 - 201206994 and the like can be used, and pyridine is preferably used from the viewpoint of stable reaction. The amount of the base to be added is easily removed, and the viewpoint of easily obtaining a high molecular weight body is preferably 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride. The solvent used for the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone for the solubility of the monomer and the polymer, and one type or two or more types may be used. In the case of mixing, the concentration at the time of synthesis is less likely to cause precipitation of a polymer and a high molecular weight body is easily obtained, and is preferably 1 to 30% by mass, more preferably 5 to 20% by mass. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyglycolate is preferably as far as possible for dehydration, and it is preferable to prevent the outside air from being mixed in a nitrogen atmosphere. (3) In the case where a polyamic acid is synthesized from a tetracarboxylic acid diester and a diamine, a polyphthalate is synthesized by subjecting a tetracarboxylic acid diester to a diamine by a condensation polymerization method. [化37]

\〇ίΓ • Ο Α Αι Aq- Ο Ο i Λ-ORi Specifically, the tetracarboxylic acid diester and the diamine are in the presence of a condensing agent, a base, and an organic solvent, at 0 ° C to 150 ° C, preferably It can be synthesized in a range of 0 ° c to 100 ° C for 30 minutes to 2 4 hours, preferably 3 to 1 hour. As the condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride -30-201206994 can be used. Salt, N, N'. carbonyldiimidazole, dimethoxy-1,3,5-triazaphenylmethyl oxime, 0-(benzotriazole-1.yl)-oxime, Ν ,Ν',Ν'-tetramethylurea cation tetrafluoroborate, 〇·(benzotriazol-1-yl)-oxime, Ν,Ν',Ν'-tetramethylurea cation hexafluorophosphate, (2,3-Dihydro-2-thio(keto)yl-3-phenyloxazolyl)phosphonic acid diphenyl ester or the like. The amount of the condensing agent to be added is preferably 2 to 3 moles per mole of the tetracarboxylic acid diester. The above-mentioned base can be used in an amount in which the amount of the base of the tertiary amine such as pyridine or triethylamine is easily removed, and it is easy to obtain a high molecular weight body, and is 2 to 4 times the molar amount relative to the diamine component. It is better. Further, in the above reaction, when Lewis acid is used as an additive, the reaction can be efficiently carried out. The Lewis acid is preferably lithium halide such as lithium chloride or lithium bromide. The amount of Lewis acid added is preferably 1.01.0 times moles relative to the diamine component. In the synthesis method of the above three polyglycolates, a high molecular weight polyglycolate can be obtained, and the synthesis method of the above (1) or (2) is particularly preferable. The solution of the polyamido vinegar obtained by the above method can precipitate a polymer when it is injected into a lean solvent with sufficient stirring. After several times of precipitation and washing with a poor solvent, the refined polyphthalate powder can be obtained after normal temperature or heat drying. The poor solvent is not particularly limited and is generally, for example, water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene or the like. <Production Method of Polylysine> The polyamic acid represented by the above formula (4) can be a tetracarboxylic dianhydride represented by the following formula (14) -31 - 201206994 and the formula (15) The diamine compound is represented by a polycondensation reaction. [化38]

0 0

Specifically, the tetracarboxylic dianhydride and the diamine are used in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours. It is preferably synthesized by reacting for 1 to 12 hours. The organic solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone in terms of solubility of the monomer and the polymer. These may be used alone or in combination of two or more. The concentration of the polymer is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint of not easily causing precipitation of the polymer and easily obtaining a high molecular weight body. The polylysine obtained by the above method can be recovered by injecting a polymer when the reaction solution is poured into a poor solvent in a sufficient agitation. Further, after a plurality of precipitations, washing with a poor solvent, and drying at room temperature or heating, a purified polyamic acid powder can be obtained. The poor solvent is not particularly limited, and is generally, for example, water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene or the like. &lt;Polyurinate having a thermally dissociable protecting group&gt; The polyglycolate having a thermally dissociable protecting group according to the present invention, -32-201206994 is a repeating unit represented by the above formula (1) Polyurethane sulphate </ RTI> and a polyphthalate oxime (i) satisfying the conditions of any one of the following (i) to (iii), wherein X!, Yi or both of the formula (1) have A monovalent or divalent substituent of at least one structure selected from the group consisting of the following formulas (2) and (3). (ii) Ai'A; or both of the formula (1) is a monovalent or divalent substituent having a structure selected from the group consisting of the following formulas (2) and (3) (iii) The oxime, Y2 or both of the formula (1) are monovalent or divalent substituents having at least one structure selected from the group consisting of the following formulas (2) and (3), Further, A, A2 or both are monovalent or divalent substituents having at least one structure selected from the group consisting of the following formulas (2) and (3). [化39]

Di 〇

| II —N— (2) —Βι—^ Ο~~〇2 (3) In the formula (2), 〇! is a protecting group for an amine group, which is a functional group which can be substituted by a hydrogen atom via heating. The structure of the time is not particularly limited. D, the structure which can effectively carry out the dissociation reaction at a baking temperature of at the time of producing the liquid crystal alignment film is preferably tert-butoxycarbonyl or 9-fluorenylmethoxy A carbonyl group is more preferred as a tert-butoxycarbonyl group. In the formula (3), : is a single bond or a divalent organic group. Preferred examples of the divalent organic group, such as an alkyl group, an extended aryl group, or the like, which may contain an ether bond, a guanamine bond, an ester bond, a thioester bond or a thioether bond; . Further, -33-201206994, in the formula (3), the atom to which the ester group is bonded is carbon. 〇1 is a monovalent or divalent substituent of the structure represented by the formula (2) of 4^-butoxycarbonyl or 9-fluorenylmethoxycarbonyl, for example, having the first or second order represented by the following formula Method for the action of an amine-based compound with di-tert-butyl dicarbonate in the presence of a base, or a compound having a primary or secondary amine group in the presence of a 9-mercaptomethyl chloroformate base The preparation is not particularly limited as long as it is a known method. [40]

The compound having a substituent prepared by the above method can be synthesized by adding a tetracarboxylic acid derivative or a precursor thereof or a diamine compound or a derivative thereof, and having a substituent having a functional group substituted by a hydrogen atom by heat treatment. The polycarboxylic acid derivative having the thermally dissociable protecting group of the present invention can be obtained from a raw material of a polyglycolate based on a tetracarboxylic acid derivative and/or a diamine. In the formula (3), hydrazine 2 is a protective group of a carboxyl group, and the structure thereof is not particularly limited as long as it is a functional group substituted by a hydrogen atom via heating. D2' is also used in the production of a liquid crystal alignment film at a temperature of 150 ° C to -34 - 201206994 as follows (D2-1 3 00 ° C, the structure can be effectively dissociated, preferably The functional group of (D2-1) to (D2-5) is more preferably, and the following formula) is more preferable. [化41]

(D2-5) In the formula (D2-2), R1Q is an alkyl group having 1 to 5 carbon atoms, and specific methyl (Me) group, ethyl group, propyl group, butyl group, pentyl group or tert-〇D2 is The structural substituent represented by the formula (3) of the above formula (D2-1), for example, can react a carboxyl group represented by the following formula with a tert-butyl alcohol counter-method, a carbon-carrying chlorine compound and tert-butyl alcohol. The method is prepared by a method of reacting a halogenated tert-butyl group, but it is not particularly limited as long as it is known. The compound having the base obtained by the above method is added to a tetracarboxylic acid derivative or a precursor thereof or a diamine or a precursor thereof to synthesize a tetracarboxylic acid having a substituent having a functional group hydrogenated by heat treatment. When the acid derivative and/or the diamine are used as a raw material of the polyamidomate, the polyfunctional amine ester having the excipient protecting group of the present invention can be obtained. For example, a method such as a butyl group such as a J 1 valence or a carboxyl group may be substituted with a compound and may be pyrolyzed -35 - 201206994

X: F, Cl, Br, I In the structural unit contained in the polylysine having a thermally dissociable protecting group of the present invention, at least one of the groups selected by the groups of the formulas (2) and (3) is substituted. The position of the base may be the position of X丨, Υι, A丨, and A2 of the formula (1). Wherein, the structure of the formula (1) has a form of at least one substituent selected from the group consisting of the formulas (2) and (3), and A!, A2 or both of the formula (1) For the form of at least one substituent selected in the group of the formulas (2) and (3), the simplicity of the monomer and the ease of handling the monomer are obtained when the monomer of the raw material of the polyphthalate is synthesized. It is preferable from the viewpoint of sex and the like. The polylysine having a thermally dissociable protecting group of the present invention may contain the formula (1) and does not exist in any position of X丨, γ丨, A丨, A2 (2) And the structural unit of the substituent represented by (3) may also be used. When the amount of introduction of the substituent represented by the formulas (2) and (3) is too small, the effect of suppressing the fine concavities and convexities caused by the phase separation of the polyglycolate and the polyamic acid is lowered, so X丨, Y丨, The content ratio of the substituent represented by the formulas (2) and (3) in the position of the —- and the 项--, is based on the -36-201206994 structural unit represented by the formula (!), 0.05 or more is preferable, and 10·10 or more is particularly preferable. For example, the structural unit represented by the formula (1) contained in the polyglycolate is only "in the formula (1) and in the Υι, respectively a substituent having one type selected from the group consisting of formulas (2) and (3), and eight or A2 is a substituent of one type selected by the group of formulas (2) and (3) In the case of the structural unit, the content of the substituent represented by the formulae (2) and (3) in the polyglycolate is 4·00. Specific examples of the substituent having a functional group substituted with a hydrogen atom by heat treatment represented by the above formulas (2) and (3) are, for example, the following (D-1) to (D-24), but are not limited thereto. The content. H3CPH3 V/CH3 H3C CH3 0hTCH3 —(CH2)n NH ~0—(C H2)n —NH n = 1 ～10 (DD η = 1~10 (D-2) on XCH2)n-NH {nn = 1~10 CH3 -〇-2-(CH2)n~NH-f CH3 n = WO Ηίξ (D-3) 0 0 (D-4) 9 -.......P ... ^Η-(ΟΗ2)η-ΝΗ-( CH3 η = 1-10 CH33 (D-5) 'HN^(CH2)n-NH-(〇CHs 1~10 cfl3 (D-6) 37- 201206994 44] -(CHj)^〇+Sh3 n= 1-10 CH3 (D-7) ch3 ten CH3 M〇CH3 (D-θ) y-〇-(CH2)n ° n = 1H0 (I&gt;9) CH3 〇-j—CH3 CH3 n = 1-10 CH3 (D-10) 〇V^CH^〇+Sh3 π =1-10 CH3 (D-11) &gt;(C^〇+ch3 n = 1~10 CH3 (D-12) [化45] —(εΆέΗ3

-〇-(〇H2)nN CH3 'CH3 o tH2 n = 0-10 (D-13) n=1~10 (D-^) CH3 :H3 h3c^Hj °^〇^ch3 〇V°_(CH2 n'NfcH2-&lt; CH3 (D-15) CH3 ch3 o H31 ch3 H3CwCH^, ch3 0-T-CH3 "γπ3 〇un2—^ JTXM, uj,- n = i~i〇(D-16) CH3 n = 1~10. Ten CH3 n /n.7. 〇10 CH3 n=1~!0(0-18) CH3

Ch, n = 1~10 (D-17) CH3 [化46] 〇ch3 -(CH2)n-CH"-〇10CH3 'CH3 HN^O n h3^ rw, 0-10 CH3 (D-19) o ch3 -〇-(CH2)n*9H-JL〇-|_CH3 ΗΝ^,Ο CH3 hH^V n = 0-10 h3u CH3 (D-20) —Q 〇CH3 (CHA-CH-^-O+ CHa HN^O CH3 ΠΙΜ^ν^ H3cv〇n H3C CH3 =0-10 (D-21) [Chem. 47]

A ch3 -nh bcH2)^°f^ 〇HcH2)^°tT q ^ ^ 〇H-aC n = Π-1Π λ η = Π.1Π HsC^bHa 0-10 (D-21) H3C qn = 0- 10 h3c^ch3 (°-22) n = 0-10 h3C^ch3 (_ 〇CH3 HN-iCHaJn-CH-^Ol-CHs —i HN^O CH3 ° h3〇.〇n = 〇-l〇H3C^ H3 (D.24) -38-201206994 Further, the diamine compound containing a substituent having a functional group substituted with a hydrogen atom by heat treatment represented by the above formulas (2) and (3) is, for example, the following formula ( D-25) The diamine compound of the following (D-35) is not limited to these contents.

[化49]

〇ch3 I cHi HN ^h3 ' CH3 called fly h3 nh2 (D-27) ch3 ch3 H3C-f-〇0 ten CH3 ch3 &gt;=〇〇=( ch3 HN-^^--NH (D-28) [ 50]

P-29)

Η2ν-^_/-νη2 (D-30), h3c ch3

NH CH, H3^H33 35

O' yo ch3心也3 H2N-^_&lt;/-NH2 (D-33) ch3 h3cJ^ch3 〇y〇,(CH2)3—NH -nh2 (CH2)3-NH P-31) 〇&lt;λΌ h3cH^ch3 ch3 -39 - 201206994 [化51]

(D-34)

