TW200804517A - Liquid crystal aligning film composition, liquid crystal aligning film and liquid crystal display element - Google Patents

Abstract

An aligning film hard to be reduced by rubbing treatment is sought. An aligning film composition and an aligning film making the aligning characterist appear uniformly are sought. An aligning film and a liquid crystal display element fabricated with a high yield rate are sought. Therefore, this present invention provides a liquid crystal aligning film composition including at least one group chosen from groups composed of polyeater-polyamide acid (Al) and its imidization compound "polyeater-polyimide (A2)". The polyeater-polyamide acid (Al) is obtained by at least using polyhydroxy compound (al), diamine (a2) and a compound (a3) having at least two acid anhydride radicals.

Description

。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 (2) A composition for an alignment film used in a liquid crystal display element or the like, a solubilizing acid solution has been practically applied, and the above solubility is applied. In the present invention, when the surface of the alignment film is subjected to a rubbing treatment to exhibit a dissimilarity characteristic, the private/sigma film is generated and dust or static electricity is likely to be generated. For example, if 2, dust adheres to the surface of the alignment film, resulting in poor display. In addition, when the directional film was used for the TFT element, the circuit was damaged and the yield was lowered due to dust and static electricity. An alignment film that is not easily scratched by rubbing treatment by S2. The present invention provides an alignment film and a liquid crystal which are prepared in a high yield in the composition of the alignment film which exhibits a characteristic sentence. [Invention] The present invention provides a liquid crystal alignment obtained by the following composition. a film composition, a group of elements, etc. ^ film and liquid crystal display having the liquid crystal alignment film [1] liquid crystal alignment film a 1, A includes a group selected from the group consisting of the following 4, and A, a polymer represented by the following formula (3) and a polyester comprising a constituent unit represented by the following formula (3) and the following formula (2_1} - One or more groups of polyimine (A2), wherein the dotted line indicates a linking site, and R11, r21, r22, r3], r32, and R each independently represent a carbon atom of 2 to loo. Organic group.

II II Q NH-R12-NH.......

Η〇〇〇 / XC〇〇H

(2-1) 11 " 99 C\ C 一〇--R ——〇 \21

Η〇〇〇 / XC〇〇H

[2] A liquid crystal alignment film composition comprising a polymer A, the polymer A comprising a group selected from the group consisting of polyester-polyglycine (A1) and poly-polyimine (A2) One or more kinds of the polyester-polyaminic acid (A1) include a constituent unit represented by the following formula (!) and one or more constituent units selected from the following formula (2-21) and the following formula (2-22) represents The constituent unit of the group consisting of the constituent units, the polyester-polyimine (A2) includes a constituent unit represented by the following formula (3) and one or more constituent units selected from the following formula (2-21) And a constituent unit of a group consisting of constituent units represented by the following formula (2-22), and the formula 200804517 12 , 21 t23

In the middle, the dotted line indicates the joint, Rn, Ru, R21, R23, R, 24

R 31 R32 and R33 each independently represent an organic group having 2 to 100 carbon atoms - (1)

〇 II -C 〇 II /C-NH- >12

R 11

HOOC COOH # 〇II -c 〇 Vli 123 C——〇一 R23-〇 21

R HO—C XC—OH (2-21)

〇〇 〇H II li 124 ------C, JZ—〇一RZ4-〇----------一(2-22) >21

HO-C XC-OH

II II 〇 〇

7 200804517 Λ Liquid crystal alignment film composition, including polymer A, polymer '匕 ♦ ester poly phthalic acid (A1) and polyester-polyimine (A2) group of - or - In the above, the poly-proline (A1) includes a constituent unit represented by the following formula (1) and one or more constituent units selected from the following formula (2_31), represented by the following formula (2-32). The constituent unit and the constituent unit of the following formula (2_33) are not formed into a unit, and the poly-I-imine (A2) comprises a constituent unit represented by the following formula (3) and one or more selected from the group consisting of (2-31) The constituent unit of the constituent unit represented by the following formula (2_32) and the constituent unit represented by the following formula (2-33), where the dotted line indicates the joint position, R] 1. R12, R21, r25, r26, r27, R31, R32 and R33 each independently represent an organic group having 2 to 1 Å carbon atoms. ,土 II ? 〇 —...c /0—NH—R12—NH------- /H\ V (1)

HOOC7 XCOOH

8 200804517 〇II c 〇II l25 C——〇一R25—〇-

R 21 H〇一 CII 〇 C-OHII 〇 (2-31) # 〇

OH /C - 〇一R26 - 〇

R 21 HO-CII 〇 C-OHII 〇

One C〇〇H (2-32) 3 3 (2- 200804517 [4] A composition for a liquid crystal alignment film comprising a polymer A, the polymer A comprising a polyester-polylysine (A1) and a One or more groups of polyester-polyimine (A2) obtained by polyester-polyaminic acid (A) oxime imidization, polyester-polyglycine (A1) is It is obtained using at least a polyvalent hydroxy compound (al), a diamine (a2), and a compound (5) including two or more acid anhydride groups. [5] The composition for a liquid crystal alignment film according to [4], wherein the polybasic composition is #

The compound (al) is a diol represented by the following formula (5-1): wherein R5! is an organic group having 2 to 100 carbon atoms. [6] The composition for a liquid crystal alignment film according to [5], wherein the poly(A)-polyamic acid (4) comprises a composition represented by the following formula (1). The following formula (4) indicates that the constituent unit 'poly I polyienimine (A2) includes a constituent unit represented by the following formula (3) and a formula represented by the following formula (2-1), wherein R11, R12, R2] , R3i, : 33 dotted line table is not connected, ^ ^ and R respectively represent an organic group with a carbon number of 2 to 100. Anti-people

〇 〇 II II -----c /C-NH-R12-NH....... (1) / \

HOOC COOH 〇 〇 一-cv /έ 一〇——R22—〇----------- XR21 A” / \

HOOC COOH ίο 200804517

[7] The liquid crystal alignment film composition according to [4], wherein the polyvalent hydroxy compound (al) is a triol represented by the following formula (5-2), wherein R52 represents a carbon number of 2 to 100. Organic group.

The liquid crystal alignment film composition according to the above [7], wherein the polyester-polylysine (A1) comprises a constituent unit represented by the following formula (1) and an or A constituent unit of a group consisting of a constituent unit represented by the following formula (2-21) and a constituent unit represented by the following formula (2-22), and the polyester polyimine (A2) includes the following formula (3) a constituent unit represented by the group of one or more constituent units selected from the following formula (2-21) and a constituent unit represented by the following formula (2-22), wherein the dotted line The linking sites are represented, and Rn, R12, R2, R23, R24, R31, R32 and R33 each independently represent an organic group having 2 to 100 carbon atoms. 〇 〇 II II 19 ------ C /C—NH—R12—NH.....— (1) \11 / \

HOOC COOH 200804517 〇 c ,c—〇一 r23-〇

II (2-21) R21

H〇一C C-OH

II II 〇 〇 〇 II -c

OH 〇II .24 /C—0—R-0

R 21 (2-22)

HO—C C—OH &

OHC

N oyc \ one

2 3 R

N

R /33 one (3) \

H〇〇C

COOH

[9] The liquid crystal alignment film composition according to [4], wherein the polyvalent hydroxy compound (al) is a tetrahydric alcohol represented by the following formula (5-3), wherein R53 represents a carbon number of 2 to 100. Organic group.

OH

HO-R53-OH

OH (5-3) [10] The composition for liquid crystal alignment film according to [9], wherein the polyester-polyfluorene 12 200804517

The amine acid (A1) includes a constituent unit represented by the following formula (1) and one or more constituent units selected from the following formula (2-31), a constituent unit represented by the following formula (2-32), and the following formula (2) -33) The constituent unit of the group consisting of the constituent units represented by the constituent unit, the polyester-polyimine (A2) includes a constituent unit represented by the following formula (3) and one or more selected from the group consisting of the following formula (2-31) The constituent unit of the constituent unit represented by the following formula (2-32) and the constituent unit represented by the following formula (2-33), wherein the dotted line indicates the joint portion, Rn, R12, and R21 R25, R26, R27, R31, R32 and R33 each independently represent an organic group having 2 to 100 carbon atoms. 〇 〇 II II 19 ........cv (1) V11 / \

H〇〇C C〇〇H 13 200804517

R 21

〇 〇 II l25 ,c—〇一r25~〇- I \ 〇 c—OH (2-31) 〇II ......c, HO-C〆II 〇

R 〇 〇

OH /C——〇一R26—〇21 〇C—OHII 〇〇〇OH ——C yC——0—R^—〇-- \ R 21 I / \ OH HO-C II 'C-〇H II II 〇II 〇〇H 〇li 〇II IS ——c II c II c r32—r/ 'I / \ / V/ H〇〇C cc 〇II c- ,33

The composition for a liquid crystal alignment film according to any one of [4] to [10] wherein a polyhydric hydroxy compound (al) is used in the liquid crystal alignment film according to any one of [4] to [10]. Is one or more selected from the group consisting of the following compounds,

HO—\ /—OH HO〆 H HO—丨, —OH OH OH OH

15 200804517 The diamine (a2) is one or more selected from the group consisting of the following compounds,

H2n-^-o-{34i〇-〇-〇-i U Bu 3 2 16 93⁄4 200804517

17 200804517 A compound comprising 2 or more acid anhydride groups 3) is one or more selected from the group consisting of the following compounds.

〇

P

[12] The composition for a liquid crystal alignment film according to any one of [1] to [1], wherein the polyester-polyamido acid (?) or the polyester_polyimine (Α2) is a second 〇·5~19 mol amine group of amine (a2), including 2 or more acid anhydride groups: 1.5 to 20 moles of anhydrate of the substance (a3) and j mole of the polybasic compound (4) Every reaction is obtained. The composition for liquid crystal alignment film according to any one of [1] to [12], wherein the carrier (9) polymer (8) comprises a group selected from the group consisting of poly (proline) (B1) amine (B2). — The brewing acid (B1) includes a gentleman represented by the following formula (1), ^_水^, and a composition of the early formula, and the polyimine (B2) includes the composition of the following formula (4). In the formula, a R12, R4 and a sub-class of ^, /, ▲ table is not connected, Rl1, 蜀 table is not an anti-atomic number of 2~1〇〇 organic base (1) 200804517 〇〇it II 19 'C JZ-NH-R12-NH-

\r11 H〇〇C C〇〇H

[14] The composition for liquid crystal alignment film according to any one of [1] to [12], further comprising a polymer (B) comprising a polymer selected from the group consisting of poly(proline) (B1) and One or more groups consisting of polyimine (B2) obtained by polyaminic acid (B1) quinone imidization, poly-proline (B1) is at least using diamine (a2) and including 2 One or two or more acid anhydride group-containing compounds (a3). [15] The composition for liquid crystal alignment film according to [14] wherein the diamine (a2) is one or more selected from the group consisting of the following compounds,

H2N~^^-(CH2)4<

(CH2)3 ❿. servant

Nh2 — — h2n~(^-s-^-nh2 19 200804517

H2n-(^o-^)

b Bu 3 Latch 2^~^~^~0-(CH2)4-Cm^~^~NH2 2 ?H3

20 200804517 The compound (a3) comprising two or more acid anhydride groups is one or more selected from the group consisting of the following compounds.