(D-35) &lt;Liquid crystal alignment agent&gt; The liquid crystal alignment agent of the present invention is in the form of a solution obtained by dissolving the polylysine having a thermally dissociable protective group and polylysine in an organic solvent. The molecular weight of the polyamidomate having a thermally dissociable protecting group is preferably from 2,000 to 500,000, more preferably from 5,000 to 300,000, particularly preferably from 1 to 〇〇1, 000. Further, the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, particularly preferably 5,000 to 50,000 Å, and the weight average molecular weight of the polyamic acid is preferably 2,00 0 to • 40. - 201206994 500,000 is better, more preferably 5,000~300,000, especially good is 10,000~100,000. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, particularly preferably from 5,000 to 50,000. The polyglycolate having a thermally dissociable protecting group has a smaller molecular weight than polyglycolic acid, and can reduce minute irregularities formed by phase separation. The difference in weight average molecular weight of the polylysine having a thermally dissociable protecting group and polyamic acid is preferably from 1,000 to 200,000, more preferably from 5,000 to 150,000, and particularly preferably from 10,000 to 100,000. In the liquid crystal alignment agent of the present invention, the ratio of the polyamidomate to the polyamido acid having a thermal dissociation protecting group (polyperurethane/polyglycine) is 1/9 of the mass basis. 9/1 is better. The ratio is preferably 2/8, and particularly preferably 3/7 to 7/3. When the ratio is in this range, a liquid crystal alignment agent having both excellent liquid crystal alignment and electrical properties can be provided. The liquid crystal alignment agent of the present invention does not need to be examined as long as it is in the form of a solution obtained by dissolving a polylysine having a thermally dissociable protecting group and a polylysine in an organic solvent. For example, a method in which a powder of a polyphthalate and a poly-proline is mixed and dissolved in an organic solvent, a method in which a powder of a polyphthalate is mixed with a solution of a poly-proline, a polyglycolate solution, and A method of mixing a powder of poly-proline, a method of mixing a polyphthalate solution with a poly-proline solution. In view of the fact that even if the good solvent used for dissolving the polyphthalate and the poly-proline is different, a uniform polyaramate-polyglycine mixed solution can be obtained to use the polyamine. The method of mixing the acid ester solution with the polyaminic acid solution is more preferable. Further, 'the poly-lysine having a thermally dissociable protecting group and/or poly-p-41 - 201206994 amine acid is produced in an organic solvent, may be in the form of the obtained reaction solution, or the reaction solution may be suitably used. The solvent dilution can also be obtained. Further, in the case where the polylysine having a thermally dissociable protecting group is produced in a powder form, a solution obtained by dissolving it in an organic solvent may be used. The concentration of the polyglycolate and polylysine in the liquid crystal alignment agent of the present invention (in the case of the present invention, also referred to as a polymer) can be appropriately changed depending on the thickness of the coating film to be formed. However, from the viewpoint of forming a coating film which is uniform and free from defects, it is preferably 1% by mass or more, and more preferably 10% by mass or less from the viewpoint of storage stability of the solution. The organic solvent containing the liquid crystal alignment agent of the present invention is not particularly limited as long as it can uniformly dissolve the solvent of the polymer component of the lysine having a thermally dissociable protective group and polylysine. Specific examples thereof include, for example, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone , N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-pyrrolidone, fluorene-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl hydrazine, γ - Butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, 3-methoxy-oxime, guanidine-dimethylpropionamide, and the like. These may be used alone or in combination of two or more. Further, even if it is a solvent which does not uniformly dissolve the polymer component, it may be mixed with the above organic solvent as long as it does not precipitate a polymer. In the liquid crystal alignment agent of the present invention, when a decane coupling agent is added, it may be added to the polyphthalate solution, the polyaminic acid solution, or added to the polyphthalate solution and the polyaminic acid solution before being mixed. Both the polyamidate solution and the polyaminic acid solution are acceptable. Further, it may be added to a polyphthalate-poly-42-201206994 proline acid mixed solution. The decane coupling agent is added for the purpose of improving the adhesion between the polymer and the substrate, and the method of adding the decane coupling agent is, for example, added to a polyamic acid solution which can be interposed between the inside of the film and the substrate, and the polymer and After the decane coupling agent is sufficiently reacted, it is preferably mixed with the polyamidate solution. When the amount of the decane coupling agent is too large, the unreacted substance will have an adverse effect on the liquid crystal alignment property, and when it is too small, the adhesion effect will not be exhibited, so the solid content of the polymer is 0.01 to 5.0 weight. % is preferably, preferably 0 _ 1 to 1.0% by weight. The liquid crystal alignment agent of the present invention may further contain a solvent which improves the uniformity of the coating film when the liquid crystal alignment agent is applied to the substrate, in addition to the organic solvent for the purpose of dissolving the polymer. The solvent is generally a solvent which has a lower surface tension than the above organic solvent. Specifically, for example, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-single Methyl ether-2 -acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, dipropylene glycol, 2_(2-ethoxypropoxy)propanol, lactate A Ester, ethyl lactate, n-propyl lactate, η-butyl lactate, isoamyl lactate, and the like. These solvents can be used in combination of the two types. The liquid crystal alignment agent of the present invention may contain various additives such as a decane coupling agent or a crosslinking agent. In the case where a decane coupling agent or a crosslinking agent is added, in order to prevent precipitation of the polymer, a poor solvent is added to the liquid crystal alignment agent, and it is preferred to add it beforehand. Further, in the case of baking the coating film, in order to effectively carry out the ruthenium imidization of the polyamine-43 - 201206994 acid ester, a ruthenium hydride promoter can be added. Specific examples of the decane coupling agent will be listed below, but the decane coupling agent to be used in the liquid crystal alignment agent of the present invention is not limited to these contents. 3-aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-(2-aminoethyl)aminopropylmethyldimethoxy Baseline, 3-aminopropyltrimethoxydecane, 3-phenylaminopropyltrimethoxysilane, 3-triethoxydecyl-N-(1,3-dimethyl-butylene) An amine decane coupling agent such as propylamine or 3-aminopropyldiethoxymethyl decane; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (2 methoxy) Ethoxy)decane, vinylmethyldimethoxydecane, vinyltriethoxydecane, vinyltriisopropoxydecane,allyltrimethoxydecane, P-styryltrimethoxydecane Vinyl decane coupling agent; 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxy An epoxy-based decane coupling agent such as decane, 3-glycidoxypropylmethyldimethoxydecane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane: 3-A Acryl isopropyloxymethyl dimethoxy decane, 3- a methacrylic decane couple such as a propylene propylene oxypropyl trimethoxy decane, a 3-methyl propylene methoxypropyl methyl diethoxy decane, a 3-methyl propylene oxypropyl triethoxy decane Mixture; 3-acrylic decane coupling agent such as propylene oxypropyltrimethoxy decane; urea-based decane coupling agent such as 3-ureidopropyltriethoxy decane; bis(3-(triethoxy) Sulfonyl decane coupling agent such as decyl)propyl)disulfide or bis(3-(triethoxydecyl)propyl)tetrasulfide: 3-hydrothiopropylmethyldimethoxy Hydrogenthio-based decane coupling agent such as decane, 3-hydrothiopropyltrimethoxydecane, 3-octyl sulfonium-44 - 201206994 -1-propyltriethoxy decane; 3-isocyanate propyl three Isocyanate decane coupling agent such as ethoxy decane or 3-isocyanate propyl trimethoxy decane; aldehyde decane coupling agent such as triethoxy decyl butyl aldehyde; triethoxy decyl propyl methylamino group A urethane-based decane coupling agent such as a formate or (3-triethoxydecylpropyl)-t-butylcarbamate. Specific examples of the ruthenium imidization accelerator of polyglycolate are as follows, but the ruthenium-improving accelerator which can be used for the liquid crystal alignment agent of the present invention is not limited to these contents. [Chem. 52] HS^O S--. 0 D-ΝΉΟΗ D-M&gt;T〇l· OH (B-5) (^6)

(B-1) (B-2) [Chem. 53]

D-NH OH (B-9)

D-NH OH (B-10)

D-NH OH (B-11) D OH (B-12)

D-NH

D-NH OH (B-15)

(B-16)

D in the above formula (B-1) (B-17) each independently represents tert--45-201206994 butoxycarbonyl, or 9-fosylmethoxycarbonyl. Further, when a plurality of Ds exist in one formula (Β-Μ)~(Β_ΐ7), they may be the same or different from each other. The content of the ruthenium iodide promoter is not particularly limited as long as the effect of promoting the heat imidization of the polyglycolate is obtained. In other words, if the lower limit is to be expressed, it is preferably 〇.〇1 mol or more, preferably more than 1 mole of the phthalate moiety of the following formula (16) contained in the polyphthalate. For more than 5 moles, the best is more than Moer. Further, the main body of the hydrazine imidization promoter remaining in the film after baking is reduced to a minimum amount which adversely affects various characteristics of the liquid crystal alignment film, in other words, if desired When it is an upper limit, it is preferably 2 mol or less, more preferably 2 mol or less, based on the valinate moiety of the following formula (16) contained in the polyglycolate of the present invention. Below the Moh, the best is below 5 Mo.化 II Η , C—N- (16)

C-OR

II ο In the case where a ruthenium hydride promoter is added, since it can be subjected to hydrazine imidization by heating, it is preferably added after dilution with a good solvent and a poor solvent; liquid crystal alignment film &gt; -46 - 201206994 In the liquid crystal alignment film of the invention, the liquid crystal alignment agent obtained by the above method is applied to a substrate, and the coating film obtained by drying and baking is applied. If necessary, the coating film surface may be subjected to an alignment treatment such as rubbing. The substrate of the liquid crystal alignment agent of the invention is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate or a polycarbonate substrate can be used. Further, when a substrate such as an ITO electrode is used for the purpose of liquid crystal driving, it is preferable from the viewpoint of simplifying the process. Further, since the reflective liquid crystal display element is only a single-sided substrate, an opaque substance such as a germanium wafer can be used. In this case, a material such as aluminum which reflects light can be used as the electrode. The coating method of the liquid crystal alignment agent of the present invention, for example, a spin coating method, a printing method, an ink jet method, or the like. The drying and baking steps after the application of the liquid crystal alignment agent of the present invention may be carried out at any temperature and time. Usually, the organic solvent and the like are sufficiently removed, and dried at 50 ° C to 120 ° C for 1 minute to 10 minutes, and then baked at 150 ° C to 300 ° C for 5 minutes to 120 minutes. The thickness of the coating film after baking is not particularly limited. Generally, when it is too thin, there may be a fear of lowering the reliability of the liquid crystal display element, 5 to 300 nm, preferably 10 to 2 00 nm. The coating film is subjected to an alignment treatment such as a rubbing method or a photo-alignment treatment method, but the liquid crystal alignment agent of the present invention is particularly useful for the case of using a photo-alignment treatment method. Specifically, for example, a method of irradiating the surface of the coating film with a polarized light in a specific direction, and if necessary, adding a heat treatment of -47 to 201206994 at a temperature of 150 to 25 0 ° C to impart a liquid crystal alignment energy thereto. . It is also possible to use a wavelength of the ray to be ultraviolet or visible light having a wavelength of 100 nm to 800 nm. Among them, it is preferable to use ultraviolet rays having a wavelength of 100 nm to 400 nm, and it is particularly preferable to have a wavelength of 200 nm to 400 nm. Further, in order to improve the liquid crystal alignment property, the coating substrate may be heated to 50 to 25 (TC, and radiation may be used. In the alignment treatment or the like, the irradiation amount of the radiation is 1 to 10,000. The range of mJ/cm2 is preferably in the range of 100 to 5,000 mJ/cm2. The liquid crystal alignment film produced by the above method can form a stable alignment in a specific direction. [Embodiment] [Examples] The present invention will be described in more detail below by way of examples, but the present invention is not limited by the above. In the following, the abbreviations of the compounds used in the examples and comparative examples, and the measuring methods of various characteristics are As shown below. 1,3DMCBDE-C1: Metbis(chloro-yl)-l,3-dimethylcyclobutane-2,4-dicarboxylate DA-1: Formula (D-25) above BDA: 1,2,3,4-butane tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride NMP: N-methyl-2-pyrrolidone γ-BL : γ·butyrolactone-48- 201206994 BCS : butyl-cellulosin PAE: polyphthalate PAA: poly-proline DA-2: the above formula (D-29) DA-3: the above formula (D-30) D A-4 : Formula (D-28) D A-5 : Formula (DA-32) DA-6: η DA-7 of the above formula (DA-35): Formula (DA-7) DA-8: Formula (DA-8) DAH-1 : Formula (DAH-1 ) DAH-2 : Formula (DAH-2 ) AD-1 : Formula (AD-1): AD-2: Formula ( AD-2) AD-3: Formula (AD-3) below AD-4: Formula (AD-4) -49 - 201206994 [Chem. 55]

(DA-8)

[Viscosity] In the synthesis example, the viscosity of the polyphthalate and the polyaminic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample volume of 1.1 mL, and a conical mixer TE-1 ( 1°34', R24), temperature 25 °C measured -50-201206994 [Molecular weight] Further, the molecular weight of polyglycolate was measured using a GPC (Crystal Gel Permeation Chromatography Analyzer) device to collect The number average molecular weight (hereinafter also referred to as Μη) and the weight average molecular weight (hereinafter also referred to as Mw) were calculated in terms of ethylene glycol and polyethylene oxide. GPC device: manufactured by Shodex Co., Ltd. (GPC-101) Pipe column: manufactured by Shodex Co., Ltd. (inline type of KD803, KD805)

Column temperature: 50 ° C Dissolution: N,N-dimethylformamide (additive is lithium bromide - water and Li (HBr) is 30 mmol / L, phosphoric acid. Anhydrous crystals (〇-dish acid) 30 mmol/L, tetrahydrofuran (THF) 10 ml/L) Flow rate: 1.0 ml/min Standard sample for the calibration line: TSK standard polyethylene oxide manufactured by Tosoh Corporation (weight average molecular weight (Mw) approx. 900,000, 150,000, 100.000, 3,000), and polyethylene glycol (a peak top molecular weight (Mp) of about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories. In the measurement, in order to avoid overlapping of the peaks, samples of 4 kinds of mixed materials such as 900, 0 0 0, 1 0 0, 0 0 0, 1 2,000, and 1,000, and 3 types of 1 50,000, 30.000, and 4,000 were respectively measured. Mix 2 samples such as samples. [Measurement of Average Thickness of Center Line] The coating film of the liquid crystal alignment agent obtained by spin coating was dried on a hot plate at -51 - 201206994 temperature of 80 ° C for 5 minutes at a temperature of 25 ° ° The hot air circulating oven of C was baked for 1 hour to form a coating film having a film thickness of 1 〇〇 nm. The film surface of the coating film was observed by an atomic force microscope (AFM), and the average thickness (Ra) of the center line of the film surface was measured to evaluate the flatness of the film surface. Measuring device: L-trace detection microscope (manufactured by SII Technology Co., Ltd.) [Voltage retention rate] The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode and dried on a hot plate at a temperature of 80 ° C. In a minute, a hot air circulating oven of 250 ° C was baked for 60 minutes to form a coating film having a film thickness of 100 nm. The 254 nm ultraviolet light was irradiated onto the coating film surface at 100 mJ/cm2 through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Two sheets of the substrate with the liquid crystal alignment film are prepared, and the liquid crystal alignment film surface of the substrate on one side is dispersed with a particle sizer having a diameter of 6 μm, and then the two substrates are combined in an antiparallel manner in the alignment direction, and only remain. Outside the liquid crystal injection port, the other surrounding portions were sealed, and an empty cell with a cell gap of 6 μm was obtained. Liquid crystal (MLC-204 1, manufactured by Merck) was injected into the empty cell at a normal temperature, and the liquid crystal cell was obtained by blocking the injection port. The method for measuring the voltage holding ratio of the liquid crystal cell is carried out in the following manner. A voltage of 4 V was applied to 60 μ3, and the voltage after 16.67 ms was measured, and the fluctuation caused by the initial enthalpy was calculated as the voltage holding ratio. In the measurement, the temperature of the liquid crystal cell was set to 23 ° C, 6 (TC, 90 ° C, and the respective temperatures were measured. • 52 - 201206994 [Ion Density] The ion density of the liquid crystal cell was measured. The measurement was carried out in the following manner. The measurement was carried out using a 6254 liquid crystal physical property evaluation device manufactured by Toyo Kogyo Co., Ltd. The triangular wave of 10 V and 0.01 Hz was applied to calculate the area corresponding to the ion density of the obtained waveform by a triangle approximation as the ion density. The temperature of the liquid crystal cell is set to 23 ° C ' 60. (:, and the respective temperatures are measured. [AC-driven burn-in of the FFS-driven liquid crystal cell] The liquid crystal alignment agent is applied by spin coating On the glass substrate, an IT crucible electrode having a first layer electrode shape of 50 nm and a second layer insulating film having a thickness of 5 nm and a third layer having a comb shape as an electrode is formed. The edge electric field switching (Fringe Field Switching: hereinafter, also referred to as FFS) of the ITO electrode (electrode width: 3 μm, electrode spacing: 6 μηι, electrode height: 50 nm) was performed on a glass substrate of an electrode for driving at 80 ° C. 5 minutes on the hot plate After the clock, the film was baked at a temperature of 250 ° C for 60 minutes to form a film having a film thickness of 1 〇〇 nm. The ultraviolet film of 254 nm was irradiated with a polarizing plate at 100 mJ/cm 2 . In addition, a substrate having a liquid crystal alignment film is attached, and a glass substrate having a columnar distance controller having a height of 4 μm which is not formed on the opposite substrate is formed into a coating film by the same method, and is subjected to alignment treatment. The two substrates are printed as a group, and the sealing agent is printed on the substrate, and the other substrate is oriented in the direction of the alignment of the liquid crystal alignment film surface. After the bonding is performed, the sealing agent is hardened to make an empty space. In this empty cell, liquid crystal MLC-2041 (manufactured by Merck) was injected by a vacuum injection method, and the injection port was closed to obtain a liquid crystal cell by FFS. The temperature of the FFS-driven liquid crystal cell at 58 ° C was measured. After the lower VT characteristic (voltage-transmittance characteristic), a rectangular wave of ±4 V/1 20 Hz was applied for 4 hours. After 4 hours, the voltage was cut off and placed at a temperature of 58 ° C for 60 minutes, and then the VT was measured again. Characteristics, calculate the transmittance before and after the application of a rectangular wave is 50 ° / [Evaluation of voltage accumulation characteristics] [Evaluation of charge accumulation characteristics] The FFS-driven liquid crystal cell was placed on a light source, and VT characteristics (voltage-transmittance characteristics) were measured, and then a rectangular wave of ±1.5 V/60 Hz was applied. The transmittance (Ta). Then, after applying a rectangular wave of ±1.5 V/60 0 Hz for 10 minutes, the DC IV was overlapped and driven for 30 minutes. The DC voltage was cut off, and the transmittance after 1 minute of AC driving was measured ( Tb), the difference between 1 and Ta, the difference in transmittance (a.) dimethyl 1,3-bis(chlorocarbonyl)-1,3-dimethyl ring produced by the voltage remaining in the liquid crystal display element Synthesis of Butane-2,4-Dicarboxylate (1,3DMCBDE-C1) Synthesis of (a-Ι)Dicarboxylic Acid Dialkyl Ester-54- 201206994 [化56]

Under a nitrogen flow, a 3 L (liter) four-necked flask was charged with hydrazine, 3-dimethylcyclobutane._1,2,3,4-tetracarboxylic dianhydride (a compound of formula (5-1), Hereinafter, referred to as 1,3-DM-CBDA) 220g (0.981 m〇l), with methanol 2200g (6.87 mol, l〇wt times relative to 1,3-DM-CBDA), at 65 °C The mixture was heated under reflux to form a homogeneous solution in 30 minutes. The reaction solution was stirred in this state under heating and reflux for 4 hours and 30 minutes. This reaction liquid was measured using a high-speed liquid chromatography analyzer (hereinafter abbreviated as HPLC). After the solvent was distilled off using an evaporator, ethyl acetate 1 3 0 1 g was added, and the mixture was heated to 80 ° C to reflux for 30 minutes. Subsequently, the internal temperature was cooled to 25 ° C at a rate of 2 to 3 ° C per 1 minute, and stirred at 25 ° C for 30 minutes in this state. The precipitated white crystals were taken out by filtration, and the crystals were washed twice with ethyl acetate (1,1 g), and then dried under reduced pressure to give white crystals of 3.97 g. This crystal was analyzed by 4 NMR, and the crystal structure was analyzed by X-ray to confirm that it was Compound (1_1) (relative area of HPLC: 97.5%) (yield 3 6 -8 %). *H NMR (DMSO-d6, 5 ppm); 12.82 (s, 2H), 3.60 (s &gt; 6H), 3.39 (s, 2H). 1.40 (s &gt; 6H). -55- 201206994 (a-2 ) Synthesis of 1,3-DM-CBDE-Cl [Chem. 57]

Under a nitrogen flow, a compound (1-1) 234.15g (0.81 mol) and n-heptane 1170.77g (11.68 mol. 5wt times) were added to a three-liter four-necked flask, followed by the addition of pyridine 0.64 g (0.01 mol). The mixture was heated and stirred to 75 ° C with stirring using a magnetic stirrer. Subsequently, 289.93 g (11.68 mol) of sulfinium chloride was added dropwise over 1 hour. Foaming started immediately after the dropping, and the reaction solution formed a uniform solution 30 minutes after the completion of the dropping, and the foaming was stopped. Subsequently, in this state, after stirring at 75 ° C for 1 hour and 30 minutes, the solvent was distilled off to an amount of 924.42 g in an evaporator and a 40 ° C water bath. Further, the mixture was heated at 60 ° C to dissolve the crystals precipitated when the solvent was distilled off, and the insoluble matter was distilled off by hot filtration at 60 ° C, and then the filtrate was cooled to 2 ° C per 1 minute. 5 °C. After stirring for 30 minutes in this state at 25 Torr, the precipitated white crystals were taken out by filtration, and the crystals were washed with η-heptane 2 64.2 lg. After drying under reduced pressure, 226.09 g of white crystals were obtained. Subsequently, 226.09 g of the white crystals obtained and 452.18 g of η-heptane obtained above were added to a three-liter four-necked flask under a nitrogen stream, and then at 60. (: The crystals were dissolved by heating and stirring. Then, the crystals were precipitated by cooling at a rate of 1% per 10 minutes to 25 ° C. After stirring in this state at 25 t for 1 hour, precipitation was carried out. The white crystals were taken out by filtration, and the crystals were washed with η-hexane 1 1 3.04 g, and then dried under reduced pressure to give white crystals of 2 〇 3 9 丨g. This crystallization-56-201206994 was analyzed by 4 NMR. It was confirmed that the compound (3-1) was dimethyl-1-1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4-dicarboxylate (1,3_DM-CBDE- C1) (relative area of HPLC 99.5%) (yield 77.2%) 〇'H NMR (CDC13 &gt; 5 ppm): 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s, 6H). Example 1) The diamine compound (DA-1) was synthesized by the 4-step process shown below. Step 1: Synthesis of Compound (A5)

HN ch3 -o+ch3 ch3 (A5) In a 500 mL eggplant flask, propargylamine (8.81 g, 160 mmol), N,N-dimethylformamide (112) were added sequentially. (M)), potassium carbonate (18. 5g &gt; 134 mmol), allowed to reach 〇 ° C, dissolved in t-butyl bromoacetate (21.9 g, 112 mmol) of N,N-dimethylformamide (80 The resulting solution was added dropwise with stirring over a period of about 1 hour. After the completion of the dropwise addition, the reaction solution was returned to room temperature and stirred for 20 hours. Subsequently, the solid matter was removed by filtration, and 1 L of ethyl acetate was added to the filtrate, and washed with 300 mL of water for 4 times and 300 mL of saturated saline for 1 time. Subsequently, the organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. Finally, the residual oil was distilled under reduced pressure at 0.6 Torr, 70 s to give N-yne-yield as a colorless liquid, &lt;RTIgt;&lt;/RTI&gt; The yield was 12.0 g and the yield was 63%. Step 2: Synthesis of Compound (A6) [Chem. 59] ch3 0-CH3

In a 1 L eggplant type flask, the above-mentioned N-propargylaminoacetic acid t-butyl (12.0 g, 70.9 mmol) and dichloromethane (600 mL) were added as a solution, and the dicarbonic acid was dissolved in ice-cooled stirring. A solution of di-t-butyl ester (15.5 g, 7 〇.9 mmol) in dichloromethane (100 mL) was added dropwise over one hour. After the completion of the dropwise addition, the reaction solution was returned to room temperature and stirred for 20 hours. After the reaction was completed, the reaction solution was washed with 300 mL of saturated brine and dried over magnesium sulfate. Subsequently, the solvent was distilled off under reduced pressure to give a pale yellow liquid of N-propargyl-N-t-butoxycarbonylaminoacetic acid t-butyl ester (compound (A6)). The yield was 18.0 g' yield was 94 ° /. . Step 3: Synthesis of Compound (A7) -58- 201206994