The composition for a liquid crystal alignment film according to [15], wherein the acid _ includes a constituent unit represented by the following formula (1), and the poly-methane =

Machine group. ..., do not independently indicate that the number of carbon atoms is 2~

〇 II -C

R 11 C—NH—R12. One Nhl·

HOOC COOH

The liquid crystal alignment film composition according to any one of [13], wherein the composition for liquid crystal alignment film contains 1 to 50% by weight of polyamic acid (B1) and Polyimine (B2). [18] The composition for a liquid crystal alignment film according to [12], which further comprises an epoxide (C). [19] The composition for a liquid crystal alignment film according to [18], wherein the epoxy compound (C) is one or more selected from the group consisting of compounds represented by the following formulas (C1) to (C5), In the formula, η is an integer of 0 to 10.

22 200804517 〇 〇 〇 CH〇—C CH〇 〇 -〇——CH〇—CH—CHo\/ 〇 (C1) o;

V 〇- :〇 (C2) , ch2—〇c〆li 〇 CH, -〇

〇

f^N (C3) 〇 O:

〇 (C4) 23 200804517

(C5) [20] The liquid crystal 所述 as described in [18] or [19] contains a liquid crystal with a phase (C). In the weighting/0% oxygen compound [21] A liquid crystal alignment film obtained by, for example, a composition for a liquid crystal alignment film. [22] - A liquid crystal display element, including its moon. X LZi" is a liquid crystal alignment. It is a scorpion, and it has a special limitation. In the present specification, the "polyaminic acid" diimine (tetra) is not particularly limited as long as it is y which is a composition having both a guanamine and a ship. In the present specification, the term "polymerization" is not particularly limited as long as it is a compound having a structure of both an ester and a quinone. In the present specification, the "polyester-polyglycolic acid" is not particularly limited as long as it has a compound having both S曰 and feminic acid. According to the composition for an alignment film according to the preferred embodiment of the present invention, a film is obtained, and even if it is subjected to a rubbing treatment, an alignment film having less scratching, uniform alignment, and excellent alignment characteristics can be obtained. The alignment film obtained from the composition for an alignment film according to the preferred embodiment of the present invention and the liquid crystal display element using the alignment film can be produced in a high yield. The liquid crystal display element according to a preferred embodiment of the present invention has high contrast. The above and other objects, features, and advantages of the present invention will become more apparent from the aspects of the appended claims. [Embodiment] The first aspect of the present invention is a composition for a liquid crystal alignment film, comprising a water a substance A'. The polymer a includes a polyester-polyamide (A) and a poly-poly One or more of the groups consisting of imines (A2). According to a second aspect of the invention, the composition for a liquid crystal alignment film according to the second aspect of the invention further comprises a composition of a polymer B, wherein the polymer B comprises a poly(protonic acid) (B1) and a polyimide (B2). The group consisting of -= more than one species. A-A third aspect of the present invention is a liquid crystal alignment film obtained from the composition for a liquid crystal alignment film of the present invention, and a liquid crystal display element having the alignment film.

The composition for the liquid crystal alignment film of the prior art 1 includes the polymer A, and the polymer A includes the polymer selected from the group consisting of polyester_polyglycine (A1) and polyester yoghurt (A2). One or more of the group consisting of. " JL Jucool-Polyuran Brewing (a η ester-polyproline (the structure of Α η 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚The following three compounds are preferable, and the following three compounds are preferable. [1] Polyester-polyaminic acid (AH) The structural unit represented by the above formula (1) and the above formula (2, 1) represent a constituent unit of 25 200804517 [2] Polyester-polyaminic acid (A1-2) The structural unit represented by the above formula (1) and one or more constituent units selected from the above formula (2-21) and the above formula (2-22) a compound of a constituent unit of a group consisting of the constituent units; [3] a polyester-polyproline (A1-3), a constituent unit represented by the above formula (1), and one or more selected from the above a compound of the constituent unit represented by the formula (2-31), the structural unit represented by the above formula (2-32), and the constituent unit of the constituent group represented by the above formula (2_33). - The terminal structure of the polyamic acid (A1) is, for example, an acid anhydride group, an amine group, a hydroxyl group or the like. In the above formula (1), formula (1), formula (2-21), and formula (2-22) In the formula (2-31), the formula (2-32), and the formula (2-33), an organic group having a tetravalent carbon number of 2 to 100 is independently represented by R2, and R22 represents a divalent carbon. An organic group having an atomic number of 2 to 100; R23 and R24 each independently represent a trivalent organic group having 2 to 100 carbon atoms; and R25, R26 and R27 each independently represent a tetravalent carbon atom of 2 In the present specification, the "organic group" is not particularly limited, and examples thereof include a cigarette having a carbon atom number of 2 to 1 Å which may have a substituent. Specific examples of the monovalent organic group include an alkoxy group having 2 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and an amine having a substituent. a decane 26 which may have a substituent, 200804517, an alkylthio group which may have a substituent (-SY1, wherein γ1 represents an alkyl group having 2 to 20 carbon atoms which may have a substituent), may have a substituent An arylthio group (-SY2 wherein Υ2 represents an aryl group having 6 to 18 carbon atoms which may have a substituent.), an alkylsulfonyl group which may have a substituent (- S02Y3, wherein γ3 represents an alkyl group having 2 to 20 carbon atoms which may have a substituent.) an aryl group fluorenyl group which may have a substituent (-S02Y4, wherein Y4 represents a carbon atom which may have a substituent It is an aryl group of 6 to 18. In the present specification, a hydrocarbon having a "hydrocarbon having 2 to 20 carbon atoms" may be either a saturated or unsaturated acyclic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon. When the hydrocarbon having 2 to 20 carbon atoms is an acyclic hydrocarbon, it may be a linear hydrocarbon or a branched hydrocarbon. The "hydrocarbon having 2 to 20 carbon atoms" includes: an alkyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and a carbon number. Is a di-dialkyl group of 4 to 20, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an aryl group having 7 to 20 carbon atoms, and 4 carbon atoms; a cycloalkyl group of -20 or a cycloalkenyl group having 4 to 20 carbon atoms. φ In the present specification, the "alkyl group having 2 to 20 carbon atoms" is preferably an alkyl group having 2 to 10 carbon atoms, and more preferably an alkyl group having 2 to 6 carbon atoms. The alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second-stage butyl group, a third-order butyl group, a pentyl group, a hexyl group, and a dodecane group. Base. In the present specification, the "alkenyl group having 2 to 20 carbon atoms" is preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 6 carbon atoms. Examples of the alkenyl group are not particularly limited, and examples thereof include a vinyl group, an allyl group, and 27 200804517 propylene group, isopropenyl group, 2-mercapto-1-propenyl group, 2-mercaptoallyl group, and 2-butyl group. Alkenyl and the like. In the present specification, the "alkynyl group having 2 to 20 carbon atoms" is preferably an alkynyl group having 2 to 10 carbon atoms, and more preferably an alkynyl group having 2 to 6 carbon atoms. The example of the alkynyl group is not particularly limited, and examples thereof include an ethynyl group, a propynyl group, and a butynyl group.

In the present specification, the "alkanediyl group having 4 to 20 carbon atoms" is preferably an alkadienyl group having 4 to 10 carbon atoms, more preferably an alkadienyl group having 4 to 6 carbon atoms. The example of the alkadienyl group is not particularly limited, and examples thereof include a 1,3-butadienyl group and the like. In the present specification, the "aryl group having 6 to 18 carbon atoms" is preferably an aryl group having 6 to 10 carbon atoms. The aryl group is not particularly limited, and examples thereof include a phenyl group, a 1-nyl group, a 2-nyl group, a phenanthryl group, a biphenyl group, an enyl group, and a phenanthryl group. In the present specification, the "alkylaryl group having 7 to 20 carbon atoms" is preferably an alkaryl group having 7 to 12 carbon atoms. Examples of the alkaryl group are not particularly limited, and examples thereof include o-nonylphenyl group, m-nonylphenyl group, p-nonylphenyl group, 2,3-fluorenylbenzyl group, 2,4-fluorenylbenzyl group, and 2,5-methyl group. Benzyl, o-isopropylphenyl, m-isopropylphenyl, p-cumyl, mesityl, and the like. In the present specification, the "aralkyl group having 7 to 20 carbon atoms" is preferably an aralkyl group having 7 to 12 carbon atoms. Examples of the aralkyl group are not particularly limited, and examples thereof include a benzyl group, a phenethyl group, a diphenyl fluorenyl group, a triphenyl fluorenyl group, a 1-naphthyl anthracenyl group, a 2-naphthoquinone group, and a 2,2-diphenyl group. Base, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl and the like. 28 200804517 In the present specification, the "cycloalkyl group having 4 to 20 carbon atoms" is preferably a cycloalkyl group having 4 to 10 carbon atoms. The example of the cycloalkyl group is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like. In the present specification, the "cycloalkenyl group having 4 to 20 carbon atoms" is preferably a cycloalkenyl group having 4 to 10 carbon atoms. The example of the cycloalkenyl group is not particularly limited, and examples thereof include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.

In the present specification, the "alkoxy group having 2 to 20 carbon atoms" is preferably an alkoxy group having 2 to 10 carbon atoms, and more preferably an alkoxy group having 2 to 6 carbon atoms. The alkoxy group is not particularly limited and includes ethoxy, propoxy, butoxy, pentyloxy and the like. In the present specification, the "aryloxy group having 6 to 20 carbon atoms" is preferably an aryloxy group having 6 to 10 carbon atoms. The aryloxy group is not particularly limited, and examples thereof include a phenoxy group, a naphthyloxy group, and a biphenyloxy group. In the present specification, "alkylthio (-SY1, wherein Y1 represents a group having 2 to 20 carbon atoms which may have a substituent.)" and ":": a sulfonic acid group (_S〇2Y3, wherein Y3 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. Among them, Y1 and Y2 are preferably an alkyl group having 2 to 10 carbon atoms, more preferably an alkyl group having 2 to 6 carbon atoms. base. The example of the alkyl group is not particularly limited, and examples thereof include a mercapto group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second-order butyl group, a third-order butyl group, a pentyl group, a hexyl group, and twelve Alkyl and the like. In the present specification, "arylthio group (-SY2, wherein Y2 represents an aryl group having 6 to 18 carbon atoms which may have a substituent.)" and "arorene thiol 29 200804517 wx ZX has a carbon atom having a substituent. In the case of the square group of 6 to 1 glycerol.), Y and γ4 are preferably an arylaryl group having 6 to 10 carbon atoms, and are not particularly limited. Examples thereof include a phenyl group, a naphthyl group, and 2 -naphthyl, anthracenyl, biphenylyl, anthracenyl, phenanthryl and the like. It is possible to "hydrocarbon having 1 to 12 carbon atoms", "alkoxy having 2 to 20 carbon atoms", "aryloxy group having 6 to 2 carbon atoms", "amine group", "= group" Substituents are introduced into the "sulphur-based", "arylthio", "burning sulphuric acid-based" spheroids. The above substituents may be exemplified by, for example, a Sa group, a thiol group, a arylamino group, a blocked hydrocarbon group, a trimethyl sulphate group, an amine group, a linyl group, a thio group, a aryl group, an exact group, an exact group, an imido group, and a halogen. Substituent or alkoxy groups. In this case, a maximum number of substituents of one or more than up to the substitutable group may be introduced to the substitutable position, and it is preferred to introduce 1 CI 4 substituents. When the number of substituents is two or more, the substituents may be the same or different. In the present specification, examples of the "amino group which may have a substituent" are not limited, and examples thereof include an amine group, a diammonium group, a decylamino group, a nonylphenylamino group, a phenylamino group and the like. In the present specification, examples of the "nonylalkyl group which may have a substituent" are not limited, and are, for example, dinonylalkyl, diethyl decyl, tridecyl decyl, triethyl decyl, tridecyl decane , triethoxyalkyl, _ 笨 曱 矽 矽 、 alkyl, triphenyl decyl, triphenyloxy decyl, dimethyl fluorenyl hydroxy, silk, dimethyl oxy 7 Alkyloxyphenyl and the like. Specific examples of the monovalent organic ruthenium are listed above, but in the present specification, 30 200804517 2, a specific example of an organic group is further added to the organic group, and a valence number is described in the book. As a specific example, in the book, the number of the two valences added to the three-group group is as follows: 1. The valence of the monovalent group can be exemplified by the specific number of valences described in the specification. & face towel adds 3 more in this manual to capture β2] 1〇0. Among them, it is preferred that the carbon exemplifies a hydrocarbon having a carbon number of 2 to • or a balance of or not 4 to 18, which may be an aromatic, or a saturated or unsaturated acyclic hydrocarbon. And the skeleton of the skeleton, the group consisting of the skeleton shown by the formula, selects the joint of the wet line table.

〇

;D

hydrocarbon. Among them, R22 may be a hydrocarbon having 2 to 100 carbon atoms or a hydrocarbon having 2 to 20 carbon atoms, and may be an aromatic hydrocarbon or a hydrocarbon, a saturated cyclic hydrocarbon or a saturated or unsaturated group. Non-circular. When it is acyclic oxygen, [two is a linear hydrocarbon or a branched hydrocarbon. Heterogeneous atoms such as nitrogen or sulfur may be contained in the molecular lean frame. Specifically, it is preferable to select the splicing portion from the group consisting of the skeletons shown in the structural formula table 200804517. The lunar frame, in the formula, the dotted line indicates the connection /C咔—— H2C—CH2

-H2C

R23 in this specification can list steam + mountain hydrocarbons. Among them, a saturated or unsaturated cyclic hydrocarbon having a carbon number of 3 to 2 〇 = 2 to 1 Å or a saturated or non-fishing rod is preferable, and when it is an aromatic hydrocarbon or a smoke, it may be a linear hydrocarbon. Can be ^ non-hetero. It is a hetero atom such as acyclic oxygen, nitrogen or sulfur. Presented as two. The structural formula can be selected from the group consisting of _ bone_ in the molecular skeleton. In the wood type, the dotted line indicates even ^ch2 ch2 CH? .CH〇

XH .CH2 , CH CH2

OH

/OH 炽 = r24 in the specification may include a hydrocarbon having a carbon number of 2 to 100 and preferably having a carbon number of 3 to 2 Q, which may be an aromatic = attenuated ± or unsaturated cyclic hydrocarbon or saturated. Or unsaturated non-circular glow. When the package is =' ^ to be a linear hydrocarbon, it may be a branched hydrocarbon. ☆ 子骨众^表 A hetero atom such as a gas, nitrogen or sulfur. Specifically, it is preferable to select a skeleton from a group consisting of a moon frame of the 卞 妹 妹 齐 , , , , 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 Among them, in order to clarify the binding position to OH in the formula (2-22), OH bonded to R24 is also included.

R25 in the present specification may be a hydrocarbon having 2 to 100 carbon atoms. Among them, a hydrocarbon having 3 to 20 carbon atoms is preferable, and it may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or a saturated or unsaturated acyclic hydrocarbon. When it is an acyclic hydrocarbon, it may be a linear hydrocarbon or a branched hydrocarbon. The molecular skeleton may include a hetero atom such as oxygen, nitrogen or sulfur. Specifically, a skeleton selected from a group consisting of skeletons represented by the following structural formulas, in which a broken line indicates a joint portion, is preferable.

R26 in the present specification may be a hydrocarbon having 2 to 100 carbon atoms. Among them, a hydrocarbon having 3 to 20 carbon atoms is preferable, and it may be an aromatic fumes or a saturated or unsaturated cyclic hydrocarbon or a saturated or unsaturated acyclic hydrocarbon. When it is an acyclic hydrocarbon, it may be a linear hydrocarbon or a branched hydrocarbon. The molecular skeleton may include a hetero atom such as oxygen, nitrogen or sulfur. Specifically, a skeleton selected from the group consisting of skeletons shown in the following structural formula table 33 200804517 is preferable, and a broken line indicates a joint portion. Among them, in order to clarify the binding position to OH in the formula (2-32), OH bonded to R26 is also included. N2 — c H 〇 1 2 cl H2 9

OH H2 c H c- H -c CH;

H2 X H2 ic c-〇 Η -c .H2 c OH-CH2 CH2---

——ch2 ch2--- R27 in the present specification may be a hydrocarbon having 2 to 100 carbon atoms. Among them, a hydrocarbon having 3 to 20 carbon atoms is preferable, and it may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or a saturated or unsaturated non-cyclic smoke. When it is an acyclic hydrocarbon, it may be a linear hydrocarbon or a branched hydrocarbon. The molecular skeleton may include a hetero atom such as oxygen, nitrogen or sulfur. Specifically, it is preferable that the skeleton shown in the group consisting of the skeletons represented by the following structural formulas is not connected to the dotted line. Among them, in order to clarify the binding position to OH in the formula (2-33), OH bonded to R27 is also included. .

CH9—OH \H2 C / -CH〇 CH2-〇H—CH2

^〇H2 /CH / OH ~CH

OH OH—CH 2 CH 2 — OH—CH 2 CH 2 — /CH 2 /CH ^OH OH —CH 〇Η 2 OH —CH 2 CH ——— -ch 2 ch 2 —oh The composition for liquid crystal alignment film of the present invention contains Polyester-polyamide 34 200804517 Acid (Al) having a polystyrene-equivalent weight average molecular weight (Mw) of 5,000 to 500,000, more preferably 10,000 to 200, as measured by gel permeation chromatography (Gpc). When the composition for a liquid crystal alignment film of the present invention is applied to a substrate, it is necessary to dilute the polymer component contained in the solvent in advance in order to adjust the film thickness. Therefore, the polyester in the composition for a liquid crystal alignment film _ The concentration of the polyamic acid (A1) is not particularly limited. When the solid content is 40% by weight or less, the viscosity of the composition for a liquid crystal alignment film is most suitable, and in order to adjust the film thickness, it is necessary to use a diluent for the composition of the film. It is preferable because the solvent is easily mixed into the liquid crystal alignment film composition. When the coating is carried out by a spin coating method or a printing method, in order to maintain the film thickness favorably, the concentration of the polyester-polyglycine (A1) is preferably 20% by weight or less. In other coating methods, such as dip coating or ink jet method, the concentration of the polyester-polyaminic acid (A1) can be further lowered. On the other hand, when the concentration of the polyester-polyglycolic acid (A1) is 1% by weight or more, the film thickness of the resulting alignment film tends to be uniform. Therefore, the concentration of the polyacetal-polyaminic acid (A1) in the composition for a liquid crystal alignment film is preferably from 1 to 5 % by weight. When the coating composition is applied by a usual spin coating method, a printing method, or the like, the composition of the liquid crystal alignment film is preferably a polyester-polyaminic acid (A1) = / Chen, preferably 1 to 4% by weight, more preferably weight. %. However, when an inkjet method or the like is used in the coating method of the π lacquer, a more dilute/shortness (for example, 0.1 to 5 weight ❹/〇) can be used. Polyproline (A1) Drum Method 4 Acid-Polyamic Acid (A1) For example, at least a polyhydroxyl group 35 200804517 (al), a diamine (a2) and having 2 or more anhydride groups can be used. The compound (a3) is prepared, but is not limited to this preparation method. When at least a polyhydric hydroxy compound (al), a diamine (a2), and a compound (a3) having two or more acid anhydride groups are used to prepare a polyester-polyglycine (Al^l), the polyester· R]1 in the constituent unit represented by the formula (?) and R2 in the constituent unit represented by the formula (H) contained in the poly-proline (AM) are compounds having two or more acid anhydride groups ( Residue of a3); φ in the formula (n): R22 in the structural unit is a residue of the polyvalent hydroxy compound (al); and the residue of the diamine (a2) in the structural unit represented by the formula. Similarly, when at least a polyhydric hydroxy compound (al), a diamine (& 2), and a compound having 2 or more acid anhydride groups (&3) are used to prepare a polyester-polyglycolic acid (A1- 2), in the polyester-polyaminic acid (A1_2), the RU in the two female constituent units and the R2 in the formula represented by the formula (2-21) or the formula (2-22) have two Or 2 or more acid-based compounds 3 = a group, R23 in the constituent unit represented by the formula (2-21), and the formula (2, R24 in the under-unit, the residue of the polybasic compound (al) The residue in the structural unit of the base = white is the residue of the working amine (f)). In the same manner, when at least a polyhydric hydroxy compound (al) or a diamine having 2 or more acid groups (4) is used to prepare the poly(acid) (A1-3), the polyacetic acid-polylysine ( R1 in the female unit of the formula (1) contained in A1_3), and formula (2_M), formula (Μ2) or R2 in the constituent unit of the formula (1, having two or more acid anhydride groups) R25 in the constituent unit represented by the formula (2-31), R26 in the constituent unit of the formula (4), and 36 in the constituent unit represented by the formula (2-33). 200804517 Polyfilament compound (al) Residue; r]2 in the structural unit represented by the formula (1) is a residue of the diamine (a2). Hereinafter, the polybasic compound (4) which can be used for obtaining the poly-succinylamine (Ai), The diamine (a2) and the compound (a3) having two or more acid anhydride groups will be described. 1^2.1 polybasic compound "η In the present invention, the polyhydroxylated monic acid (al) used for synthesizing the polyester-polyglycine (A1) may have two or more permeation groups. The diol represented by the formula (IV), the diol represented by the formula (5-2), and the tetrahydric alcohol represented by the formula (5-3) are exemplified, and the binary represented by the formula (5-1) is exemplified. In the alcohol, Rsi is not particularly limited as long as it is a divalent organic group having 2 to 100 carbon atoms. In the triol represented by the formula (5-2), R52 is a trivalent carbon atom. The organic group of 2 to 100 is not particularly limited. In the tetrahydric alcohol represented by the formula (5-3), R 53 may be an organic group having a tetravalent number of carbon atoms of from 2 to 100. In the present invention, specific examples of the polyvalent hydroxy compound (al) for synthesizing the polyester-polyglycine (A1) include: 200804517 polyethylene glycol having a molecular weight of 1,000 or less;