In a 300 mL four-necked flask, 2-iodo-4-nitroaniline (22.5 g, 85.4 mmol), bis(triphenylphosphine)palladium dichloride (1.20 g 5 1.71 mmol), copper iodide ( 0.651 g, 3.42 mmol), after substitution with nitrogen, diethylamine (43.7 g, 598 mmol), N,N-dimethylformamide (128 mL) was added and stirred under ice-cooling - Propargylamino-Nt-butoxycarbonyl acetic acid t-butyl ester (27.6 g, 102 mmol) was stirred at room temperature for 20 hr. After the completion of the reaction, 1 L of ethyl acetate was added, and the mixture was washed three times with 150 mL of a 1 mol/L ammonium chloride aqueous solution, and once with 150 mL of saturated brine, and dried over magnesium sulfate. Subsequently, the solid which was obtained by distilling off the solvent under reduced pressure was dissolved in ethyl acetate (200 mL), and 1 L of hexane was added, followed by recrystallization. The solid was collected by filtration and dried <RTI ID=0.0>################################################################################## (Compound (A7)). The yield was 23.0 g and the yield was 6 6 %. Step 4: Reduction of Compound (A7) in a 500 mL four-necked flask, and adding the aforementioned 2-{3-(Nt-butoxycarbonyl-Nt-butoxycarbonylmethylamino)-propynyl)} -4-Nitroaniline (-59-201206994 22.0g &gt; 54.2 mmol), and 'Ethanol (200g), after the reaction system was replaced with nitrogen, palladium carbide (2.20g) was added, and the reaction system was replaced by hydrogen. Stir at 48 ° C for 48 hours. After completion of the reaction, palladium carbide was removed by filtration through cerite, activated carbon was added to the filtrate, and the mixture was stirred at 50 ° C for 30 minutes. Subsequently, the activated carbon was filtered, and the organic solvent was evaporated under reduced pressure, and the residue was evaporated to dryness to give the diamine compound (DA-1). The yield was 19.8 g and the yield was 96%. The diamine compound (DA-1) was confirmed by using 4 NMR. 1H NMR (DMSO-de): 56.54-6.42 (m &gt; 3H, Ar), 3.49 &gt; 3.47 ( each s, 2 Η, NCH 2 CO 21 - B u ) , 3.3 8 -3.3 0 ( m , 2H, CH2CH2N), 2.5 1-2.44 (m, 2H, ArCH2), 1.84- 1.76 (m, 2H, CH2CH2CH2), 1.48- 1.44 (m, 1 8H, NC02t-BufPCH2C02t-Bu). (Synthesis Example 2) A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and 4,4'-diaminodiphenylmethane (4.486 g (22.63 mmol)) was placed, and DA-1 2.147 g was weighed. After (5,658 mmol), 121.37 g of NMP and 5.16 g (65.19 mmol) of pyridine as a base were added, followed by stirring to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-C1 8.8 3 84 g (27.16 mmol) was added, and the mixture was reacted for 4 hours under water cooling. After 4 hours, 134.86 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 ° C) for 15 minutes. The obtained solution of the polyglycolate was poured into 1 3 49 g of water in a stirred mixture, and the precipitated white precipitate was collected by filtration, and then washed once with 1 349 g of water, and washed with -60-201206994 1349 g of ethanol. One time, 337 g of ethanol was washed three times. After drying, white polyphthalate resin powder ll. 〇 4 g was obtained. The yield was 81.91⁄4. Further, the molecular weight of the polyamidomate was Mn = 15,205, Mw = 3G, and 219. The obtained polyacetate resin powder 969 〇g was placed in a 200 ml Erlenmeyer flask, and after adding NMP 98.7394 g, it was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-1). ° (Comparative Synthesis Example 1) A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and after placing 4,4'-diaminodiphenylmethane 8.0102 g (40.35 mmol), NMP 158.1 was added. g, 7.20 g (91.03 mmol) of pyridine as a base, and stirred to dissolve. Next, this diamine solution was stirred, and 1,3DM-CBDE-C1 1 2.3 4 1 9 g (3 7.9 3 mmol) was added, and the mixture was reacted under water cooling for 4 hours. The obtained solution of the polyamidate was poured into 175 7 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1757 g of water and 1757 g of ethanol for 1 time, 43 9 g of ethanol was washed 3 times, and after drying, 16.63 g of a white polyphthalate resin powder was obtained. The yield was 94.6%. Further, the molecular weight of the polyglycolate was Mn = 10,180 and Mw = 21,476. 1 4.8252 g of the polyacetate resin powder obtained by weighing the scale was placed in a 200 ml Erlenmeyer flask, NMP99.3 048 g was added, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE). -2). (Synthesis Example 3) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, -61 - 201206994 was weighed to 7.9693 g (40 mm 〇l) of 4,4'-diaminodiphenylamine, and added. NMP 31.7 g was stirred and dissolved in nitrogen gas continuously. The diamine solution was added with 7.1339 g (36.01 mmol) of BDA, and then added with NIyIP to have a solid content concentration of 25% by mass, and stirred at room temperature for 24 hours to obtain a solution of polyamine acid (PAA-1). . The polyglycolic acid solution has a viscosity of 2680 mPa.s at a temperature of 25 °C. Further, the molecular weight of the polyamic acid was Mn = 8,176 and Mw = 16,834. (Synthesis Example 4) 4,4'-diaminodiphenylamine 5.979 1 g (30.01 mmol), 3,5-diamine was weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 3.0446 g (20.01 mmol) of benzoic acid was added, and 39.69 g of NMP was added thereto, and the mixture was continuously stirred and supplied with nitrogen to dissolve. This diamine solution was added with 9.8379 g (49.65 mmol) of BDA, and NMP was added thereto so that the solid content concentration was 25% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamine. The polyamic acid solution has a viscosity of 8000 mPa.s at a temperature of 25 °C. Further, the molecular weight of the poly-proline was Mn = 13,696, Mw = 28, 61 9 . The obtained polyamic acid solution 5.53 55 g was placed in a 50 ml Erlenmeyer flask, and 8.3744 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyhydric acid solution (PAA-2) in an amount of 1% by mass. ). (Synthesis Example 5) 4,4'-diaminodiphenylamine 3_6652g (18.39 mmol) and 3 were weighed in a 1-mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, -62-201206994. 6992 g (4.595 mmol) of 5-diaminobenzoic acid was added, and 39.36 g of NMP was added thereto, and the mixture was continuously stirred and supplied with nitrogen to dissolve. The diamine solution was stirred, and 4.3326 g (22.09 mmol) of CBDA was added thereto, and NMP was added thereto so that the solid content concentration was 15% by mass, and the mixture was stirred at room temperature for 24 hours to obtain polylysine (PAA-3). Solution. The polyamic acid solution had a viscosity of 669 mPa.s at a temperature of 25 °C. Further, the molecular weight of the poly-proline was Mn = 16,902, M w = 3 4, 8 6 5 〇 (Synthesis Example 6), and was weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 1.48 g (9.23 mmol) of 4'-diaminodiphenyl ether and 2.1025 g (13.82 mmol) of 3,5-diaminobenzoic acid were added, and 39.7 g of NMP was added thereto, and the mixture was continuously stirred and supplied with nitrogen to dissolve. The diamine solution was added with 4.8162 g (22.08 mmol) of PMDA, and NMP was added thereto so that the solid content concentration was 15% by mass, and the mixture was stirred at room temperature for 24 hours to obtain polylysine (PAA-4). Solution. The polyamic acid solution had a viscosity of 257 mPa.s at a temperature of 25 °C. Further, the molecular weight of the polyamic acid was Mn = 13,620, Mw = 28,299 〇 (Example 1) The polyphthalate solution (PAE-1) obtained in Synthesis Example 2 was weighed and 1.52 89 g and the polymerization obtained in Synthesis Example 3 were collected. 0.5184 g of a proline solution (PAA-1) was placed in an Erlenmeyer flask, and after adding NMP 2.0050 g and BCS1.01 g, the mixture was stirred for 30 minutes with a magnetic mixer of -63 to 201206994 to obtain a liquid crystal alignment agent (I). (Example 2) 1.5246 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 2 and 1.4067 g of the polyamidic acid solution (PAA-2) obtained in Synthesis Example 4 were placed in an Erlenmeyer flask and added. After NMP 1.0960g and BCS1.0112g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (II). (Example 3) 1.5119 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 2 and 1.0074 g of the polyamidic acid solution (PAA-3) obtained in Synthesis Example 5 were placed in an Erlenmeyer flask and added. After NMP 1.5 183 g and BCS 1.03 13 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (III). (Example 4) 1.5018 g of the polyphthalate solution (PAE-1) obtained in Synthesis Example 2 and 1.1 008 g of the polyamidic acid solution (PAA-4) obtained in Synthesis Example 6 were placed in an Erlenmeyer flask and added. After NMP 1.4859 g and BCS 1.0214 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (IV). (Comparative Example 1) A polyphthalate solution (PAE-2) obtained in Comparative Synthesis Example 1 was weighed. 3. 〇〇g and a polyamic acid solution (PAA-1) obtained in Synthesis Example 3 (1.0A) were placed in a triangle. After adding Ν Μ P 3 · 9 9 g and BCS 2.0 1 2 8 g to the flask, the mixture was stirred for 30 minutes in a magnetic-64-201206994 mixer to obtain a liquid crystal alignment agent (a). (Comparative Example 2) 1.5119 g of the polyphthalate solution (PAE-2) obtained in Comparative Synthesis Example 1 and the polyamine acid solution (PAA-2) obtained in Synthesis Example 1.43 3 4 g were placed in a conical flask. After adding NMP 1.0903 g and BCS 1.0271 g, the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (b). (Comparative Example 3) A polyphthalate solution (PAE-2) obtained in Comparative Synthesis Example 1 was weighed. 3. 〇〇g and a polylysine solution (PAA-3) obtained in Synthesis Example 5 were placed in a triangle of 2.0141 g. Into the flask, 3.01 g of NMP and 2.0111 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (c). (Comparative Example 4) 1.5206 g of the polyphthalate solution (PAE-2) obtained in Comparative Synthesis Example 1 and 1.0258 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 6 were placed in an Erlenmeyer flask. After adding NMP 1.483 8g' BCS 1.0418g, the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (d). (Comparative Example 5) 3.1281 g of the polyphthalate solution (PAE-1) obtained in Synthesis Example 2 was placed in an Erlenmeyer flask, and NMP 1.0911 g and BCS 1.05 3 2 g were added, and the mixture was stirred for 30 minutes using a magnetic stirrer. Liquid crystal alignment agent (e). -65-201206994 (Example 5) The liquid crystal alignment agent (I) obtained in Example 1 was filtered using a filter of 1 · 〇μπι, and then spin-coated on a glass substrate with a transparent electrode at a temperature of 80 ° The hot plate of C was dried for 5 minutes, and baked at a temperature of 2 5 for 1 hour to form a coating film having a film thickness of 1 〇〇 nm. The average thickness (Ra ) of the center line of the coating film was measured. The measurement results are shown in Table 1 below. (Examples 6 to 9 and Comparative Examples 7 to 10) Except for the liquid crystal alignment agents (II) to (IV) and (a) to (d) obtained in the above Examples 2 to 4 and Comparative Examples 1 to 4 Each of the other coating films was formed in the same manner as in Example 5. The film surface of each coating film was observed using AFM. Further, the average thickness (R a ) of the center line of each coating film was measured. The measurement results are shown in Table 1 below. [Table 1] Liquid crystal alignment 剤 composition (stick ratio [%]) Average thickness of center line [nm] PAE PAA Example 5 (I) P AE-1 (5 0) P AA- 1 (5 0) 0 42 Example 6 (II) PAE-1 (5 0) PAA-2 (5 0) 0. 76 Example 7 (III) PAE-1 (5 0) PAA-3 (5 0) 0. 78 Example 9 (IV) PAE- 1 (5 0) PAA- 4 (5 0) 2. 14 Comparative Example 7 (a) PAE- 2 (5 0) PAA- 1 (5 0) 11. 41 Comparative Example 8 (b) PAE- 2 (5 0) PAA- 2 (5 0) 13.53 Comparative Example 9 (C) PAE- 2 (5 0) PAA- 3 (5 0) 9. 41 Comparative Example 1 0 (d) PAE- 2 (5 0) PAA-4 (5 0) 23.36 -66-201206994 As shown in Table 1, it was found from the results of Examples 5 to 9 and Comparative Examples 7 to 10 that the liquid crystal alignment agent of the present invention was confirmed to reduce the cause The fine concavities and convexities generated by the phase separation of the polyphthalate from the polyamic acid to obtain a smooth film surface (Example 1 〇) The liquid crystal alignment agent (I) obtained in Example 1 was filtered using a filter of 1.0 μm Then, it was spin-coated on a glass substrate with a transparent electrode, dried on a hot platen at a temperature of 80 ° C for 5 minutes, and baked at a temperature of 250 ° C for 1 hour to form a film thickness of 1 〇〇 nm. Coating film. The coating film surface was irradiated with ultraviolet rays of 254 nm at 100 rnJ/cm2 through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Prepare two sheets of the substrate with the liquid crystal alignment film, and spread the 6 μm distance adjuster on the liquid crystal alignment film surface of one of the substrates, and then combine the alignment of the two substrates in an anti-parallel manner to retain only the liquid crystal. Except for the inlet, the other circumferences were sealed, and an empty cell with a cell gap of 6 μm was produced. Liquid crystal (MLC-204 1, manufactured by Merck Co., Ltd.) was vacuum-injected into the empty cell at normal temperature, and the liquid crystal cell was obtained by blocking the injection port. The liquid crystal cell was measured for its voltage holding ratio, and then its ion density was measured. Voltage retention and ion density. The measurement results are shown in Table 2 below. (Example 1 1 to 1 3 and Comparative Example 1 1 to 1 5 ) Each of the liquid crystal alignment agents (II) to (IV) and (a) to (1) obtained in the above Examples 2 to 4 and Comparative Examples 1 to 5 was used. Other than e), liquid crystal cells were each produced in the same manner as in Example 1. The voltage holding ratio of -67-201206994 was measured for each liquid crystal cell, and then the ion density was measured. The measurement results of these voltage holding ratios and ion densities are shown in Table 2 below. [Table 2] Voltage holding ratio [%] Ion density [PC] 23X: 60*C 903⁄4 23t: 60t: Example 1 0 99.7 Ί 99. 1 93. 9 5 81 Example 1 1 99. 7 99.2 93. 9 12 120 Example 1 2 99. 7 99.2 94.0 10 91 Example 1 3 99. 6 99.3 95. 5 10 497 Comparative Example 1 1 99.6 98.8 94. 8 22 122 Comparative Example 1 2 99.5 98.9 94.6 2 163 Comparative Example 1 3 99.5 98.7 94.0 57 278 Comparative Example 1 4 95.2 87.0 88.4 1663 2790 Comparative Example 1 5 99.9 99.2 92. 6 12 87 As shown in Table 2, the results of Examples 10 to 13 and Comparative Example 1 5 were confirmed. The liquid crystal alignment agent of the present invention can provide a liquid crystal alignment film having an equivalent or higher reliability with respect to a liquid crystal alignment agent obtained by containing only a polyphthalate. Further, as a result of Examples 1 to 13 and Comparative Examples 1 to 14 , it was confirmed that the liquid crystal alignment agent of the present invention was polymerized with a polyphthalate having a low-polarity substituent which did not dissociate via heat. A liquid crystal alignment agent of lysine can obtain a liquid crystal alignment film having higher letterability. (Example 1 4) The liquid crystal alignment agent (I) obtained in Example 1 was filtered using a filter of 1 μm, and then applied by spin coating onto a glass substrate to form a first layer having a film thickness of 50 nm. The ΙΤΟ electrode, the second layer is a nitride film having a thickness of 500 nm as an insulating film, and the third layer is a comb-shaped ITO electrode (electrode width: 3 μηι, electrode spacing: 6 μm, electrode height: 50 nm) FFS The driving electrode is on the glass substrate. After drying on a hot plate at 80 ° C for 5 minutes, it was baked in a hot air circulating oven at 250 ° C for 60 minutes to form a coating film having a film thickness of 100 nm. -68- 201206994 The 254 nm ultraviolet light was irradiated onto the surface of the coating film with a polarizing plate at 100 mJ/cm2 to obtain a substrate with a liquid crystal alignment film. Further, a coating film was formed in the same manner as the glass substrate having a columnar distance controller having a height of 4 μm which is not formed on the opposite substrate, and subjected to alignment treatment. The two substrates were used as a group, and the sealant was printed on the substrate, and the other substrate was bonded to the liquid crystal alignment film surface at an orientation of 0°, and then the sealant was cured to prepare an empty cell. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the empty cell by a vacuum injection method, and the injection port was closed to obtain an FFS driving liquid crystal cell. The FFS drives the liquid crystal cell, and its AC drive burn-in characteristics and charge accumulation characteristics are evaluated. The results are shown in Table 3 below. (Examples 15 to 17 and Comparative Example 16) The same procedure as in Example 14 except that each of the liquid crystal alignment agents (II) to (IV) and (e) obtained in the above Examples 2 to 4 and Comparative Example 5 was used. The method separately produces an FFS driving liquid crystal cell. The evaluation of the AC drive burn-up characteristics and the charge accumulation characteristics of each FFS-driven liquid crystal cell was carried out. The results are shown in Table 3 below. [Table 3] AC drive burn-in [V] Charge accumulation characteristics [%] Example 1 4 0.08 0.57 Example 1 5 0. 12 0. 74 Example 1 6 0. 14 0.21 Example 1 7 0. 12 0. 00 Comparative Example 1 6 0. 10 3.30 As shown in Table 3, the results of Examples 14 to 17 and Comparative Example 16 were found to be -69-201206994 'confirm that the liquid crystal alignment agent of the present invention' can be obtained with a small AC drive. A liquid crystal alignment film having a degree of burntness and having a small residual voltage. (Synthesis Example 7) Synthesis of Diamine Compound (DA-2) (Precursor Synthesis 1) [Chem. 61]

1) bh3thf

2) aq. HCI

3) aq. NaOH is connected to a 1L four-necked flask with a Dim roth tube and a 100 mL dropping funnel. 'Add 2_cyano-4_nitroaniline (15g, 92 mm〇1)' reaction system After replacing with nitrogen, 400 mL of THF was added and cooled to 〇t: » Next, a boron-THF complex (1M in THF, 100 mL, 100 mm 〇i) was added dropwise via a dropping funnel over 30 minutes. It was confirmed that a yellow solid was precipitated from the gas generated in the reaction system. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 Torr. After the completion of the reaction, hydrochloric acid (2N, 200 mL) was added, and the mixture was stirred at room temperature for 2 hrs, and then aqueous sodium hydroxide (2N, 250 mL) was added at 10 ° C to form an assay. The organic layer was washed with a saturated aqueous solution of brine (500 mL) and dried over magnesium sulfate. The yield is H.9g, the yield is 77% 〇 (precursor synthesis 2) -70-

201206994 [化62] Plant nh2 /=( Boc2〇/CH2CI2 °2N^ ^~nh2 -- c In the 1L eggplant flask, add the aforementioned cyano reduction (4.6 0g, mmol) and dichloromethane (900 mL) To the solution, dit-tert-butyl ester (6.00 g, 27.5 mmol) was added, and the mixture was stirred at room temperature (20 ° C) for 3 days. After the reaction was completed, the reaction solution was washed with saturated brine and dried over magnesium sulfate. The solid which precipitated was concentrated under reduced pressure, and then crystallised from ethyl acetate-hexanes to afford crystals of EtOAc (yield: 5.2 g, y. 27.5 Stirred under carbonic acid, with the amount of acid

The Boc adduct (5.11 8.7 mmol) and ethanol (40 ml) were added to a 100 mL eggplant type flask, and the reaction system was replaced with nitrogen and then platinum oxide (500 mg) was added thereto, and then the reaction system was replaced with hydrogen. The suspension-forming reaction mixture was stirred at room temperature for 15 hours. After the completion of the reaction, ethanol was added to dissolve the precipitated white solid, and the mixture was filtered with vermiculite. The filtrate was concentrated, and the obtained peach solid was obtained from ethyl acetate·hexanehexanes, and yellow, and the crystals of the crystals were obtained. The yield was 3.40 g and the yield was 77%. The 1H-NMR of the obtained solid was measured to confirm the formation of DA-2. 'H-NMR ( DMSO-d6 » δρριη ) : 1·44 ( s,9H ) , 3.87 (d, J = 6.3Hz, 2H) , 4.10~4.30(m,4H) ' 6.27 ( dd , J = 2.4Hz &gt; 8.1Hz &gt; 1H ) , 6.31 (d, :J = 2.4Hz, 1H ) ' 6.38 ( d &gt; J = 8. 1 Hz ) , 7.14 (t, J = 6.3Hz, lH). (Synthesis Example 8) Synthesis of diamine compound (DA-3) (Synthesis of N-Boc-propargylamine) [Chem. 64]

In a four-necked flask, propargylamine (25.18 g, 0.448 mol), triethylamine (55.52 g, 0.549 mol), and dichloromethane (400 ml) were added, and the reaction solution was cooled in a water bath (20 ° C). Di-tert-butyl dicarbonate (118.15 g, 0.541 mol) was added dropwise over 30 minutes. After the completion of the dropwise addition, the mixture was stirred for 2 hours, and then 300 ml of a saturated saline solution and 200 ml of dichloromethane were added to the reaction mixture, followed by extraction. The resulting organic layer was dried over magnesium sulfate. After removing the desiccant, the resulting solution was distilled off to give a pale yellow oil (0 il). N-Boc-propargylamine (yield: 47.01 g, yield: 67.6%) obtained as a white solid was purified using recrystallization (hexane). (Synthesis of nitroplasts) -72- 201206994 [Chem. 65]

To a four-necked flask after nitrogen substitution, 2-iodo-4-nitrol 5.11 g, 19.4 mmol), bis(triphenylphosphine)pin (II) di (281.7 mg, 0.401 mmol) were added to confirm Copper (160.7 mg mmol) and diethylamine 30 ml were stirred at room temperature (2 Torr). Subsequently, Boc-propargylamine (3.72 g, 24_0 mmol) was added and stirred at room temperature (20 ° C) for 4 hours. After confirming the raw material with HP LC, 200 ml of ethyl acetate and 200 ml of an aqueous solution of 1 Μ ammonium chloride were added, followed by taking. The obtained organic layer was washed twice with a 1M aqueous solution of ammonium chloride and dried over magnesium sulfate. After the desiccant was removed, the filtrate was concentrated and purified by a ruthenium chromatographic column chromatography (ethyl acetate:hexane = 3:7). 4 · 9 7 g, yield 8 8.0 %. (Synthesis of DA-3) [Chem. 66] Aniline (chloride, 0.844 after 10 minutes, after the loss, extraction of anhydrous sulfur gel tube yield is

7 mmol was placed in a four-necked flask, and the above nitro group (12.45 g, 42. -73 - 201206994) was added, and suspended in 200 ml of ethanol. After degassing and nitrogen substitution, palladium carbide (1.23 g) was added, and the mixture was replaced with hydrogen, and stirred at room temperature (20 ° C) for 2 days. After filtration using vermiculite to remove palladium carbide and distilling off the solvent, the obtained solid was dissolved in 100 ml of toluene, and then 50 ml of hexane was added thereto to carry out recrystallization. The obtained solid was dried under reduced pressure to give pale brown solid (yield: 9· 13 g, yield: 80.6%). The W-NMR of the obtained solid was confirmed to be DA-B 〇!H-NMR (DMSO-de » δρρηι): 1.38 ( s &gt; 9Η ) '1.57 (q, J = 7.2 Hz, 2H ), 2.30 (t , J = 7.2Hz &gt; 2H ) , 2.94 ( quin, J = 6.0Hz, 2H ) ' 3.88~4.22(m,4H), 6.22 (dd , J = 2.1Hz, 8. 1Hz, 1H ) , 6.2 5 ( d, J = 2 · 1 Hz, 1H ), 6.37 ( d, J = 8.1 Hz, 1H ) ' 6 · 8 4 ( t, J = 6.0 Η z, 1 H ) 〇 (Synthesis Example 9) Diamine compound ( Synthesis of DA-4) [67]