HCT

,〇H HO〆 丫 HCT v ,〇,v ,〇H

OH

OH

OH OH H〇, /〇,

, 〇 / \^ 丫 'OH tetrapropylene glycol, polypropylene glycol with a molecular weight of 1000 or less H〇〆

OH HO" OH HO" H〇〆

OH

OH

OH

HCT

OH

HCT

^〇H HCT

OH

〇H

OH OH

OH

HCT ▽丫 HO" OH H〇〆

OH 38 200804517

OH HO

OH

OH H〇, H〇, H〇,

〇H H〇,

OH

OH

OH

OH H〇, HO. H〇,

OH

OH H〇, HO,

.OH

OH

OH

39 200804517

OH

OH

OH

1,2-decanediol, 1,12-nonanediol;

40 200804517

OH

OH 1 "〇H OH I H〇- 1 H〇〆 \/〇H HO- OH OH H〇- OH 1 ~〇H ～〇H

HO,丫丫 '〇H OH OH OH

HO 〇H second fourth grade pentaerythritol, bisphenol A (trade name), bisphenol S (trade name), bisphenol F (trade name), diethanolamine and triethanolamine, trade name "SEO-2" (曰Huashi Chemical Co., Ltd., the product name "SKYCHDM" (manufactured by Shin Sakamoto Chemical Co., Ltd.), the trade name "Ricabinol HB" (manufactured by Shin-Nippon Chemical and Chemical Co., Ltd.), and the compound of the following formula (A) Wherein, RA1 and RA3 each independently represent -(CH2)x-CKCH2)y-; X and y each independently represent an integer of 1 to 15; RA2 represents an alkylene group having 1 to 5 carbon atoms; m is 2 An integer of ~50. A2

R HO- >A1 -RM-SKO-Si 丨, A2 -rA3_〇h R A2

FT " " (A) From the viewpoint of reducing the liquid crystal alignment formed by the obtained liquid crystal alignment boat composition 41 200804517 When the film is used in the rubbing treatment, when the polyhydric hydroxy compound (al) uses a glycol, it is preferred to:

More preferably:

When the polyvalent hydroxy compound (al) uses a triol, it is preferred to:

(5) 丫八丫)Η ΗΟ’^γ^ΌΗ ?Η L ,, 〇H

—OH

OH When a polyvalent hydroxy compound (al) is a tetrahydric alcohol, it is preferred to: 42 200804517

The polyester-polyglycine (Al) used in the present invention is preferably a trihydric or tetrahydric alcohol, and most preferably three, in terms of viscosity and molecular weight adjustment, in comparison with a diol. Alcohol. Further, the polyvalent hydroxy compound (al) may be used singly or in combination of two or more kinds. 1·2·2 Diamine In the present invention, the diamine (a2) used in the synthesis of the polyester-polyglycine (Α1) is not particularly limited, and specific examples are: bis[4-(4-aminobenzene) Oxy)phenyl]indole, bis[4-(3-aminophenoxy)phenyl]indole, bis-p-(4-aminophenoxy)phenyl], [4-(4-amine) Phenyloxy)phenyl][3-(4-aminophenoxy)phenyl], [4-(3-aminophenoxy)phenyl][3-(4-aminophenoxy) a compound represented by the formula (9): wherein R 3 and R 4 independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group; and R 5 independently represents a methylene group, a phenylene group or an alkyl group; Substituted; X independently represents an integer from 1 to 6; y is an integer from 1 to 10): 43 200804517 R3 R3 H2N-eR5^Si-〇^s|^R5^NH2 R4 R4 (b), 4, 4' -diaminodiphenylnonane, 4,3'-diaminodiphenylnonane, 3,3'-dimercapto-4,4'-diaminodiphenylmethane, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, m-phenylenediamine, pair Phenylenediamine, isophthalamide, p-benzodiazepine, 2,25-diaminodiphenylpropane, benzidine 1,1-bis[4-(4-aminophenoxy) Φ phenyl]cyclohexane, U-bis[4-(4-aminophenoxy)phenyl]-4-indolylcyclohexane Alkane, bis[4-(4-aminobenzyl)phenyl]decane, 1,1-bis[4-(4-aminobenzyl) stupid], hexane, 1,1-bis[4 -(4-Aminoguanidino)phenyl]-4-methyl-sodium hexidine A and a compound represented by the following formula. 44 200804517

R, Rl=H, CH3, C2H5yC3Ul, C4U9, C5Hn 〇CH3, OC2H5, OC3H7, CI, Br, I, OH

R, R, = H, CH3, C2H55C3H7, C4H9, C5H11

OCH3, OC2H5, OC3H7, a, Br, l, OH

H2N

2

SH NH〇

H2N

SH

45 200804517

R=CH3, C2H5, C3H7, C4H9, C5H] 1, C6H13; C7H15

H2n

R

R=H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl5Br, IJ〇H

R=H, CH3, C2H5, C3H7, C4H9, C5H! 1 OCH3, OC2H5, OC3H7, Cl, Br, I, OH

R=H, CH3, C2H5, C3 H7, C4H9, C5H 11 〇CH3, OC2H5, 〇C3H7, Cl, Br, I, 〇H

R=H, CH3, C2H5, C3H7, C4H9, C5Hl 】 〇CH3, 〇C2H5, 〇C3H7, Cl, Br, I, 〇H

R=H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, 〇H

H2N

R 2 H, CH3, C2H5, C3H7, C4H9, C5H11 〇CH3, 〇C2H5, OC3H7, Cl, Br, I, 〇H

R=H, CH3, C2H5, C3H7, C4H9, C5Hl 1 〇CH3, 〇C2H5, OC3H7, Cl, Br, I, 〇H

C- h2n

2

R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 〇CH35〇C2H5,〇C3H7,Cl,Br,I,OH

11=2-10

46 200804517 # Η,Νθ^δί

Nh2 h NH〇^sONH2 H2NG-s-<c^s-(ch^s- n=2~10 "NHo, NH2 h2n -s-(ch2)-〇一(ch2)-s- H〇N ^~^ η n a-〇r 众-an=2~10 h2N〇~s-[

Nh2 47 200804517 h2n^

Ll 仏-[

s-CT NH〇 h2N〇~s-[

-aNH2 H2N^s-a(CH2^s-crNH, n=2~10 NH9 , NH〇

H2n^~s-(ch4t〇T( 2)n SJ η2ν〇^-〇Γ \,s-〇T n=2~10 /=n NH2 H〇N^l s-(ch2) - s ~O~ S-(CH2)-S-, NH? 9 n=2~10 'NH〇H2N〇^S~(CH2)n-〇^3^〇~(CH2)irS" n=2~10 , NH? H2nO ~S-(CHfS o (2)nn=2~10 48 200804517

S-(CH2)-S η /

H〇N

〇一(ch2)-〇. n /

H〇N

S—(CH2)—S n i

n=2~10

n=2~10

11=2-10

49 200804517

.〇-(CH2)- H2N 一 〇- n=2 ～7 50 200804517

n=2~7

n=2 ～7 π—2~7, P—1~2

n=2 ～7

n=2~7

n=2~7, P=l~2 200804517

OR R-CH35C2H55C3H7?C4H9,C5Hi 1 R=CH3,C2H5,C3H75C4H9;C5Hll

H2n ί h\2n R=CH3,C2H5,C3H7,C4H9,C5Hl 1 R'=CH3,C2H5,C3H7,C4H9,C5Hi1 R=CH3,C2H5,C3H7,C4H9,C5Hi 1 R[=CH3,C2H5,C3H75C4H9, C5Hl 1

52 200804517

H2n

Och3 h2n

53 200804517

In the above specific examples, from the viewpoint of liquid crystal alignment, 4,4'-diaminodiphenyl decane, 3,3'-diaminodiphenyl decane, and 3,3'-dimethyl group are preferable. -4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-amine Phenoxy)phenyl]hexafluoropropane, m-phenylenediamine, p-phenylenediamine, isophthalamide, p-benzodiazepine, 2,2'-diaminodiphenyl Propane, benzidine, 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane, U-bis[4-(4-aminophenoxy)phenyl]-4 -methylcyclohexane, bis[4-(4-aminophenyl)phenyl]decane, 1,1-bis[4-(4-aminobenzyl)phenyl]cyclohexane, 1, 1-bis[4-(4-aminophenyl)phenyl]-4-methylcyclohexene and a compound represented by the following formula. 54 200804517 h2n—nh2

H2N-^ —(CH2)2-^ nh2 H2N~^ —(CH2)3-^ —nh2 H2N-"—(CH2)4—nh2 H2N~~^~^~(CH2)5~<^^ —NH2 H2N—(CH2)6-^ —nh2 H2N~~^ ^~(CH2)7~^~~~NH2 H2N—~~>—〇—(ch2)2-〇一^~~>— Nh2 h2n—^~~o—(CH2)3-〇—^~~nh2 H2N-^ o—(CH2)4-〇—^ nh2 h2n—^~~o—(CH2)5-〇-^~~ Nh2 H2N~~<~>~~〇一(ch2)6-〇一~>-mh2 H2N-〇-(CH2)7-〇-^ nh2 —(CH2)2-<^~~&gt ;—nh2 丨h2n-^>-0-^>-(Ch2)3^^M NH〇55 200804517 (.叱)4^^>-NH2 h2n^^^o-^]^-(ch2 )5")-nh2 H2N~~^C3^°~~^~/^~(CH2)6~^~^~nh2 h2n-<^"~^>-〇-<^~-( Ch2)7·^~nh2 (CH2)2 hair (CH2)2 O~nh2 H2N-^^〇一^^-(CH2)2-^^-〇一^^nh2 h2n-(^-0-^} -(ch2)3{^0-<^^nh2 h2N~*"〇^〇^C^~(ch2)4O^〇~O-nh2 h2n-^^-0^^-(ch2)5^ ^-0^^>-nh2 (CH2)6 ^^°^G^nh2 h2n^Q>-0-^^-(ch2)7-^^-0-^^nh2 η2Ν^^〇η2Η〇_ (CH2)3 〇~ch2{^ 56 200804517 (ch2)2 ~〇Γ (ch2)6 -ο- (ch2)2 h2n (CH2)2 (ch2)7 ~Qr (ch2)2 -a- (CH2) 3 (ch2)2 (CH2)3

H2n -o- (CH2)3 (CH2)3 -a- (CH2)3 NH2 h2n (CH2)3 (CH2)4 (CH2)3 2 h2n (CH2)3 (CH2)5 -a- (CH2) 3 "0~nh h2n (CH2)3 <y (ch2)6 (CH2)3 h2n (CH2)3 V/ (CH2)7 \Jr (CH2)3 A^rNH2 -diamine oxime Further particular preference: 4,4'-Diaminodiphenylnonane, 3,3'-diphenylnonane, 3,3'-dimercapto-4,4'-diaminodiphenylnonane, diamine Diphenylpropane and the following compounds. 57 200804517 η2νΌ~ (ch2)2 争2 h2n'~<〇_ (CH2)4·