P-phenylenediamine (I6.2g, 150 mmol), hydrazine, hydrazine-dimethylformamide (200 mL), potassium carbonate (49.8 g '360 mmol), cooled in a 500 mL flask To -20 °C. A solution of N,N-dimethylformamide (100 mL) dissolved in t-butyl vinegar (58.5 g. 300 mmol) was added dropwise over 3 hours. Subsequently, it was stirred at room temperature for 20 hours. After filtering the solid in the reaction mixture by filtration, 6 L of water was poured into the filtrate to recover a crude product of the precipitated diamine compound (D). Yield -74 - 201206994 The crude product was dissolved in 100 mL of N,N-dimethylformamide and re-injected into 2 L of water to precipitate a solid. This solid was washed with methanol and dried under reduced pressure to give a pale-yellow solid diamine compound (DA-4). The yield was 25.1 g and the yield was 50%. The structure of the diamine compound (D-4) was confirmed by using 4 NMR. *H NMR ( DMSO-d6 ) : 66.3 9 ( s &gt; 4H, Ar) , 5.09 ( t, J = 6.6 Hz, 2H, NH ) , 3.64 ( d, J = 6.6 Hz, 4H, CH 2 ) , 1.39 ( s, 1 8H, t-Bu ). (Synthesis Example 10) Synthesis of diamine compound (DA-5) (synthesis of nitro group) [Chem. 68]

Boc.·glycine (10.17 g » 5 8.05 mmol) was added to a four-necked flask after nitrogen substitution to dissolve in T H F 1 50 m 1 . Thereto, N-methylmorpholine (11.93 g, 117.9 mmol) was added and cooled to -20 °C. Isobutyl chloroformate (9.99 g, 73.14 mmol) was dropped into the solution. At this time, please be careful not to let the temperature of the reaction solution reach 〇t or more. After dropping, it is stirred at -2 °C for 1 Torr. At this time, the reaction solution became cloudy. After 10 minutes, 3 60 ml of 2-amino-4-nitroaniline (8.86 g, 57.86 mmol) in THF was added dropwise using a dropping funnel. After the completion of the dropwise addition, the mixture was stirred at _ -75 - 201206994 2 Torr for 1 hour, followed by stirring at room temperature (20 ° C) for 18 hours. After 18 hours, the precipitated solid was filtered off, and the solvent of the obtained filtrate was evaporated to give a concentrate. 200 ml of ethyl acetate and 200 ml of a 1 M aqueous potassium dihydrogen phosphate solution were added to the concentrate to carry out extraction. The obtained organic layer was washed once with a 1% aqueous solution of potassium dihydrogen phosphate, once with saturated brine, twice with saturated aqueous sodium hydrogen carbonate, and once with saturated brine. The resulting organic layer was dried using anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off from the filtrate to give an orange solid. The solid was suspended in 300 ml of toluene and heated and stirred for 30 minutes. The solid was collected by absorption, and the desired nitrobenzene (yield: 9.85 g, yield: 54. (Synthesis of DA-5) [Chem. 69]

Pd-CΗ,

In the eggplant type flask, the above nitro group (9.85 g, 31.75 mmol) was added, and then 150 ml of ethanol was added. After the reaction vessel was replaced with nitrogen, palladium carbide (1.11 g, 10 mass% based on the mass of the nitro group) was added, and the mixture was replaced with nitrogen. Subsequently, the reaction vessel was replaced with hydrogen and stirred at 20 ° C for 48 hours. After completion of the reaction, the palladium carbide was removed by filtration using vermiculite, and the solvent was removed from the filtrate. To the obtained concentrate, 150 ml of toluene was added, and the mixture was heated to reflux to precipitate a solid. The precipitated solid was filtered through heat to give a thin purple -76-201206994 solid. The yield was 8.05 g and the yield was 90.4%. The W-NMR of the obtained solid was measured to confirm the formation of DA-5. iH-NMR ( DMSO-d6, δρριη ) : 1.40 ( s, 9H ) , 3.70 (d, J = 6.0Hz, 2H) ' 4.04 ( bs - 2H ) , 4.35 (bs, 2H) , 6.23 ( dd, J = 2.4Hz - 8.0Hz &gt; 1H ) , 6.48 ( d, J = 8.0Hz , 1H ) , 6.6 1 ( d, J = 2.4Hz, 1H ) , 7.05 ( t, J = 6.0Hz, 1 H) , 8.94 ( s, 1 H) » (Synthesis Example 1 1 ) Synthesis of diamine compound (DA-6) (precursor synthesis 1) [Chem. 70]

〇2n-(3-f + η2ν·^^^νη2 - Ο Μ-Ο&quot;

DMSO 2 100 ° C in a 2 L four-necked flask, put 5,5 g (489.3 mmol) of 1,5-diaminopropane, potassium carbonate 270.5 § ( 1.957 111 〇 1) 'dimethyl sulfoxide 40 (^, l. Heating and stirring at 〇〇 ° C. Next, adding 138.09 g ( 978.7 mmol) of 4-fluoronitrobenzene and 100 g of dimethyl hydrazine, and heating and stirring at 100 ° C for 4 hours. After 4 hours, the reaction solution was The mixture was poured into 5 L of water, and the precipitated yellow solid was collected by filtration. The obtained solid was washed with 3 L of water, 556 g of methanol, and dried to give a yellow solid (precursor-1). The yield was 152.71 g. Transfer-1) to the reaction used subsequently. (Precursor Synthesis 2) -77- 201206994 [Chem. 71]

Into a 2 L four-necked flask, the above (precursor-1) 100 g (290·4 mmol), N,N-dimethylaminopyridine 7.10 g (58.08 mmol), and tetrahydrofuran 800 g were placed and stirred at 10 ° C. Dissolved. Next, 152.10 g (697.0 mmol) of dit-butyl dicarbonate was placed in a dropping funnel, and the solution was dropped into a four-necked flask over 1 hour. After the completion of the dropwise addition, the reaction liquid was distilled off using an evaporator to obtain a yellow oily material. To the yellow oil (ΟΠ)-like substance, ethyl acetate was added, and then 500 ml of an aqueous solution of 1% by weight of hydrogen chloride was added, and the mixture was extracted. The obtained organic layer was washed with 500 ml of a 1% by weight aqueous solution of hydrogen chloride and washed twice with 500 ml of water, and the resulting organic layer was washed with magnesium sulfate. After the desiccant is removed, the solvent is distilled off to obtain a yellow oily substance. The yellow oil-like material was placed - later changed to a yellow solid. To the solid was added 2 -propanol (4 g), followed by &lt;&quot;&quot;&quot;&quot; The yield is 1 24.3 2g. The resulting solid (precursor-2)' can then be used in the subsequent reaction. (Synthesis of DA-6) -78- 201206994 [Chem. 72]

The above precursors _2 !〇〇.〇g (183.6 mmol) and 14-dioxane 1 500 g were placed in a 2 L four-necked flask. After the reaction vessel was replaced with nitrogen, palladium carbide (10.00 g, 1 mass% relative to the mass of the nitro group) was added and replaced with nitrogen. Subsequently, the reaction vessel was replaced with hydrogen, and stirred at 2 (TC for 24 hours. In the white solid precipitated, 8 〇〇g of acetonitrile was added to dissolve it. The reaction solution was filtered using a membrane filter (1.0 jxm) to remove Palladium carbide. The solvent was removed from the filtrate to give a white solid. To the white solid, 3 50 g of 2-propanol was added and stirred for 1 hour. After 1 hour, a solid was collected by filtration, and 300 g of 2-propanol was added to the obtained solid. After dispersing and washing with an ultrasonic device, the mixture was filtered and dried to give DA-6 as a white solid. The yield was 65.50 g, and the yield was 74%. The 1H-NMR of the obtained solid was confirmed to be DA-6. *H-NMR (DMSO-d6,5ppm) : 1 · 1 0 〜1.2 3 ( m,6 Η ) , 1.32 ( s,18H) , 3.40 ( t,J = 6.8Hz,4H ) , 5.03 ( s, 4H ) ' 6.49 ( d &gt; 8.0 Hz, 1H ) , 6.48 ( d &gt; J = 8.4 Hz - 4H ) , 6.77 ( d, J = 8.4 Hz, 4H ) (Synthesis Example 12) 1,3-double (4 -Aminophenethyl)urea synthesis-79- 201206994 [Chem. 73]

OzN ★

〇2N N〇2 U) 〇2N€t°^ (C) A —H2N〇r-%a--aNH2 2-Nestrol-substituted 4-nolecular flask at room temperature Base amine hydrochloride [A] (52.50 g, 259 mmol), (4-nitrophenyl) [B] (37.53 g, 123 mmol) and THF)' was added triethylamine (74.90 g, 740) Methyl) dimethylaminopyridine (3. Olg, 24.7 mmol) was stirred using a stirrer. The reaction was traced using HPLC, and the reaction mixture was poured into pure water (9 L), and stirred for 30 minutes. The mixture was filtered, and washed with pure water (1 L) to obtain a white solid obtained as a white solid, which was obtained from a white solid, which was purified by using an ultrasonic apparatus in methanol (48 8 g), filtered and dried to give a white solid. [C] (yield 42.3 g, yield 96%). 'H-NMR (400 MHz &gt; DMSO-d6 &gt; 6 ppm) : 8.11 4H, m ) &gt; 7.43 - 7.40 ( 4H &gt; m ) &gt; 5.89 ( 2H &gt; t) 3. 1 9 ( 4H,q ) , 2.76 ( 4H, t ). Substituting a mixture of compound [C] (42.32 g, 1 18 mmol), 5% carbon 4.2 3 g, 1 〇 wt %), 1,4-dioxane (2 0 3 1 g), replacing with hydrogen And in the presence of hydrogen, the reaction was carried out at room temperature using HP LC trace. After the reaction was completed, the fluorite was subjected to 4-nitrocarbonic acid double (1877 g 5. 4-Ν, after mechanical stirring, followed by The dispersion-washing compound-8.08 (&gt; 3.24-palladium (nitrogen was stirred. After the filter medium-80-201206994, the solvent was distilled off under reduced pressure to give a crude product as a white solid. To the crude product, 2-propanol (85 g) was added, and the mixture was washed with an ultrasonic apparatus, and then filtered and dried to obtain a white solid 1,3-bis(4-aminophenethyl)urea (yield 31.9). g, yield 91%). ^-NMR (400 MHz &gt; DMSO-d6 &gt; 5 ppm) : 6.8 5-6.82 ( 4H, m) - 6.51-6.48 ( 4H &gt; m) &gt; 5.78 ( 2H &gt; t ), 4.83 ( 4H, s) , 3. 14-3.09 ( 4H, m ) , 2.50 - 2.45 ( 4H, m ) (Synthesis Example 1 3 ) [Chem. 74]