(CH2)3 发 NH2 h2n ~(ch2)5~^~~_2 H2N——(CH2)2-^~^-(CH2)2-<^~~-NH2 h2n h2n H2N^^CH2-^^ (CH2)3 乂)-ch2{^-mh2 The diamine (a2) may be used alone or in combination of two or more. As long as it is a diamine which achieves the object, it is not limited to the compound (a3) having two or more acid anhydride groups of the above diamine 0 1·2·3. In the present invention, polyester-polyglycine (A1) The compound (a3) having two or more acid anhydride groups used in the synthesis is not particularly limited, and tetracarboxylic dianhydride is preferred. Specific examples of the compound (a3) having an acid anhydride group include a styrene-maleic anhydride copolymer, 4-(2,5-dioxotetrahydro-bite-Nan-3-58 200804517-based)-1,2 , 3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5·dioxotetrahydrofuranyl)-3-indolyl-3-cyclohexene-1,2-dicarboxylic anhydride, A compound represented by the following formula or the like. 〇

59 200804517

60 200804517

Further particularly preferred:

When two or more types are used alone or in combination, when the poly- lysine-poly-staphylin acid anhydride group used in the present invention has an acid anhydride group, it can be subjected to _-knife 1 and 兀-alcohol as needed. The reaction. Add 6] 200804517 Polyanthene of monohydric alcohol is preferred. Day ~ reading amino acid (4)), for example, the flat domain becomes good, the added - the alcohol can be exemplified by: isopropanol, allylic acid, - # x know, ethanol, i propanol, ether, propylene glycol monomethyl hydrazine : hydroxyethyl acrylate, propylene glycol monoethylammonium &|, dipropylene glycol monoethyl-glycol monoethyl ether, B: propanol early methyl ether, #alcohol, maltitol, linalool, pine oil Alcohol, vinegar, vinegar, glycidol, 3-ethyl _3; milk =, 'from the improved liquid crystal alignment _ and into the white; ^

Ϊ́ί2, in a specific example, preferred: iso(tetra), conjugated benzyl oxime propane; wherein benzyl alcohol is more preferred.甲甲" In addition, if 3-aminopropyltrimethoxy decane, 3-aminopropyltriethyl decyl decane, 3-aminopropylmethyldimethoxy decane, 3-amino Propylmercaptodiethoxydecane, 4-aminobutyltrimethoxydecane, 4-aminotrimethoxydecane, 4-aminobutylphosphonium diethoxydecane, p-aminobenzene Tris-methoxy decane, p-aminophenyl triethoxy decane, p-aminophenyl decyl decyloxy decane, p-aminophenyl methyl diethoxy oxime, inter-monthly base A monoamine containing a decane such as a dimethoxy pulverization or a m-alkyl thioglycolate, and a polyester-polylysine (Α1) having an acid anhydride group at the molecular terminal, for example, a coating film obtained The chemical resistance is improved, so it is preferred. Alternatively, a monohydric alcohol and a monoamine containing decane may be simultaneously added to the polyester-polyglycolic acid (Α1) to be reacted. 62 200804517 1Α·5豕扈suspension '酉曰酉曰-polyproline (A 1) is preferably a compound having 0.5 to 19 moles of a diamine (a2) and having 2 or more acid anhydride groups. 3) The 15 to 2 molar Mocha water is reacted with the hydroxyl hydroxyl group of the polyhydroxy compound (&1). The polyacetal-polyproline (A1) is more preferably 2 to 20 moles of water and plural of the compound (8) having 2 or more acid anhydride groups of 1 to 9 moles of the diamine (a2). The hydroxyl group (al) is obtained by reacting a 1 molar hydroxyl group. The solvent to be used for obtaining the polyester-polyglycolic acid (A1) is not particularly limited as long as it can synthesize the compound, and examples thereof include diethylene glycol monoterpene ether, monoethylene glycol diethyl ether, and diethylene glycol. Methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, 3-methoxy propionate decyl ester, 3 _Ethyl ethoxypropionate, cyclopropane, γ-butyrolactone, N_mercapto-2-pyrrolidone and N,N-dimethylacetamide. Among them, preferred are: decyl methoxypropionate, diethylene glycol decyl ethyl ether, ethylene glycol monobutyl ether, γ-butyrolactone, and N-mercaptopyrrolidone. The above solvent may be used singly or as a mixture of two or more than 9 kinds of mixed solvents. In addition to the above solvents, other solvents may be used in combination, but other solvents are preferably used in a proportion of 30% by weight or less. When the total amount of the hydroxy compound (al), the diamine (a2), and the compound (a3) having two or more acid-based groups is 1 part by weight, 1 part by weight or more than 100 parts by weight or more is used. In the case of a solvent, the reaction proceeds smoothly, which is preferable. The reaction is preferably carried out at a ratio of 1 (TC to 2 Torr (TC) for 2 hours to 2 hours. When a monoamine containing decane is added to the polyacetate/polyamine acid (A1) to react 63 200804517, it is preferred to After the reaction of the hydroxy compound (al), the diamine (a2), and the compound (a3) having two or more acid anhydride groups is completed, the reaction and the liquid are cooled to 40 ° C or lower, and then decane is added. The monoamine is made at 10 to 40. The underarm reaction is 0·1 to 6 hours. It should be noted that a monohydric alcohol can be added to the polyester-polyglycolic acid (Α1) to react it. The order of adding the reaction raw materials in the system is not particularly limited. That is, the polyvalent hydroxy compound (al), the diamine (a2), and the compound (a3) having two or more acid anhydride groups are simultaneously added to the solvent; (a2) and the polyvalent hydroxy compound (al) are dissolved in a reaction solvent, and then a compound (a3) having two or more acid anhydride groups is added; the polyvalent hydroxy compound (al) and two or more acid anhydride groups are previously prepared. Compound (5)) reacts to synthesize a copolymer, and then adds a diamine (a2) to the copolymer; previously the diamine (a2) and has 2 The compound (&3) of two or more acid anhydride groups is reacted to synthesize a copolymer, and then a method of adding a polyvalent hydroxy compound (al) to the copolymer is used in any of the four methods. Imine (Α2) Imine (A2) The polyester-polyimine (Α2) is not particularly limited as long as it has a constitution of both an ester and a quinone. The following three compounds are preferred. Π] Polyester-polyimine ( Α2-1) a constituent unit represented by the formula (3) and a compound represented by the formula (2-1); 64 200804517 [2] Polyester-polyimine (A2-2) having the formula (3) a constituent unit and a compound of one or more constituent units selected from the group consisting of the constituent unit represented by the formula (2-21) and the constituent unit represented by the formula (2-22); [3] Polyester-polythene (A2 - 3) having a constituent unit represented by the formula (3) and one or more constituent units selected from the formula (2-31), a constituent unit represented by the formula (2-32), and a formula (2 33) A compound constituting a constituent unit of a group consisting of units. The terminal of the polyacetamide-polyimine (A2) is, for example, an acid anhydride group, an amine group, a hydroxyl group or the like. (3) In the case of 'R3' and R33, an organic group having a tetravalent carbon number of 2 and 2 to 100 may be independently represented, and R32 may be a divalent organic group having 100 carbon atoms. R31 and r33 in the atomic book can be independently listed as a hydrocarbon having a valence of 4 to 100, and a hydrocarbon having 3 to 20 carbon atoms is preferable. Or a saturated or unsaturated cyclic hydrocarbon or a saturated or unsaturated heterogeneous molecular skeleton may include an oxygen atom, a nitrogen atom or a sulfur atom, etc., and may be exemplified by a divalent carbon atom of 2 to Among the hydrocarbons or hydrocarbons, a hydrocarbon having 3 to 2 carbon atoms is preferred, and may be an aromatic substructure 2: an unsaturated cyclic hydrocarbon or a saturated or unsaturated acyclic hydrocarbon. In other words, a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom.疋, Equation (2-1), Formula (2_21), Formula (2-22), Formula (rush), 65 200804517 Formula (2_32), R(] in Equation (2·33), and R2]~R27 As mentioned above. The chemical resistance of the film obtained from the composition for liquid crystal alignment film of the present meal is generally preferably that the higher the molecular weight of the polyester polyimine (A2), and the solubility with respect to the solvent is usually polyester-poly. The lower the molecular weight of the quinone imine (A2), the more desirable. Therefore, the weight average molecular weight of the polyacrylamide (A2) contained in the composition for a liquid crystal alignment film of the present invention is preferably 5,000 to 500,000 ', more preferably ι 〇 〇〇 2 〇〇, 〇 Hey. In the present invention, the content of the polyester-polyimine (A2) in the composition for a liquid crystal alignment film (when also including polyglycolic acid (A1), refers to polyacetamide-polylysine ( A1) and the total content of the polyester-polyimine (A2) are not particularly limited, and are preferably 1 to 50% by weight, more preferably 1 to 40% by weight, particularly preferably 2%, based on the total amount of the composition for the liquid crystal alignment film. 30% by weight. When it is in the above concentration range, the viscosity of the composition for a liquid crystal alignment film is most suitable, and coating with a uniform film thickness can be formed by coating with various coating methods, and therefore it is stopped. The preparation method of the polyester "polyimine (A2) used in the present invention can be, for example, at least a polyvalent hydroxy compound (al), a diamine (a2) and having two or more acid anhydride groups The polyester-polyimine (A1) prepared by the compound (a3) is imidized to prepare. 6 Mixture of proline (A1) and polyester-polyimine (A2) can be mixed by separately mixing polyester_polyglycine (A1) and polyester-polyimine (A2) A part of the polyester-polyaminic acid (A1) is imidized, etc., and is prepared in 66 200804517. When the above preparation method is employed, R3] and R33 in the constituent unit represented by the formula (3) contained in the polyester-polyimine (AH) and R21 in the constituent unit represented by the formula (2_^ have 2 The residue of the compound (a3) of the hydrazone or the quinone; and the residue of the component (a2) in the structural unit of the compound represented by the formula (2-1). When the polyester-polylysine (A1-2) oxime prepared by using at least a polyvalent hydroxy compound (al), a diamine (a2), and a compound having 2 or more acid anhydride groups 仏3) is imidized When the polyester-polyimine (A2_2) is prepared, the sum R and the formula (2-21) or the formula in the constituent unit represented by the formula (3) contained in the poly(indenyleneimine) (A2-2) R2 in the structural unit represented by (2-22) is a residue of the compound (n) having two or more acid anhydride groups; R23 in the structural unit represented by the formula and formula (2-22) R24 in the constituent unit is a residue of the polyvalent hydroxy compound (al); R, a diamine residue of the composition | represented by the formula (3). In the same as in the early 7", when the polyhydroxy compound (al), the diamine, and the compound (a3) having two or more acid anhydride groups are used, the polyester-polyamine (A1-3) is prepared. When imidization to prepare polyester_polyimine (A2_3), R33 and formula (2- in the constituent unit represented by formula (3) contained in poly(J) polyimine (A2-3) 31) The R21 represented by the formula (2_32) or the formula (5) 3) is a residue of a compound (phantom) having two or more acid anhydride groups. R25 in the structural unit represented by the formula (2-31), R in the constituent represented by the formula (2_32) and r27 in the constituent unit represented by the formula (2-33) are the residues of the polyorganism 67 200804517-based compound (al); R32 in the constituent unit represented by the formula (3); It is the residue of the diamine (a2). ~

聚合物.Polymer B The composition for liquid crystal alignment film of the second aspect of the present invention comprises a polymer A and a polymer B, and the polymer A includes a polyester-polyamide (A1) and a polyester-polyfluorene. One or more groups consisting of imines (A2);

The polymer B includes one or more selected from the group consisting of polylysine (B1) and polyimine (B2). UUI Amine Acid (B1) Composition of Amine Acid (B1) The polyamic acid (B1) is not particularly limited as long as it is a compound having a guanamine structure, and is a compound having a unit of a branch (1). The constituent unit represented by the formula (1) constituting the polylysine (B1) is the same as the formula (1) showing the constituent unit constituting the poly-polyaminic acid (A1). Method for Producing Amine Acid (B1) Poly(A) can be prepared, for example, by using at least a diamine (a2) and a compound (IV) having 2 or more acid anhydride groups, but the method of preparation is also secreted. ^ At least a diamine (IV) and a wide object (4) having 2 or more acid anhydride groups are used to prepare a poly-acid (in the case where the poly-bristamine (bi) contains a constituent unit represented by the material ί(1) R11 is a residue of the compound (IV) having two or more oxime anhydride groups; R]2 is a residue of the diamine (10). The diamine (tetra) which can be used for obtaining polylactoic acid (BD) and having 2 68 200804517 or more than two acid compounds (4) are the same as the diamine (a2) which can be used to obtain the polychatogene (A1) and the compound (a3) having two or more acid groups. 1 polyimine

AlAil imine (Β2他缉忐,

The term "imine" (B2) is not limited as long as it is a compound having a constituent of decylamine, but is preferably a formula (4) having a constituent unit represented by formula (4): 珉xKfc imine (B2) In addition, the tetravalent organic group having a carbon number of 2 to 100 may be used, and r42 is not particularly limited as long as it is an organic group having a divalent carbon atom of 2 to 1 Å. R41 in the present specification includes a tetravalent hydrocarbon having 2 to 2 carbon atoms and preferably having a carbon number of 3 to 2 Q, which may be an aromatic hydrocarbon or a saturated or unsaturated cyclic hydrocarbon or saturated or Unsaturated acyclic hydrocarbons. The I sub-framework may include a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom. R42 in the present specification may be a hydrocarbon having a divalent carbon number of 2 to 100, preferably having a carbon number of 3 to 2 G, and may be an aromatic fluorene or a residual or unsaturated hydrocarbon. And or unsaturated non-ring furnaces. A hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom may be included in the two sub-framework. 0 Polyimine The polynymine (IV) used in the present invention can be prepared, for example, by using at least a diamine (a2) and a compound (4) having two or more acid anhydride groups. 69 200804517 Polyamine (B1) The imidization is carried out for preparation. When the above production method is employed, R4i in the structural unit represented by the formula (4) contained in the polyimine (B2) is a residue of the compound (a3) having two or more acid-based groups; R42 It is the residue of the diamine (a2). A mixture of polyamic acid (B1) and polyimine (B2) can be obtained by mixing separately synthesized poly-aramidic acid (B1) and polyimine (B2) to polylysine (B1). A part of hydrazine imidization or the like is prepared. The composition of the liquid crystal alignment film according to the second aspect of the present invention includes at least one of polyamine (B1) and polyimine (B2). The content of polyamic acid (B1) and cimetil (B2) (when both polyamines (B1) and polyimine (B2) are included) is not particularly limited, as opposed to The total amount of the composition for the liquid crystal alignment film is preferably 1 to 5 % by weight, more preferably 2 to % by weight. Therefore, if it is in the above concentration range, the effect can be maintained for the frictional cut and the alignment can be improved. The composition for a liquid crystal alignment film of the present invention may include an epoxy compound (C) as needed. The epoxy compound (c) used in the invention is not particularly limited as long as it has an epoxy group, and a compound having two or more ethylene oxides is preferred. In the present invention, the content of the epoxy resin in the composition for a liquid crystal alignment film is not particularly limited, and is preferably 0.1 to 40% by weight, more preferably 〇 2 to 3 % by weight. When the content of the epoxy resin is in the above-mentioned concentration range, the coating film formed of the composition for a liquid crystal alignment film is not easily scratched by the rubbing treatment, and the durability is good. When the content of the epoxy resin is in the above concentration range, the heat resistance and chemical resistance of the above coating film become good, which is preferable. Specific examples of the epoxy compound (C) include a bismuth a type epoxy resin, a glycidyl ester epoxy resin, an alicyclic epoxy resin, and a monomer having an epoxy group: A copolymer of a polymer and a monomer having ethylene oxide and another monomer, and the like. More specifically, the epoxy resin may be exemplified by the trade name "Epycoat" (Epycoat 815), "Epycoat 825", "Epycoat 827", and the compound "Epycoat 828" represented by the above formula (C4). "Epycoat 190P", "Epycoat 191P" (above, oiled SHELLEPOXY), trade name "Epycoat 1004", "Epycoat 1256" (above, manufactured by Nippon Epoxy Co., Ltd.), trade name "AralditeCY177" The compound "Araldite CY184" (manufactured by CIBAGEIGY Co., Ltd.) of the above formula (C1), the product name "Celoxide 2021P" represented by the above formula (C2), and "EHPE-3l5〇" (DICEL Chemical Industry Co., Ltd.) The compound "TECMORE VG3101L" (manufactured by Mitsui Chemicals Co., Ltd.) and the compound represented by the above formula (C5), which are represented by the above formula (3), are "4,4,-methylenebis(N,N-). Diglycidyl aniline) (made by ALDORICH). In the liquid crystal composition of the present invention, the mixture "Epycoat 828" of the compound of the formula (C4) and the compound "Araldite CY184" represented by the above formula (C1) (manufactured by CIBAGEIGY Co., Ltd., Japan) In the above formula (C2), 200804517 i = main "feloxide 2021 p" (DICEL Chemical Industry Co., Ltd.), the product name "TECMORE VG3101L·", manufactured by Mitsui Chemicals Co., Ltd., and the above formula The compound "4,4,-methylene group (N,N--glycidylaniline)" (manufactured by ald〇rich Co., Ltd.) represented by (C5) is preferable because it has good transparency and flatness. Specific examples of the monomer having ethylene oxide include (indenyl) glycidyl acrylate, (mercapto)acrylic acid 3, 'epoxycyclohexyl ester and (meth)acrylic acid methyl glycidyl ester. Specific examples of the other monomer copolymerized with the monomer having ethylene oxide include (meth)acrylic acid, methyl (meth)propionate, and ethyl (meth)acrylate. Isopropyl methacrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, butyl (meth) acrylate, (cyclo) propionate (Meth) acrylate, (meth) acrylic acid 2- to PEG, 2-hydroxypropyl (meth) acrylate, styrene, methyl styrene, chloromethyl styrene, (3 -Ethyl-3-epoxypropane: !: complete) methyl (meth) acrylate, cyclohexylmaleimide, imine and N-phenyl maleimine. Preferable specific examples of the polymer of the monomer having ethylene oxide include polyglycidyl methacrylate and the like. Preferable specific examples of the copolymer of the monomer having ethylene oxide and other monomers include decyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate. Copolymer, butyl methacrylate-glycidyl methacrylate copolymer, h hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl epoxidized) methyl (曱) Acrylate··glycidyl methacrylate copolymer and styrene-methyl propylene 72 200804517 acid glycidyl ester copolymer. The composition of the liquid crystal alignment film of Maoyue is composed of acid (4)) and its compound (tetra) (iv) imine (a kind of A2 amine), but it can also be obtained according to the required characteristics.

Epoxy hardening such as antibacterial agent, antistatic agent, _ mixture, trimellitic acid, etc. is called 'amine-based compound, solvent, and other additives. The additive such as the surface active i is added to, for example, a composition for a liquid crystal alignment film, and is dissolved and reused. ^ ^q" (1) Surfactant For example, when it is desired to improve coatability, a surfactant may be added according to the purpose. Specific examples of the surfactant to be added to the composition for a liquid crystal alignment film of the present invention include: trade name r]Byk_3〇〇", "Byk-306", "Byk-335", "Byk-310", Hydrazine-based surfactants such as "Byk-341", "Byk-344", "Byk-370", and (BYKCHEMIE); trade names "Byk-354", "ByK-358", "Byk-361" (Acrylic surfactants such as BYK CHEMIE); fluorine-based surfactants such as "DFX-18", "FTERGENT 250", and "FTERGENT 251" (manufactured by NEOS). The above surfactants may be used singly or in combination of two or more. The surfactant is an additive for improving wettability, flatness, or applicability to the underlying substrate, and is preferably used by adding 200804517 〇·〇1 to 1% by weight to the liquid crystal alignment film composition. (2) Antistatic agent The antistatic agent to be added to the composition for a liquid crystal alignment film of the present invention is not particularly limited, and a general antistatic agent can be used. Specific examples thereof include metal oxides such as oxygen, tin, tin oxide and cerium oxide composite oxides, tin oxide and indium oxide composite oxides, and fourth-order ammonium salts. These antistatic agents may be used singly or in combination of two or more. = The electric agent is an additive for preventing electrification, and it is preferable to add 〇·〇 to the liquid crystal alignment amine composition~! Use % by weight. (3) Coupling agent The coupling agent added to the composition for liquid crystal alignment film of the present invention may be a conventional coupling agent. The nucleating agent to be added is preferably a stone agent, and specific examples thereof include a trifilium-based compound or a di-ruthenium complex. Preferable are, for example, γ-vinylpropyltricarbadecane, γ-vinylpropyltriethoxydecane, decylmercaptopropyl decane, ercaptopropyltrimethoxydecane: γ-stone^ Soil methyl diethoxy decane, γ-propylene decyl propyl triethoxy: two: its γ_: acryloyl propyl propyl methyl dimethoxy decane, γ-methyl propyl dimethoxy Decane, γ-mercaptopropenyl propylmethyldiyl;: group; women: base 曱 美 、, 、, γ-glycidoxypropyl three _. ^ ^ γ 钿 钿 甘油 甘油 氧基Propylmethyldiethoxy oxime, hydrazine glycerol oxygen, I 2 7 β υ 二 diethoxy decane, γ·aminopropyl methyl dimethoxy 74 200804517 矽 矽, γ-amino group Propyltrimethoxy decane, γ-aminopropylmethyldimethoxy oxime, γ-aminopropyltriethoxy oxalate,|aminoethyl iminopropylmethyldi Methoxy decane, N-Aminoethyl _γ-aminopropyltrimethoxy oxysulfide, Ν-aminoethylaminopropyldiethoxylate β, Ν 基 个 胺Trimethoxy decane, Ν-phenyl _γ-aminopropyl triethoxy decane Ν- stupid dimethyl-aminopropyl group _γ_ Silane Yue group, phenylamino 1-yl methyl diethoxy ㊉ burning, (iv) propyl methyl dimethoxy-wire burning, Ah _