In a 500 mL reaction vessel, compound (b) (50.00 g 229 mmol), pyridine (〇.5〇0g, 〇·63 2 mm〇1), compound (c (6 3.02 ' 5 04 mmol ), acetonitrile) were added. (3〇〇g), the reaction was heated and refluxed under a nitrogen atmosphere. After the reaction was completed, it was cooled to 2 〇t: after -81 - 201206994, filtered and washed with acetonitrile (1 〇〇g) to obtain a thick Next, 2-propyl alcohol (300 g) and distilled water (1 〇〇g) were added to the crude product, followed by heating under reflux. Then, the mixture was cooled to 20 ° C, and the solid was filtered, using 2-propanol (1 g) After washing and drying, the compound (d) was obtained (yield: 37.8 g, yield: 37%). W-NMR (4 NMR spectrometry) (400 MHz, DMSO-d6, σ (ppm)): 8.07 ( 2H,s) ,5 . 1 5 - 5.1 4 ( 2 H,m ) &gt; 4.62 (2H,t) , 4.59-4.49 ( 4H,m ) , 4.38 ( 2H,q) in a 500 mL reaction vessel Compound (d) (20.00 g, 44.0 mmol) and yttrium chloride (120.0 g, l. 〇im〇l) were added and heated to reflux. After 30 minutes, after cooling to 20 ° C, sulfinium sulfonate was added. Chlorine (120.0g, 1.01 mol)' After heating for 2 hours, the excess sulfinium chloride was distilled off under reduced pressure and washed with hexane (200 g). Next, in the crude product, dichloromethane was added at 20 °C. After stirring (200 g), a solution of the compound (c) ( 12.1 g. 96.8 mmol), pyridine (13-93 g, 176 mmol), dichloromethane (10 g) was slowly added dropwise thereto, and after stirring for 1 hour, Compound (c) (12 lg · 96.8 mmol) and hydrazine (13.93 g, 176 mmol) were added. After the reaction was completed, the solvent was evaporated and washed with distilled water (144 g) to give a crude product. THF (144 g) The crude product was added, washed at 23 ° C, filtered, and washed with tetrahydrofuran (130 g), distilled water (I70 g), methanol (150 g), and dried to give (AD-4) (yield: 17.72 g). , Yield: 6 2%). 'H-NMR ('Η NMR spectroscopy) (400 MHz, DMSO-d6, σ -82 - 201206994 (ppm)): 8.17 ( 2 Η &gt; s ) , 5.18-5.13 ( 2H &gt; m) &gt; 4.64- 4.53 ( 6H,m ) , 4.37 ( 2H,q ). (Synthesis Example 1 4) 2,4-bis(methoxycarbonyl)cyclobutane-1,3-dicarboxylic acid l〇.2〇46g was weighed in a 300 mL four-necked flask equipped with a stirring device. (3 9.22 mmol), after adding 181.2 g of NMP, it was stirred to dissolve. Subsequently, 8.90 g (87.90 mmol) of triethylamine, 3.8987 g (36.05 mmol) of p-phenylenediamine, and 0.9528 g (4.02 mmol) of DA-2 were weighed and stirred to dissolve. This solution was stirred, and after adding (2,3-dihydroxy-2-thio(keto)yl-3-benzoxazolinyl)phosphonic acid diphenyl 33.74 g (88.01 mmol), NMP 3 was further added. 2 g, reacted under water cooling for 4 hours. The obtained polyamine lysate solution was poured into 1 〇 9 〇g of 2-propanol under stirring to 'filter the precipitate which was precipitated, and then washed 5 times with 540 g of 2-propanol, and dried. Polyurethane resin powder. The molecular weight of the polyglycolate was Mn = 5210 and Mw = 8 755. In a 50 ml Erlenmeyer flask, 2.4495 g of the obtained polyphthalate resin powder was weighed, and NMP 22.1 54 1 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-3). ). (Synthesis Example 15) 'Weighing 2,5·bis(methoxycarbonyl)terephthalic acid 1.2736 g (4.51 mmol) ' 2,4-dual in a 200 mL four-necked flask equipped with a stirring device Methoxycarbonyl)cyclobutane-1,3-dicarboxylic acid 2.691 5g (10.34 -83 - 201206994 mmol), and after adding 73.20 g of NMP, it was stirred and dissolved. Subsequently, 3.34 g (33.01 mmol) of triethylamine, 3.43 76 g (12.01 mmol) of 1,3-bis(4-aminophenoxy)propane, and DA-2 0.7 1 22 g (3.000 mmol) were weighed and stirred. Let it dissolve. The solution was stirred, and 12.65 g (33.0 mmol) of (2,3-dihydroxy-2-thio(keto)-3-phenylindolozolyl)phosphonic acid diphenyl was added, followed by NMP 10 g. The reaction was carried out for 4 hours under water cooling. The obtained polyglycolate solution was put into 53 Og of 2-propanol under stirring, and the precipitate was precipitated by filtration, and then washed with 2 10 g of 2-propanol for 5 times, and dried to obtain a poly A phthalate resin powder. The molecular weight of the polyphthalate was Mn = 10,281 and Mw = 23,163. In a 50 ml Erlenmeyer flask, 2 to 5,429 g of the obtained polyphthalate resin powder was weighed, and 2.93458 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to dissolve it to obtain a polyamidate solution (PAE-4). (Synthesis Example 16) A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and 4,4'-diaminodiphenylmethane 5. 〇〇 67 g (25.25 mmol), DA- was placed. 6 3.05 73 g (6.3 1 mmol), NMP 1 39 g, and base pyridine 5.5 7 g (7 0.3 6 mmol) were added, and the mixture was stirred and dissolved. Next, this diamine solution was stirred, and 1,3DM-CBDE-C1 9.5299 g (29.31 mmol) was added for 4 hours under water cooling. The obtained polyglycolate solution was poured into 1545 g of pure water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1545 g of pure water, once with i545 g of ethanol, and then with 3 86 g. The ethanol was washed 3 times, and after drying, a white polyphthalate resin-84 - 201206994 powder was obtained. The molecular weight of the polyglycolate is Mn = 1 43 5 9 and Mw = 3 1 55 8 . 12.31 g of the obtained polyphthalate resin powder was weighed and placed in a 50 ml Erlenmeyer flask, and 110.79 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-5). (Synthesis Example 1 7) In a 200 mL four-necked flask equipped with a stirring device, 5.5958 g (19.83 mmol) of 2,5-bis(methoxycarbonyl)terephthalic acid was weighed, and 68.70 g of NMP was added thereto. Stir to dissolve. Subsequently, triethylamine 4-01 g (39.63 mmol) and 3-aminobenzylamine 1.9611 g (16.05 mmol) of 'DA-2 0.9493 g (4.00 mmol) were added, followed by stirring to dissolve. This solution was stirred with the addition of 4-(4,6-dimethoxy-1,3,5-triazabenzene-2-yl)-4-methylmorpholine chloride (15 ± 2 weight) 16.40 g of water and water, and 7.72 g of NMP were added, and reacted under water cooling for 4 hours. The obtained polyglycolate solution was poured into 63 3 g of 2-propanol with stirring, and the precipitate was precipitated by filtration, and then washed with 210 g of 2-propanol for 5 times, and dried to obtain polyfluorene. Amine resin powder. The molecular weight of the polyglycolate was Mn = 5152 'Mw = 8788 〇 in a 50 ml Erlenmeyer flask, 2.5630 g of the obtained polyphthalate resin powder was weighed, NMP 23.0971 g was added, and the mixture was stirred at room temperature for 24 hours. This was dissolved to obtain a polyamidate solution (PAE-6). (Synthesis Example 1 8) A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere. -85-201206994 4,4'-diaminodiphenylmethane 1.5163 g (7.65 mmol), DA -l 2.8712 g ( 7.57 mmol), 73.3 g of NMP and 2.82 g (3 5.59 mmol) of pyridine as a base were added, and the mixture was stirred and dissolved. Next, the diamine solution was stirred, and 1,3DM-CBDE-C1 4.8 5 8 3 g (14.94 mmol) was added, and the reaction was carried out for 4 hours under water cooling. After 4 hours, NMP 8 1.44 g was added to the reaction solution. Stir at temperature (20 ° C) for 15 minutes. The obtained solution of the polyglycolate was poured into 850 g of 2-propanol under stirring, and the precipitated white precipitate was collected by filtration, and then washed with 17 g of 2-propanol for 5 times, and dried. A white polyphthalate resin powder was obtained. The molecular weight of the polyglycolate was Mn = 21514, Mw = 43 900 °. The obtained polythene phthalate resin powder 2.1 684g was placed in a 50 ml Erlenmeyer flask, and NMP 19.2226g was added and stirred at room temperature. It was dissolved in 24 hours to obtain a polyamine solution (PAE-7). (Synthesis Example 19) In a 200 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, p-phenylenediamine 1 · 73 1 2 g (1 6.01 mmol) and DA-2 0.9444 g (3.98 mmol) were weighed. Add Ν Μ P 3 2.4 7 g, stir and dissolve in nitrogen gas continuously. This diamine solution was stirred, and 4.4841 g (20.0 mmol) of 2.3.5-tricarboxycyclopentyl acetic acid dianhydride was added thereto, and NMP was added thereto so that the solid content concentration became 15% by mass, and the mixture was stirred at room temperature for 24 hours. The solution has a viscosity of 5 80 mPa · s at 25 ° C. After adding NMP 23.2 8 g to the solution to a solid concentration of 10% by mass, 6.04 g (40·5 mmol) of 1-methyl-3-ρ·metrizene was added, and the mixture was stirred at room temperature for 4 hours. After 4 hours -86 - 201206994, the reaction solution was poured into 28 6 g of 2-propanol with stirring, and the precipitate was separated by filtration, and then washed with 140 g of 2-propanol for 5 times. Polyurethane resin powder. The molecular weight of the polyglycolate was Mn=1 6532, Mw = 5〇698 〇 in a 50 ml sample tube in which a stir bar was placed, and the obtained polyphthalate resin powder 2.207 8 g was weighed and added to NMP 1 9.7894. g, stirred at room temperature for 24 hours to dissolve, to obtain a polyamidate solution (PAE-8). (Synthesis Example 20) A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and 1.9995 g (13.28 mmol) of 4-amino-N-methylphenethylamine was placed, and DA-5 0.93 79 g was placed. (3.35 mmol), 130.70 g of NMP and 3.80 g (37.54 mmol) of pyridine as a base were added, followed by stirring to dissolve. Next, this diamine solution was stirred, and 1,3DM-CBDE-C1 5.0894 g (15.65 mmol) was added, and the mixture was reacted for 4 hours under water cooling. The obtained solution of the polyamidite was put into 688 g of 2-propanol under stirring to 'filter out the precipitated white precipitate' and then washed 5 times with 172 g of 2-propanol. Amine resin powder. The molecular weight of the polyamidomate was Mn = 73 3 1 and Mw = 14716. 1.9755 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and NMP 17.73 4 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-9). . (Synthesis Example 2 1) -87- 201206994 Placed in a nitrogen atmosphere with a 100 mL four-necked flask equipped with a stirring device. - phenylenediamine 0.6005 L (5_55 111111〇1), 0-8-4 0.2334g (0.694 mmol), DA-3 0.1 849g (0.693 mmol), then added 49.80 g of NMP as a base pyridine 1.15 g (14.56 mmol) After that, it was stirred to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-C1 2.2550 g (6.94 mmol) was added, and the mixture was reacted under water cooling for 4 hours. The obtained polyglycolate solution was poured into 277 g of water with stirring, and the precipitated white precipitate was collected by filtration, followed by washing with 69 g of water for 5 times, and dried to obtain a white polyphthalate resin powder. The molecular weight of the polyglycolate was Mn = l 69 1 9 and Mw = 2798 2 . 2.0204 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and 18.18836 g of GBL was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-10). (Synthesis Example 22) 2,5-bis(methoxycarbonyl)terephthalic acid 2.2570 g (8.00 mmol) '2,4-bis(methoxy) was weighed in a 300 mL four-necked flask equipped with a stirring device. 3.0206 g (11.61 mmol) of cyclocarbonyl-cyclobutane-1,3-dicarboxylic acid was added to Ν Μ P 1 Ο Ο . 3 5 g, and stirred to dissolve. Subsequently 'Addition of triethylamine 4.45 g (43.98 mmol), 1,5-bis(4-amine basic oxy)propane 3.0934 g (11.98 mmol), 1,3 -bis(4-aminophenethyl)urea 1.201 8g (4.03 mmol) and DA-3 1.065 3 g (4.02 mmol) were stirred and dissolved. Add this solution (2,3·dihydroxy-2-thio(keto)-3-benzoquinazolinyl)phosphonic acid diphenyl 16.92g -88- 201206994 (44.14 mmol ) with stirring. NMP 1 3 · 14 g was added and reacted under water cooling for 4 hours. The obtained polyamidate solution was poured into 890 g of 2-propanol under stirring, and the precipitate was separated by filtration, and then washed with 300 g of 2-propanol for 5 times, and dried to obtain polyamine. Acid resin powder. The molecular weight of the polyamine amine ester was Mn = 9170 and Mw = 19990. 1.8720 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and NMP 1 6.9543 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-11). . (Synthesis Example 2 3) A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and 3.02 g (27.93 mmol) of p-phenylenediamine, 173.0 g of NMP, and 5.16 g of pyridine as a base (65.25) were placed. After mmol), it was stirred to dissolve. Next, this diamine solution was stirred, and 8.09 g (27.23 mmol) of dimethyl 2,4-bis(chlorocarbonyl)cyclobutane-1,3-dicarboxylate was added, and the mixture was reacted for 2 hours under water cooling. The obtained solution of the polyglycolate was poured into 100 g of water, and the precipitated white precipitate was collected by filtration, and then washed with 300 g of 2-propanol for 5 times, and dried to obtain a white polyphthalate resin powder. . The molecular weight of the polyperurethane was Mn = 1 0820 and Mw = 29 1 97. The obtained polypalmitate resin powder 1.53 09 was placed in a 50 ml Erlenmeyer flask, and 13.811 g of NMP and 16.69279 g of N,N-dimethylformamide were added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved. A polyamine solution (PAE-12) was obtained. -89- 201206994 ' - ) Take 01 scale m, m in 30 bottles 6 burn C / g □ 9 7 four 7 L7 m 1 o acid 20 A two of benzene loaded to mix} &gt; stirrer 24 has carbonyl attached The group was formed into 3.7712 g (14.49 mmol) of oxydimethyl bis(methoxycarbonyl)cyclobutane-1,3-dicarboxylic acid, and after adding 14.61 g of NMP, it was stirred and dissolved. Subsequently, 4.25 g (42.0 mmol) of triethylamine and 5.423 9 g (21.0 mmol) of 1,3-bis(4-aminophenoxy)propane were added, followed by stirring to dissolve. While stirring this solution, 16.91 g (44.11 mmol) of (2,3-dihydroxy-2-thio(keto)-3-phenylindolozolyl)phosphonate diphenyl ester was added, followed by addition of NMP 2 5 · 8 1 g, reacted for 4 hours under water cooling. The obtained polyamidate solution was poured into 1 224 g of methanol under stirring, and the deposited precipitate was collected by filtration, and then washed four times with 408 g of methanol, and dried to obtain a polyphthalate resin powder. The molecular weight of the polyglycolate was Mn = 15103 and Mw = 324,83. The obtained polyphthalate resin powder 1. g 172g was placed in a 50 ml Erlenmeyer flask, and NMP 9.4167 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-13). ). (Synthesis Example 25) A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and 4,4'-diaminodiphenylmethane was placed at 5.586 g (25_26 mmol), 1,5-bis ( After 1.8 064 g (6.31 mmol) of 4-aminophenoxy)pentane, 272 g of NMP and 5.69 g (71.88 mmol) of pyridine as a base were added, followed by stirring to dissolve. Next, the diamine solution was stirred, and 1,3DM-CBDE-C1 9.7356 g (29.94 mmol) was added, and the mixture was reacted under water cooling for 4 hours - 90 - 201206994. The obtained solution of the polyglycolate was added to 143 6 g of pure water under stirring to remove the white precipitate which was precipitated, and then washed once with 146 g of pure water and once with 146 g of ethanol. Further, it was washed three times with 386 g of ethanol to dry the white polyphthalate resin powder. The polyglycolate has a molecular weight of Mn = 1550 and Mw = 3021 9. 11.89 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and NMP 100.7 ml was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-14). . (Synthesis Example 26) After weighing 2,7141 g (13.16 mmol) of 2,5-bis(methoxycarbonyl)terephthalate in a 200 mL four-necked flask equipped with a stirring device, NMP 7 2.3 lg was added, followed by stirring. Let it dissolve. Subsequently, 0.71 g (7.01 mmol) of triethylamine and 1.7112 g (14.01 mmol) of 3-aminobenzylamine were added, followed by stirring to dissolve. This solution was stirred and added 4-(4,6-dimethoxy-1,3,5-triazabenzene-2-yl)-4-methylmorpholinium chloride (15±2 weight) 1 1.6258 g of water and substance), 12.91 g of NMP was further added, and the reaction was carried out for 4 hours under water cooling. The obtained polyamidate solution was poured into 616 g of methanol under stirring, and the precipitate was precipitated by filtration, and then washed with 616 g of methanol for 4 times, and dried to obtain a polyphthalate resin powder. The molecular weight of the polyphthalate was Mn = 7234 and Mw = 1 55 77. The obtained polyphthalate resin powder 1.1 3 25 g was weighed and placed in a 50 ml Erlenmeyer flask, and 10.1925 g of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (P AE- 1 5 ). -91 - 201206994 (Synthesis Example 7 7) A 300 mL four-necked flask equipped with a stirring device was placed in a nitrogen atmosphere, and after placing 7.01 g (64.82 mmol) of ρ-phenylenediamine, NMP 108 g and γ-BL 324 g were added. After 11.55 g (146 mmol) of the pyridine as a base, it was stirred and dissolved. Next, this diamine solution was stirred, and 1,3DM-CBDE-C1 1 9.783 8 g (60.85 mmol) was added, and the mixture was reacted under water cooling for 4 hours. The obtained polyphthalate solution was poured into 1881 g of 2-propanol under stirring, and the precipitated white precipitate was collected by filtration, followed by washing with 94 Og of 2-propanol for 5 times, and dried to obtain a white polyamine. Ester resin powder. The molecular weight of the polyglycolate was Mn=11325, Mw=24387 °. 1.2019 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and N,N-diethylformamide 10.81 was added. 71 g was stirred at room temperature for 24 hours to dissolve to obtain a polyamidate solution (PAE-16). (Synthesis Example 2 8) A 300 mL four-necked flask equipped with a stirring device was set in a nitrogen atmosphere, and 3.0144 g (20.07 mmol) of 4-amino-N-methylphenethylamine was placed, and NMP 148.88 g was added. After 4.65 g (46.01 mmol) of the pyridine as a base, it was stirred and dissolved. Next, the diamine solution was stirred, and 1,3DM-CBDE-C1 6.23 90 g (19.19 mmol) was added, and the mixture was reacted under water cooling for 4 hours. The obtained solution of the polyglycolate was put into 7 84 g of water under stirring, and the precipitated white precipitate was collected by filtration, and then washed with 784 g of water and 196 g of 2-propanol for 3 times, and dried to obtain a white aggregate. A phthalate resin powder. The molecular weight of the polyfluorene-92-201206994 aminate is Mn = 8 69 1 and Mw = 203 1 1. 1.9144 g of the obtained polyphthalate resin powder was placed in a 50 ml Erlenmeyer flask, and NMP 1 7.2026 g was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-17). . (Synthesis Example 29) 3,5-diaminobenzoic acid 20_08388 (132.〇111111〇1) and 0-8-7 were weighed in a 1〇〇mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 1.3254g (88.0 mmol), after adding 268.48g of NMP, it was stirred and continuously dissolved in nitrogen. The diamine solution was stirred and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 42.4946 was added. g (216.7 mmol), further added NMP to a solid concentration of 20% by mass, and stirred at room temperature for 24 hours to obtain a solution of polyamine acid (PAA-5). The polyamic acid solution has a viscosity of 2156 mPa.s at a temperature of 25 °C. Further, the molecular weight of the poly-proline is Mn = 1 8 7 9 4 ' Mw = 63 3 87. (Synthesis Example 3 0 ) 4,4'-diaminodiphenylamine 3.5843 g ( 17.99 mmol) and DA-7 2.9064 were weighed in a 1 mL mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. g (12.0 mmol), force D into 55.58 g of NMP, and continuously dissolved in nitrogen to dissolve. The diamine solution was stirred, and 5.7653 g (29.40 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was added to make the solid content concentration 15% by mass at room temperature. Stir for 24 hours. The resulting polyamic acid solution had a viscosity of 1 269 mPa·s at a temperature of 25 °C. Further, -93-201206994, the molecular weight of the poly-proline is Mn = 1 5559 and Mw = 43490. Further, 0.0368 g of 3-glycidoxypropylmethyldiethoxysilane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-6). (Synthesis Example 3 1 ) 3,5-diaminobenzoic acid 1.21338 (7.97 111111〇1), 4,4'-two was weighed in a 1〇〇mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 6.8216 g (31.98 mmol) of aminodiphenyl-N-methyl-amine was added to 44.03 g of NMP, and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was stirred, and BDA7.1310 g (36.0 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Next, 14.62 g of NMP and 0.8713 g (3.99 mmol) of pyromellitic dianhydride were added. Further, N MP was added to have a solid content concentration of 18% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 577 mPa·s at a temperature of 25 °C. Further, the molecular weight of the poly-proline was Mn = 1 265 6 and Mw = 28487. Further, 0.0480 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-7). (Synthesis Example 32) 3.56 1 g (24.02 mmol) of 3,5-diaminobenzoic acid was weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and 1,4-double (