^ propyl methoxy methoxy decane, propyl propyl decyl diethoxy decane, hydrazinopropyl triethoxy decane, 7 - isocyanate propyl methyl diethoxy oxime, γ - isocyanic acid S is a propyl triethoxy group, and the like. Among them, preferred are: γ-ethyl propyl dimethoxy decane, γ-acryl propyl propyl tridecyl oxy decane, 丫 曱 丙 propyl propyl propyl tri methoxy wei, γ · isocyanate s For the purpose of propyl triethoxy decane and the like. One hole can be used alone (four) or two kinds of mixing #. It is preferable to use ～~3% by weight to the liquid crystal alignment film composition. (4) Epoxy curing agent, and the epoxy added to the (tetra) liquid crystal alignment film is hard to be used: a usual epoxy curing agent is used. Specifically, it can be as follows. New Zealand and its derivatives, dicyandiamide, multi-read anhydride and the like. More specifically, it can be 』,,,,,,,,,,,,,,,,,,,,,,,,,,, Double (arrogant) rebellious ethyl)-5-isopropyl B-containing urea and other organic acids, second brewing; 2', 4 diamine ^ 75 200804517 -6-[2'~ethyl cyanosine_(p) An imidazole derivative such as mercapto imidazole, 2-phenylmethyldiazine, phenylimidazole, phenyl-4-benzenedicarboxylic anhydride, or triamyl imidazole; an phthalic anhydride or the like. Among them, an acid such as a transparent ?-cyclohexane tricarboxylic anhydride is preferred. Further, trimellitic acid and 1,2,4-cyclohexane tricarboxylate may be used alone or in combination of the above epoxy hardeners. Use ' can also be two or two

The epoxy curing agent is preferably used in an amount of 5 wt% of the liquid crystal. Addition of 0.05 (5) Amine-based compound to the composition for the alignment film:): The compound of the present invention: The composition of the liquid crystal alignment film may be added with an aminoalkyl sulfonated compound: a p-aminophenyl trimethoxy stone - k, f: «phenyldiethoxy 9 fluorene, m-aminophenyl trimethoxy oxime, m-fee phenyl diethoxy wei, aminopropyl tributary oxime, amine Propyl triethoxy stone, etc.

The above-mentioned amine-based compound can be used singly or in combination of two or more kinds. > The amine-based compound is an additive for improving the adhesion to the substrate, and is preferably used by adding 0 to 22% by weight to the liquid crystal alignment film composition. (6) Solvent The solvent which can be contained in the composition for a liquid crystal alignment film of the present invention is not particularly limited as long as it dissolves the polymer A or the polymer B contained therein. Solvents include a wide range of polymers such as polyaminic acid and soluble polyimine, and are suitably selected for the general purpose of the preparation process or use. The spoon and the agent can be exemplified as follows. The phase amine is a solvophilic non-small early ^^ 士# lysine or soluble 酽 酽 dimethyl dimethyl group, :: : amine: - two, acetyl group, bis gamma propyl "Ν, Ν - Diethyl ketoamine, diethyl ethanoamine, base m to improve the applicability of the helmet, Y dinella, etc. L7 alkyl shovel, 3 帀 I, ..., ..., examples of his solvent can be listed Ex.1 samaryl, 3mT oxy 1 ^. oleic acid alone, etc., ethylene glycol mono-succinct, dip-alone, single-ethyl: ethane glycol ethylene glycol monoalkyl or phenyl b Ganzi; monoalkyl alcohol monobutyric acid, oxime; ^ - > σσ early 'Fanji S fans, Bingdi soil a temple Bingyi early; J: complete ether, malonic acid ketone, Dipropylene glycol monomethyl dipropylene glycol monobutyl ^ (tetra) diacid pyrrolidine bis, dimethyl (tetra) N decyl diethylene glycol monoethyl ether, propylene glycol monobutyl ^ dipropanol: two early Zheng Zaojia:, Er Er Gan Alcohol methyl ethyl ether, "oxy- or the like: combined with t it alone, it is also possible to mix two or more kinds of solid humans" using various agents to make the solid moon beans in the liquid crystal alignment film composition The content is set to be 1 to 60% by weight. (7) Other additives The composition for the brighteners can also be used together with the polyester, the acrylic polymer, and the like, without damaging the hair, the outer circumference (preferably 2% by weight of the composition for the liquid crystal alignment film). A polymer such as an acrylic polymer is used in a mixture of 77 200804517. The composition for a liquid crystal alignment film of the present invention can be added thereto with a dicarboxylic acid or a derivative thereof and the present product polyamine or tetracarboxylic dianhydride, a dicarboxylic acid or a derivative thereof, without impairing the purpose. The known reaction should be a polymer component such as polyamidoximine. Applying the composition of the present invention to the surface of a substrate such as glass or a substrate provided with glass such as indium tin oxide or a shirt color filter, the composition is dehydrated by dehydration. The closed-loop reaction may be formed by - or drying to form a liquid crystal alignment film. The force u substrate may be exemplified by, for example, a good smoothness of the broken glass, such as: polyparaphenylene ester, polyparaphenylene Ethyl phthalate ester, nucleus oxy-resin, phenolic resin, polyimine, polycarb I, sulfone, polyether hard, polyether sulfimine, acetamidine cellulose, polyamino=ester, aromatic polyamine, etc. Heat-resistant resin; polystyrene, polyacrylic acid ^ methacrylate, polypropylene decylamine, polyethylene, polypropylene and other acetyl compounds; polyvinylidene fluoride and other _ lipids and their conversion The plastic film or the like, the method, the ϊϊρϊϊ table, the liquid crystal alignment film composition <, by / text, drop method, inkjet method, etc., Hu: two coated liquid crystal of the invention into dehydration: mouth Heat treatment or drying treatment in the furnace in the outer furnace, on the hot plate 78 200804517 π domain 3 ^ The U heat treatment process is generally performed at a lower temperature within the range of the dissolution of the sulphide. The U heat treatment process is generally preferably carried out at a temperature of 15 G 〜 3 (10). Q is right. The electrode provided on the substrate allows the metal such as chromium to be deposited on the glass plate by the (four) clock method. After that, it is formed by engraving money. The pre-cut shape of the resist pattern is a mask such as 2 operation, and the Wei _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The liquid crystal display element substrate on which the liquid crystal alignment film is formed. The rubbing method is preferably used in the alignment treatment, and the rubbing treatment is particularly limited, and it is preferable that the amount of the hair pushing is 02 to 0·8_, and the moving speed of the stage is 5 to 250 mm. /Sec, the roller rotation speed is 5 〇〇 2, and the rubbing treatment by the liquid-test composition of the present invention is carried out under the condition of 〇〇〇7. The Japanese and the scallops include the epoxy compound (C) of the present invention. The "Night Crystal Alignment Film" obtained by the composition for a liquid crystal alignment film may be more strongly moved than the liquid crystal alignment film which is obtained from the composition for a liquid crystal alignment film containing no epoxy compound (c), and is excellent in heat resistance. , chemical, flatness, adhesion, and splash resistance Therefore, it is preferable that the liquid crystal display element of the present invention is used in a plurality of liquid crystal display element substrates of the present invention or the liquid crystal display element substrate of the present invention and the second 79 200804517, The liquid crystal composition is filled between the substrates at intervals between the substrates, and the polarizing plate can be further attached to the above-mentioned base. The liquid crystal display element of the present invention can also be replaced by a liquid crystal display element. To make it. Washing party ί /, strip steam washing « ultrasonic washing, etc. The above two methods can be used together. Washing liquid can be used: pure water 戍 and other various SI,. #七厂和〒酉子,ethanol, Aromatic alcohols such as isopropyl alcohol, A, and dimethyl benzophenone, chlorinated sulphuric acid, and sulphonic acid, such as acetone and methyl ethyl ketone, are not limited to this. When the above washing liquid uses a washing liquid having a small amount of sufficiently purified impurities. The liquid crystal composition used in the liquid crystal display device of the present invention is not particularly limited, and various liquid crystal compositions having positive dielectric anisotropy can be used. Examples of the liquid Ba composition of U-Hyun are disclosed in Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Publication No. 5_5〇1735, Japanese Patent Publication No. 8_丨57826, and Japanese Patent Laid-Open 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Japanese Laid-Open Patent Publication No. Hei 9-235552, Japanese Laid-Open Patent Publication No. Hei 9-255956, JP-A-H09-241643 (EP885271A1), 曰本特开平平10-20401.6 (EP844229A1), 曰本特开平10-204436 Japanese Laid-Open Patent Publication No. Hei 10-231482, the Japanese Patent Publication No. 2000-087040, and the Japanese Patent Publication No. 2001-48822. Various liquid crystal compositions having a negative dielectric anisotropy can also be used. Optimum 80 200804517 Examples of liquid crystal compositions selected are disclosed in Japanese Laid-Open Patent Publication No. 5, Japanese Unexamined Patent Publication No. Hei No. 5, No. 5, No. 5, No. 5, No. 5, No. 4, No. 4, No. 4, No. 4, No. Kaiping side 10-168076 唬 报 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Japanese Patent Laid-Open No. Hei 10-237000, Japanese Patent Publication No. 4, No. 237, Japanese Patent Laid-Open No. Hei 10-237035, Japanese Patent Laid-Open No. Hei 10-237035, Beneficial Kaiping 1〇_237076, 曰本特开平10^7448号 λ report (EP967261A1 manual), Japanese special Kaikai 1〇_287874 bulletin, Japanese special Kaiping 10_ job No. 75 bulletin, Japan special Kaiping 1〇 Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 〇〇1_〇72626, 2001-192657, etc. . It is also possible to add an optically active compound to the liquid crystal composition in which the dielectric anisotropy is positive or negative for reuse. Further, in the composition for a liquid crystal alignment film of the present invention, it is also possible to use a mixture of 1, 2, and a poly-imine, a poly-s-imine, and a poly-S in a mixture of 2 or 2 (preferably within 2 G mol%). A polymer component such as a dilute acid = ^ propylene - vinegar polymer. Further, in the liquid helium alignment film of the present invention, a dicarboxylic acid or a derivative thereof which is a component of the composition for a liquid crystal alignment film can be added in a range of not more than 8: 200804517, which does not impair the object of the present invention. A reaction product of a polyamine or a tetracarboxylic dianhydride, a reaction product of a dicarboxylic acid or a derivative thereof and a diamine, and a polymer component such as a polyamine. Population Example Hereinafter, the present invention will be described by way of Examples and Comparative Examples, but the present invention is not limited to these Examples.

a compound having two or two private anhydride groups (tetraacid 2

:CBDA :PMDA

APE DDM BZ3 P1PDA 4ChBlB 16P1P 12P1P 1,2,3,4-cyclobutane tetradecanoic acid dipyrrolidine dianhydride diamine (a2) 4,4'-diaminodiphenyl@4,4 '-Diaminodiphenylmethane