4-Aminophenyl) piperidine 4.293 1 g (1.200 mmol) was added to NMP •94-201206994 36.48 g', and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was stirred, and BDA 4.7522 g ( 23.99 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Next, 6.50 g of NMP 3 and 3.408 4 g (15.63 mmol) of pyromellitic dianhydride were added. Further, NMP was added to have a solid content concentration of 15% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 1166 mPa.s at a temperature of 25 °C. Further, the molecular weight of the poly-proline is Μ η = 1 9 3 0 7 ' Mw = 42980 °. Further, 0.0483 g of 3-glycidoxypropylmethyldiethoxy decane is added to the solution. The mixture was stirred under heating for 24 hours to obtain a polyamidonic acid solution (PAA-8). (Synthesis Example 3 3 ) 3,5-diaminobenzoic acid 3.653 6 g (24.01 mmol) and DA-7 3.8715 g (15.98) were weighed in a 1 mL bottle equipped with a stirring device and a nitrogen introduction tube. Methyl) 31.75 g of NMP was added and stirred and continuously dissolved in nitrogen. This diamine solution was added to BDA 3.962 1 g (20.0 mmol) while stirring, and stirred at room temperature for 2 hours. Next, NMP25·42 g and 1,2,4,5-cyclohexanetetracarboxylic dianhydride 4.47 7 6 g (19·97 mmol) were added. Further, ΝΜP was added to have a solid concentration of 2% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 417 mPa.s at a temperature of 25 °C. Further, the molecular weight of the poly-proline is Mn=l 3 29 1 , Mw = 54029 〇, and then 3.0476 g of 3-glycidoxypropylmethyldiethoxydecane is added to the solution at room temperature. Stir for 24 hours to obtain a poly-proline solution (-95-201206994 PAA-9). (Synthesis Example 3 4 ) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.7365 g (17.99 mmol) and 2,2'-dimethyl group of 3,5-diaminobenzoic acid were weighed. 4,4'-Diaminobiphenyl 2.547 1 g (12.0 mmol), 27.32 g of NMP was added, and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was stirred, and 2.2562 g (9.02 mmol) of bicyclo[3_3.0]octane-2,4,6,8-tetracarboxylic dianhydride was added, and the mixture was stirred at 80 ° C for 3 hours. After the reaction solution was cooled to room temperature, 27-32 g of NMP and 4.5715 g (20.96 mmol) of pyromellitic dianhydride were added. Further, NMP was added to have a solid content concentration of 15% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 2190 mP a .s at a temperature of 25 °C. Further, the molecular weight of the poly-proline is Μ η = 2 3 6 3 2, M w = 5 6 8 8 1 . Further, to this solution, 3-glycidoxypropylmethyldiethoxydecane 0.03 60 g was added, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-10). (Synthesis Example 3 5 ) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 6.0854 g (40.0 mmol) of 3,5-diaminobenzoic acid was weighed, and NMP 65.5 6 g was added thereto, and the mixture was continuously fed. Stir in nitrogen to dissolve. This diamine solution was stirred, and 8.544 9 g (39.18 mmol) of pyromellitic dianhydride was added thereto, and NMP was added thereto so that the solid content concentration was 15% by mass, and the mixture was stirred at room temperature for 24-96 to 201206994 hours. The obtained polyaminic acid solution had a viscosity of 523 mPa·s at a temperature of 25 °C. Further, the molecular weight of the poly-proline is Mn = 20565, Mw = 4 7 9 1 2 〇 In this solution, 0.3% by mass of NMP solution of 3-glycidoxypropylmethyldiethoxydecane is added. 13.79 g gave a polyamic acid solution (PAA-11). (Synthesis Example 36) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 3.2,080 g (1,200 mmol) of 4,4'-diaminodiphenyl ether and DA-7 5.8 1 47 were weighed. 24.0 mmol), 60.42 g of NMP was added, and it was stirred and continuously dissolved by nitrogen gas. The diamine solution was stirred, and 7.7658 g (39.60 mmol) of 1,2,3,4-cyclobutanine tetraresic acid dianhydride was added, and NMP was added to make the solid content concentration 20% by mass, and the mixture was stirred at room temperature. hour. The resulting polyglycolic acid solution had a viscosity of 1972 mPa*s at a temperature of 25 °C. Further, the molecular weight of the poly-proline was Mn = 15159 and Mw = 38,251. Further, 0.05 04 g of 3-glycidoxypropylmethyldiethoxy decane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-12). (Synthesis Example 3 7 ) 3,5-diaminobenzoic acid 2.430 1 g (1 5.97 mmol ) and DA-8 9.4204 g were weighed in a 1 mL bottle equipped with a stirring device and a nitrogen introduction tube. (24.0 mmol), NMP 44.60 g was added, and the mixture was continuously stirred and dissolved in nitrogen-97-201206994. This diamine solution was stirred, and BDA 4.75 05 g ( 23.98 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Next, NMP 44_59 g, 1,2,3,4-cyclobutanetetracarboxylic dianhydride 3.1 054 g (15.84 mmol) was added. Further, NMP was added to have a solid content concentration of 15% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 802 mPa»s at a temperature of 25 °C. Further, the molecular weight of the poly-proline is Mn=1 326 1 and Mw = 32578 o. Further, 0.0590 g of 3-glycidoxypropylmethyldiethoxydecane is added to the solution, and the mixture is stirred at room temperature. At 24 hours, a polyamine solution (PAA-13) was obtained. (Synthesis Example 3 8 ) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 3.6504 g (23.69 mmol) of 3,5-diaminobenzoic acid and DA-7 3.8718 g (15.98 mmol) were weighed. 68.6 g of NMP was added, and it was stirred and continuously dissolved by nitrogen gas. This diamine solution was stirred, and DAH-1 1 1.5 3 87 g (39.21 mmol) was added. Further, Ν Μ P was added to have a solid content concentration of 20% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 736 mPa*s at a temperature of 25 °C. Further, the molecular weight of the poly-proline is Mn = 1 009 1 and Mw = 1951 1 » Further, 3-glycidoxypropylmethyldiethoxydecane 0.05 72 g is added to the solution at room temperature. After stirring for 24 hours, a polyamidonic acid solution (PAA-14) was obtained. -98 - 201206994 (Synthesis Example 3 9 ) 3,5-diaminobenzoic acid 3.6603 g (24.06 mmol), 1,3-double was weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. (4-aminophenylethyl)urea 4.7740g (16.0 mmol), NMP 28.5 9g was added, and it was stirred and continuously dissolved in nitrogen gas. The diamine solution was stirred and BDA 2.3782g (12.0 mmol) was added. Stir at room temperature for 2 hours. Next, force into NMP 38. 1 3g, pyromellitic dianhydride 6.0903g ( 27.92 mmol). Further, Ν Μ P was added so that the solid content concentration was 15% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 744 mPa.s at a temperature of 25 °C. Further, the molecular weight of the poly-proline is Mn = l 777 1 and Mw = 3 899 1. Further, 0.05 g of 3-glycidoxypropylmethyldiethoxy decane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-1 5 ). (Synthesis Example 40) 0.6123 g (4.00 mmol) of 3,5-diaminobenzoic acid and 4,4-diaminodiphenyl were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 3.99 g (16.06 mmol) of an amine was added, and 19.64 g of NMP was added thereto, and the mixture was continuously stirred and supplied with nitrogen to dissolve. This diamine solution was stirred, and BDA 3.1 78 0 g (16.04 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Next, NMP 8.93g' pyromellitic dianhydride 〇.8736g (4. 〇l mmol) was added. Further, NMP was added to have a solid content concentration of 18% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution has a viscosity of -99 to 201206994 8100 mPa·s at a temperature of 25 °C. 'The molecular weight of the poly-proline is Mn = 2253 7 , Mw = 7260 1 〇 Then add '3 - glycidoxypropyl methyl diethoxy decane 0.0235g' in this solution and stir at room temperature At 24 hours, a polyamine solution (PAA-1 6) was obtained. (Synthesis Example 4 1 ) 3,5-diaminobenzoic acid 3.65168 (24.〇111111〇1), 4-amino-1 was weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. ^-Methylphenethylamine 2.4070 g (16.02 mmol), NMP 66_21 g was added, and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was stirred and 8.5972 g (39.42 mmol) of pyromellitic dianhydride was added. Further, NMP was added to have a solid content concentration of 15% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyaminic acid solution had a viscosity of 488 mPa.s at a temperature of 25 °C. Further, the molecular weight of the poly-proline was Mn = 13205 and Mw = 33,511. Further, 0.0438 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-17). (Synthesis Example 42) 3,5-diaminobenzoic acid 3_65 3 2 g (24.01 mmol), DA-7 3.8 7 90 g (16.01 mmol) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. ), NMP 70.32g was added to the mouth, and it was stirred and continuously dissolved in nitrogen gas to dissolve. This diamine solution was added with stirring, and DAH-2 -100-201206994 12.0709 g (39.41 mmol) was added. Further, NMP was added to have a solid content concentration of 20% by mass, and the mixture was stirred at room temperature for 24 hours. The resulting polyamic acid solution had a viscosity of 207 mPa.s at a temperature of 25 °C. Further, the molecular weight of the poly-proline was Mn = 5269 and Mw = 12875. Further, 0.0586 g of 3-glycidoxypropylmethyldiethoxydecane was added to the solution, and the mixture was stirred at room temperature for 24 hours. , obtained a polyamine solution (PAA-18). (Example 1 8) A stirrer was placed in a 50 ml Erlenmeyer flask to collect 3.6139 g of the polyamidomate solution (PAE-3) obtained in Synthesis Example 14, and the polyaminic acid solution obtained in Synthesis Example 29 ( PAA-5) 2.7012g, adding NMP 5.7093g, BCS 3.01g, and adding 4-(t-butoxycarbonylamino)pyridine (hereinafter, abbreviated as Boc-AP) 0.l28 4g The mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (1-1). (Example 1 9) The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4040 g of the polyamidomate solution (PAE-4) obtained in Synthesis Example 15 and the polyaminic acid solution obtained in Synthesis Example 30 were weighed. PAA-6) 2.468 7g, NMP 3.2072 g, BCS 2.03 48g, and Boc-AP 0.0542 g of hydrazine imidization accelerator were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (1-2). (Example 20) -101 - 201206994 The stirrer was placed in a 50 ml Erlenmeyer flask, and the polyacetamide solution (PAE-4) obtained in Synthesis Example 15 was weighed 2.4548 g, and the polyamine obtained in Synthesis Example 31 was obtained. Acid solution (PAA-6) 2.0213g, adding NMP 3.6200g, BCS 2.0116g, adding Boc-AP 0.0415g of ruthenium promoter, stirring with magnetic stirrer for 30 minutes, liquid crystal alignment agent (1-3) . (Example 2 1) The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4232 g of the polyamidomate solution (PAE-5) obtained in Synthesis Example 16 and the polyaminic acid solution obtained in Synthesis Example 33 were weighed ( PAA-9 ) 2.4189g, adding N928 3.2928g, BCS 2.02 72g, and adding hydrazine imidization promoter to Ν-α-( 9-fluorenylmethoxycarbonyl)-Nt-butoxycarbonyl-L-histamine Acid (hereinafter, abbreviated as "1〇&lt;?-His" 0.04 16g, and stirred for 30 minutes using a magnetic stirrer, the liquid crystal alignment agent (1-4) was obtained. (Example 22) A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4238 g of the polyamidomate solution (PAE-5) obtained in Synthesis Example 16 and the polyaminic acid solution (PAA) obtained in Synthesis Example 33 were weighed. -9 ) 1.868 1 g, NMP 3.6548g, BCS 2.0158g, and Fmoc-His 0.03 72g of hydrazine imidization promoter were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (1-5). (Example 23) A stirrer was placed in a 50 ml Erlenmeyer flask, and the polyacetate solution (PAE-6) obtained in Synthesis Example 17-102-201206994 was weighed 2.4356 g, and the polycondensate obtained in Synthesis Example 34 was collected. Amino acid solution (PAA-10) 2.5278g, added NMP 3.2644g, BCS 2.0.3 66g, and then added 醯iimination accelerator Fmoc-His 〇.〇550g, stirred with magnetic stirrer for 30 minutes, to obtain liquid crystal alignment agent (1-6). (Example 24) A stirrer was placed in a 50 ml Erlenmeyer flask, and the polyphthalate solution (PAE-7) obtained in Synthesis Example 18 was weighed 2.401 2 g, and the polyaminic acid solution obtained in Synthesis Example 35 (PAA) -11) 2.4115 g, NMP 2.6514 g, BCS 2.0052g were added, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (Π-1). (Example 25) The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4130 g of the polyamidate solution (PAE-7) obtained in Synthesis Example 18 and the polyamidonic acid solution (PAA) obtained in Synthesis Example 35 were weighed. -11) 2.4216g, adding NMP 2.6780g' BCS 2.01 98g, adding 208% by mass of NMP solution (306-1g) of polyfunctional epoxy compound as crosslinking agent, and stirring for 30 minutes using a magnetic stirrer 'Get liquid crystal alignment agent (II-2). (Example 26) A stirrer was placed in a 50 ml Erlenmeyer flask, and the polyphthalate solution (PAE-4) obtained in Synthesis Example 15 was weighed 2.43 02 g, and the polylysine solution obtained in Synthesis Example 36 (PAA) ·12) 1.8678g' was added to NMP 3.8086g, -103-201206994 BCS 2.0060g, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (Π-3). (Example 2 7) The stirrer was placed in a 5 mm ml Erlenmeyer flask, and 2.4144 g of the polyphthalate solution (PAE-4) obtained in Synthesis Example 15 and the polyamidonic acid solution obtained in Synthesis Example 36 were weighed. (PAA-1 2 ) 1.8062g, adding NMP 3.8184g, BCS 2.01 68g, and adding 0.040g of (AD-2) as a polyfunctional hydroxyl group-containing compound as a crosslinking agent, and stirring for 30 minutes using a magnetic stirrer to obtain liquid crystal alignment Agent (Π-4). (Example 2 8) The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4015 g of the polyamidomate solution (PAE-4) obtained in Synthesis Example 15 and the polyaminic acid solution obtained in Synthesis Example 37 were weighed. PAA-13) l_8005g, NMP 3.8063g, BCS 2.0011g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (II-5). (Example 29) A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4120 g of the polyamidomate solution (PAE-8) obtained in Synthesis Example 19 and a polyaminic acid solution (PAA) obtained in Synthesis Example 38 were weighed. - 1 4 ) 1.8 3 8 9g' NMP 3.863 9g and BCS 2.0181g were added, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-6). -104-201206994 (Example 30) The stirrer was placed in a 50 ml Erlenmeyer flask, and the polyphthalate solution (PAE-8) obtained in Synthesis Example 19 was weighed to 2.4 l 2 g, and the synthesis example 38 was obtained. Polyacrylic acid solution (PAA-14) 1.8389 g, added NMP 3.8639 g, BCS 2.0181 g' (AD-4) 0.0318 g of a polyfunctional cyclic carbonate compound as a crosslinking agent, and stirred for 30 minutes using a magnetic stirrer , liquid crystal alignment agent (II-7). (Example 3 1) The stirrer was placed in a 50 ml Erlenmeyer flask, and the polyamidomate solution (PAE-9) obtained in Synthesis Example 20 (1.28 g) and the polylysine obtained in Synthesis Example 39 were weighed. Solution (PAA-1 5 ) 3.268 8 g, NMP 3.6154 g, BCS 2.059 1 g were added, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-8). (Example 3 2) The stirrer was placed in a 50 ml Erlenmeyer flask, and the polyamidomate solution (PAE-1 0 ) obtained in Synthesis Example 21 was weighed in 2.4236 g, and the polyaminic acid solution obtained in Synthesis Example 40 was weighed. (PAA-1 6 ) 2.3539 g, N782 0.3782 g, γ-BL 3.0639 g, BCS 2.0178 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (II-9). (Example 33) -105-201206994 The stirrer was placed in a 50 ml Erlenmeyer flask, and the polyphthalamide solution (PAE-5) obtained in Synthesis Example 16 was weighed 4.2045 g, and the polyamine obtained in Synthesis Example 41 was obtained. Acid solution (PAA-1 7 ) 1.22 8 1 g, NMP 2.6041 g, BCS 2.0 11 2g were added, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-1 0 ) » (Example 34) The mixture was placed in a 50 ml Erlenmeyer flask, and 2.4195 g of the polyamidate solution (PAE-11) obtained in Synthesis Example 22 and the polyamidic acid solution (PAA-5) obtained in Synthesis Example 29 were added to NMP 3.8069. g, BCS 2.0204g, stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (II-1 1 ). (Example 3 5) The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4176 g of the polyamidate solution (PAE-6) obtained in Synthesis Example 17 and the polyaminic acid solution obtained in Synthesis Example 42 were weighed. PAA-18) 2.0148g, NMP 3.8182g, BCS 2.0129g were added, and stirred using a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (11-12). (Example 36) A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.3987 g of the polyamidate solution (PAE-6) obtained in Synthesis Example 17 and a polyamidonic acid solution (PAA) obtained in Synthesis Example 42 were weighed. - 1 8 ) 2.1 543g, added NMP 3.8130g, -106- 201206994 BCS 2.0374g 'Additional (AD-3) 0_0460g of polyfunctional propylene oxide compound as crosslinking agent, stir for 3 minutes using magnetic stirrer Liquid crystal alignment agent (I -1 3 ). (Comparative Example 1 7) The stirrer was placed in a 50 ml Erlenmeyer flask, and 7.2164 g of the polyamidomate solution (PAE-12) obtained in Synthesis Example 23 and the polyaminic acid solution obtained in Synthesis Example 29 were weighed. PAA-5) 2.7470 g, NMP 2.1068 g, BCS 3.0264 g, and Boc-AP 0.1396 g of a ruthenium iodide promoter were added, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (a-1). (Comparative Example 1 8) The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4 504 g of the polyamidate solution (PAE-13) obtained in Synthesis Example 24 and the polyaminic acid solution obtained in Synthesis Example 30 were weighed. PAA-6) 2.4805g, NMP 3.2447g, BCS 2.0226g, and Boc-AP 0.0547g of ruthenium hydride promoter were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (a-2). (Comparative Example 1 9) The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4012 g of the polyamidate solution (PAE-14) obtained in Synthesis Example 25 and the polyaminic acid solution obtained in Synthesis Example 33 were weighed. PAA-9) 1.8320 g, NMP 3.8172 g, BCS 2.0195 g, and Fmoc-His 0.043 3 g of a ruthenium iodide promoter were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (a-5). -107-201206994 (Comparative Example 20) The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4017 g of the polyamidomate solution (PAE-15) obtained in Synthesis Example 26 and the polyamine obtained in Synthesis Example 33 were weighed. Acid solution (PAA-9) 2.5 777g, adding NMP 3.2518g, BCS 2.000g, adding Fmoc-His 0.0550g of hydrazine imidization promoter, stirring with magnetic stirrer for 30 minutes to obtain liquid crystal alignment agent (a-6) . (Comparative Example 2 1) The stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4 335 g of the polyamidomate solution (PAE-2) obtained in Comparative Synthesis Example 1 was weighed, and the polyaminic acid solution obtained in Synthesis Example 35 was weighed. (PAA-11) 2.4013g, adding NMP 2.623 8g, BCS 2.0 1 05g, stirring with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (b-Ι) 〇 (Comparative Example 22) Putting the stirrer into a 50 ml Erlenmeyer flask In the same manner, 2.4264 g of the polyamidate solution (PAE-13) obtained in Synthesis Example 24 and 1.8157 g of the polyamidic acid solution (PAA-12) obtained in Synthesis Example 36 were weighed, and NMP 3.8 3 5 2 g, BCS 2.0448 was added. g, stirring using a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (b-3). (Comparative Example 23) The stirrer was placed in a 50 ml Erlenmeyer flask, and the polyglycolate solution (PAE-1 7 ) obtained in Synthesis Example 28-108-201206994 was weighed 1.2049 g, and the polycondensation obtained in Synthesis Example 39 was obtained. 3.298 g of a proline solution (PAA-15), 3.6342 g of NMP and 2.0694 g of BCS were added, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment agent (b-9). (Comparative Example 24) A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4025 g of the polyamidomate solution (PAE-1 6 ) obtained in Synthesis Example 27 and the polyaminic acid solution obtained in Synthesis Example 40 were weighed. PAA-16) 2.2514 g, NMP 0.3792g, γ-BL 3.0007g, BCS 2.0015g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (b-ΙΟ). (Comparative Example 25) A stirrer was placed in a 50 ml Erlenmeyer flask, and 4.2529 g of the polyamidomate solution (PAE-1 4 ) obtained in Synthesis Example 25 and the polyaminic acid solution obtained in Synthesis Example 41 were weighed. PAA-17) 1.2473 g, NMP 2.6481 g, BCS 2.0664 g were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (b-11). (Comparative Example 26) A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4260 g of the polyphthalate solution (PAE-1 5 ) obtained in Synthesis Example 26 and the polyaminic acid solution obtained in Synthesis Example 42 were weighed. PAA-18) 2.2122g, NMP 3.8118g, BCS 2.0585g were added, and stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal alignment-109-201206994 agent (b-13). (Example 3 7) The liquid crystal alignment agent (1-1) obtained in Example 18 was filtered using a filter of 1·〇μπι, and then spin-coated on a glass substrate with a transparent electrode at a temperature of 80 ° C. The plate was dried on a hot plate for 5 minutes, and baked in a warm air circulating oven at a temperature of 230 ° C for 20 minutes to obtain a yttrium imidized film having a film thickness of 100 nm. The average thickness (Ra ) of the center line of the ruthenium-imided film was measured. The measurement results are shown in Table 4 below. (Example 3 8 to 5 2 and Comparative Example 2 7 to 3 5 ) Except each of the above Examples 19, 22, 24 to 27, 29 to 36, and Comparative Examples 17 to 19, 2 1 to 26 Each of the coating films was formed in the same manner as in Example 37 except for the liquid crystal alignment agent. The film surface of each coating film was observed using AFM. Further, the average thickness (Ra ) of the center line of each coating film was measured. The measurement results are shown in Table 4 below. -110- 201206994 [Table 4] ___——— f center average female [Ml liquid crystal alignment agent composition (mass ratio PAK %]).... ύκκ additive example 3 8 (1-1) r aCi FAt-iJ (40) (60) Boc-AP 0. 81 Example 3 9 (1-2) FAt-4 (40) Boc-AP 1. 00 Example 4 0 CI - 5) FAt-b (40) fmoc-His , • _ 0.94 Comparative Example 2 7 (a - 1) FAK-1Z (40) Boc-AP 13. 95 Comparative Example 2 8 (a-2) PAt-13 (40) Boc-AP 3. 14 Comparative Example 2 9 (a - 5 ) FAK-14 (40) Fm〇C&quot;Hi s 5. 59 Example 4 1 (II-1) Pa£-/ (40) T^A-Il (60), a 0.49 Example 4 2 (11-2> PAt-Y (40) T^A-ll (60) AD-t 0.46 Example 4 3 (II-3) FAIi-4 (40) TAA-12 (60) A 1.79 Example 4 4 (ΙΙ-4) m-4 (40) ^S)r' AD*2 1.45 Example 4 5 (II- 6) (40) (60) A 1.99 Example 4 6 (II- 7) PAt-8 (40) TAA-U (60) AD-4 1.92 Example 4 7 (II- 8) TSF9 (20) TAA-lb (80) —_· "1. 10 Example 4 8 dl-9) TAF10 (40) PAA-lb (60) - 1.16 Example 4 9 (II- 1 0) PAli-b (70) PAA-1V (30) - · 0. 37 Example 5 0 (II- 1 1 ) ΡΑϋ-11 (40) PAA&quot;i&gt; (60) A 2.29 Example 5 1 (II-1 2) TiFB (40) PAA-lt (60) - 0.79 Example 5 2 (II-1 3) Τ3ΓΕ-6 (40) paa-16 (60) AD-3 0. 80 Comparative Example 3 0 (b-1) vki~\ (40) FAA-Jl (60) A 36. 8 Comparative Example 3 1 (b-3) Pa£-13 (40) FAA-1^ (60) —* 2.39 Comparative Example 3 2 (b - 8 ) Can-ΙΪ (20) PAA-lb (80) 3.21 Comparative Example 3 3 (b-9) PAli-16 (40) PAA-16 (60) 2. 51 Comparative Example 3 4 (b- 1 0) ME-14 (70) M3R7 (30) 2.55 Comparative Example 3 5 (b-1 2) PAE-15 (40) FAA-ib (60) 1. 55 [Industrial Applicability] The liquid crystal alignment agent of the present invention can reduce the surface unevenness of the liquid crystal and the liquid crystal alignment film by reducing the fine unevenness on the surface of the obtained liquid crystal alignment film, thereby improving the voltage retention rate. Electrical characteristics such as ion density and residual DC voltage. As a result, it is known that the liquid crystal alignment agent of the present invention can be widely used for TN elements, STN elements, TFT liquid crystal elements, and even vertical alignment type liquid crystal display elements. In addition, the entire contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2010-05 8 5 52, filed on March 15, 2010, are hereby incorporated by reference herein in It is described in the Summary of the Invention. -112-

Claims (1)

201206994 VII. Patent application scope: 1. A liquid crystal alignment agent comprising the following (A) component and (B) component, (A) component: having a repeating unit represented by the following formula (1), and a polyglycolate which satisfies the conditions of any one of the following (i) to (iii) [Chemical Formula 1] (1) (wherein ^^ is a tetravalent organic group, 丫, is a divalent organic group 'R! is an alkyl group having 1 to 5 carbon atoms, and human 1 and human 2 each independently represent a hydrogen atom' or may have a substitution The alkyl group having 1 to 20 carbon atoms, the alkenyl group, and the alkyl group) (i) X, Y, or both of the formula (1) having a group consisting of the following formulas (2) and (3) a monovalent or divalent substituent of at least one selected structure, (A), A2, A2 or both of the formula (1) having a group consisting of the following formulas (2) and (3) a monovalent or divalent substituent of at least one of the selected structures, (iii) X丨, Y2 of the formula (1) or both of them having a group consisting of the following formulas (2) and (3) a monovalent or divalent substituent of at least one of the selected structures, and A, Α2 or both of them are at least one selected from the group consisting of the following formulas (2) and (3) A monovalent or divalent substituent of the structure, -113- 201206994 [化2] 〇1 Ο—Ν—(1 2 3)—Β!—L〇_〇2 (3) (Formula (2) and (3) 0, and D2 are each a protecting group which may be substituted by a hydrogen atom through heat treatment; B1 is a single bond or a divalent organic group; however, the ester group in the formula (3) Knot is a carbon atom) (B) component: a repeating unit represented by the following formula (4) of the poly acid amide, [Formula 3] There is the same definition as in the formula (1). -114- 1 _ The liquid crystal alignment agent of the first application of the patent scope, wherein the content of the (a) component and the component (B) are by mass ratio (a/B) For, 1/9 to 9/1. 2. The liquid crystal alignment agent according to claim 1 or 2, wherein the total content of the component (A) and the component (B) is 1 to 1% by mass based on the organic solvent. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the protective group is at least 1 selected from the group consisting of tert-butoxycarbonyl and 9-fluorenylmethoxycarbonyl. The basis of the species. 5. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the protecting group is tert_butyl. 6. The liquid crystal alignment agent according to any one of the first to fifth aspects of the invention, wherein the component (A) is at least one selected from the group consisting of the following formulas (5) and (6) The polyglycolic acid vinegar represented by the substituent '[4] (In the formula (5), B2 is a single bond and a divalent organic group, and R2, R3, and h each independently represent a hydrogen atom or an organic group having a carbon number of 1 to 20; [Chemical 5] o ch3 II — -β3』一〇--ch3 (6) ch3 (In the formula (6), B3 is a single bond or a divalent organic group; wherein the atom bonded by the t-butoxycarbonyl group in the formula (6) is carbon atom). 7. The liquid crystal alignment agent according to any one of claims 1 to 6, wherein the component (A) is a formula (UiY having a structure selected by the groups of the formulas (5) and (6). A liquid crystal alignment agent of any one of the above-mentioned items, wherein the component (A) is Ai of the formula (1). And A2 or both of them are polyamidomates having a substituent of at least one selected from the group consisting of formulas (5) and (6). 9. In the scope of claims 1 to 8, In any one of the liquid crystal alignment agents, the (A) component is a polyglycolate having the structure of the formula (1) represented by the following formula (7): -115-201206994, [Chem. 6] (7); Ruler 6 is a liquid crystal alignment agent of the formula: a is 1 to 4, represented by the following formula (wherein Rs is a single bond or an organic group (5) and (6) having a carbon number of 1 to 20; At least one constructed integer selected by the group). (1) The component (A) is a structure of the formula (1), and is a structure having at least one selected from the group of structures, [ 7] XX -Ο- jCu ηβ2 ~6 jCk ~0~ ~0^. JCX/ -Qt~\ jy^(xjy°xx -ο-α- Liquid crystal alignment agent is independently represented by 1 1. As claimed in the patent scope In any one of the above-mentioned formulas (1) and (4), at least 1@, -116-201206994 is selected in the group represented by the following formula: 8] Ip it CHs , P: XX 众XO: ig: 〕甘CH3 o 1 2 . The liquid crystal alignment agent of any one of claims 1 to 5, wherein 'Y1' is represented by the following formula At least one selected from the group of structures, -117- 1 1 4 · A liquid crystal alignment film which is obtained by coating, baking, and irradiating ultraviolet light of a liquid crystal alignment agent according to any one of claims 1 to 12; Liquid crystal alignment film. A liquid crystal alignment film obtained by coating and baking a liquid crystal alignment agent according to any one of claims 1 to 12. 201206994 IV. Designated representative: (1) The designated representative of the case is: None (2) The symbol of the symbol of the representative is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 1), (4) 〇〇 A2 (1) (4) -4-