1,3_bis[4-(4-aminobenzyl)phenyl]propane 3-benzyl-1,4-diaminobenzene 1,1-bis[4-(4-aminophenyl)benzene Butyl butyl cyclohexane H(4-hexadecylphenyl)methyl]_1,4-diaminobenzene 3-[(4-dodecylphenyl)methyl^, 'two Amino-based 3-({4-[4-('-pentylcyclohexyl)cyclohexyl]phenyl}methyl)diamine

:SChChPIP 3-[(4-{4-[2_(4-heptylcyclohexyl)ethyl]cyclohexyl}phenyl)fluorene 82 200804517

:7Ch2ChPlP-based]-1,4-diamine-based polyhydric hydroxy compound (aj) 1,4-butanediol __ ΒΟΗ 1,5-pentanediol: ΡΟΗ

1,2,4-butanetriol ·· BTOH

2-(hydroxyindenyl)-2-mercaptopropane-l,3·diol: TMEOH

Tetrakis (hydroxyindenyl) decane : PETOH ring gas resin (C)

Celoxide 2021P : SE2021P

Araldite CY177 : CY177

4,4,-methylenebis(N,N-diglycidylaniline): TGDDM solvent

:ΝΜΡ :GBL :BC

N-methyl-2-pyrrolidone γ-butyrolactone ethylene glycol monobutyl ether (butyl cellulase) [Synthesis Example 1] Preparation of a composition for liquid crystal alignment film (1Α), including a thermometer, a mixer, and a raw material A 200 ml four-necked flask with a gas inlet and a nitrogen inlet was charged with 196 g of CBDA (10 mmol), 2.18 g of PMDA (10 mmol), 〇.36 g of 1,4 «丁二酉 (4 mmol), 84 Jg of dehydrated 83 200804517 NMP 'under a dry nitrogen stream Mix for 1 hour at i2〇°c. After cooling to 25t:, 3.20g APE (16mmol) was added. While maintaining the temperature of the reaction system at 2 S C - for 30 hours, 38.5 g of BC and 231 g of GBL were added thereto, and the temperature was raised to 5 Torr. (: and continue to stir, when the viscosity of the composition reaches 3 〇~35 mPa_s (the reaction is terminated using an E-type viscometer, 25 〇, to obtain a polyester-polylysine liquid crystal alignment film having a solid content of 5% by weight. The composition (stomach 1A). The weight average molecular weight of the obtained composition was 23, 〇〇〇. The 疋, the average molecular weight of the weight was measured using a Gpc measuring device manufactured by Shimadzu Corporation at a column temperature of 50 C. The molar ratio of pmda, CBDA, APE, and ΒΟΗ is pmDA/CBDA/APE/BOH = 25/25/40/10. [Example 1] Preparation of liquid crystal alignment film, substrate for liquid crystal display element, and liquid crystal display element will be synthesized The liquid crystal alignment film composition 1A obtained in Example 1 was diluted with a mixed solvent of NMP/BC/GBL (=60/25/15, weight ratio) to adjust the solid content to 3 wt%, and was used as a liquid crystal alignment for coating. (varnish (1A)). The enamel (1A) was applied to a glass substrate with an electrode. The coating conditions were: 2200 rPm, 15 seconds, and 8 Å after coating. (: pre-sintering for about 5 minutes, fortune 21 (heating treatment for 3 minutes at TC, forming A liquid crystal alignment film having a thickness of about 75 nm. Using a friction treatment device manufactured by Igawa Gauge Co., Ltd., the amount of the hair on the rubbing cloth (hair length 1 rayon) is 〇.4〇mm, the moving speed of the stage The resulting alignment film was rubbed under the conditions of a production speed of 6 〇mm/sec and a roller rotation speed of 15 rpm. The slag was observed with an optical microscope of 100 times and 4 times. Cutting marks and cutting residues caused by friction treatment

5 The eight-inch display element substrate was ultrasonically washed in ultrapure water = buckle' and then dried in an oven at 12 Torr for 3 minutes. Here, the liquid B of the element B with the = pole is spread on the component sheet, and the surface on which the alignment film is formed is bonded to the inner side, and sealed with an epoxy hardener to form an anti-parallel box of 7 μm ( Antiparauei ceu). The liquid crystal composition shown below was injected into the above-mentioned case, and the injection port was sealed with a light hardener, and heat-treated at n (rc for 30 minutes, and then returned to room temperature to prepare a liquid crystal display element. 85 200804517 Liquid crystal composition

^2^5 c2h4

17wt.% 17wt°/〇 16wi% 10wt.% 5wt·% 10wt.% 6wt.% 6wt.% 13wt.%

It was confirmed by a polarizing microscope observation that the liquid crystal in the liquid crystal display element was used as a liquid crystal composition of a liquid crystal material. The NI point of this composition was ΐοο.οπ, and the birefringence was 0.093 〇. Using a polarizing microscope, the liquid was confirmed in a state where no voltage was applied at room temperature, and the alignment state of the elements was revealed. When the box is rotated, light and dark are visible, and in the dark state, no light leakage due to misalignment is found. 86 200804517 [Synthesis Examples 2 to 16] In addition to the changes in the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound used in the preparation of the composition for a liquid crystal alignment film, and the moir thereof, as shown in Tables 1 and 2, The compositions (2A) to (16A) for liquid crystal alignment films were prepared under the same conditions as in Synthesis Example 1. Table 1 Composition for liquid crystal alignment film Mohr ratio Weight average molecular weight Tetracarboxylic acid dianhydride Diamine Polybasic compound PMDA CBDA APE DDM BZ3A ΒΟΗ ΡΟΗ Synthesis Example 1 1A 25 25 40 10 23,0 (8) Synthesis Example 2 2A 25 25 40 10 25,200 Synthesis Example 3 3A 25 25 40 10 20,710 Synthesis Example 4 4A 25 25 20 20 10 22,320 Synthesis Example 5 5A 25 25 40 10 35,230 Synthesis Example 6 6A 25 25 40 10 32,850 Synthesis Example 7 7A 25 25 40 10 23,510

Table 2 Composition for liquid crystal alignment film Mohr ratio Weight average molecular weight Tetracarboxylic dianhydride Diamine Polybasic compound PMD A CBD A APE DD ΒΖ A 3 A BTO Η OH OH PETO Η Synthesis Example 8 8Α 25 25 40 7.5 Example 9 9Α 25 25 40 7.5 49,230 Synthesis Example 10 10Α 25 25 40 Ί.5 58,780 Synthesis Example 11 11Α 25 25 40 7.5 57,000 Synthesis Example 12 12Α 25 25 40 7.5 53,600 Synthesis Example 13 13 A 25 25 40 7.5 60, 550 Synthesis Example 14 14A 25 25 40 5 88,500 Synthesis Example 15 15A 25 25 40 5 83, 250 Synthesis Example 16 16A 25 25 40 5 78, 650 87 200804517 [Examples 2 to 16]

The substrates for liquid crystal display elements were produced under the same conditions as in Example 1 except that the compositions for liquid crystal alignment films (2A) to (16A) obtained in Synthesis Examples 2 to 16 were used, and were used at 1 time and 4 times. The surface of the liquid crystal alignment film was observed with an optical microscope to confirm the cutting marks and cutting residue on the surface of the substrate due to friction. An antiparallel cassette was fabricated using this substrate, and a alignment microscope was used to confirm the alignment state. The results are shown in Table 3. Table 3 Example of the state of the surface of the substrate after the varnish rubbing. The light leakage of the box was confirmed by the polarized light. Example 1A - Good light is not leaked. Example 2 2A Good light is not shallow. Example 3 3A Good light is not leaking Example 4 4A Good Light Leakage_Example 5 ------- 5A Good Light Leakage Example 6 6A Good Light Leakage Example 7 ----- 7A Good Light: 3⁄43⁄4 Example 8 —-- 8A Good light has not leaked Belle 9 -- 9A Good light is not; Drainage example 10 10A Good light does not leak Belle also Example 11 ~~—__ 11A Good light is not leaked Example 12 -- --— 12A Good light is not leaking Example 13 13A Good light is not leaking 14 14A Good light is not leaking Example 15 ^---- 15A Good light is not leaking __ Example 16 16A Good light is not leaking (Good: No cutting marks and cutting residues caused by friction were observed.) [Synthesis Example 17] Synthesis of poly-proline (17PA) to a thermometer with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet 88 200804517 200 ml Four-necked flask 3 54g4ChB1Bc7 〇nim〇1), 55g dehydrated NMP, dissolved 〇.9607g CBDA (3.5mmol), 0.77g PMDA (3.5mmol) was allowed to react for 3 hours while maintaining the temperature of the reaction system at 25C under a dry nitrogen stream, after which 25 g of BC and 25 g of GBL were added to the temperature. 50(:and|||Continue Lin, when the viscosity of the composition reaches 3〇~35mPa.s (using the E-type viscometer, 25. When the reaction is terminated, the solid comet is 5 weights/〇 contains the polyp A composition for a liquid crystal alignment film of an amino acid (17 Å). The weight average molecular weight of the obtained composition was 30,560. It should be noted that the weight average molecular weight was measured at a column temperature of 50 ° C using a GPC measuring apparatus manufactured by Shimadzu Corporation. The molar ratios of PMDA, CBDA and 4ChBlB used were PMDA/CBDA/4ChBlB = 25/25/50. [Synthesis Examples 18 to 28]

The same conditions as in Synthesis Example π except that the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound used in the preparation of the liquid crystal alignment film composition and the moir thereof were changed as shown in Tables 4 and 5, respectively. A composition for liquid crystal alignment film (18PA) to (28PA) was prepared. Table 4 Molecular composition of tetraclinic acid dianhydride diamine for liquid crystal with molar ratio film PMDA CBDA 4ChBlB 16P1P P1PDA DET Synthesis Example 17 17PA 25 25 50 ~ 25^530~ Synthesis Example 18 18PA 25 25 50 28,560 Synthesis Example 19 19PA 25 25 50 27,320 Synthesis Example 20 20PA 25"""" 25 50 ~~23〇60~ Synthesis Example 21 21PA 25 25 25 25 ~24^00~ Synthesis Example 22 · 22PA 25 25 25 25 29,580 89 200804517 Table 5 Composition for liquid crystal alignment film Mohr ratio Weight average molecular weight Tetracarboxylic dianhydride diamine PMDA CBDA 12P1P SChChPlP 7Ch2ChPlP PI PDA Synthesis Example 23 23PA 25 25 50 23,560 Synthesis Example 24 24PA 25 25 50 30,650 Synthesis Example 25 25PA 25 25 50 31,230 Synthesis Example 26 26PA 25 25 25 25 34,650 Synthesis Example 27 27PA 25 25 25 25 32,650 Synthesis Example 28 28PA 25 25 25 25 32,110 Aroma [Synthesis Example 29] The polyester-polyfluorene obtained in Synthesis Example 12 The liquid crystal alignment film composition (12A) of the amino acid and the polyamine acid-containing liquid crystal alignment film composition (17PA) obtained in Synthesis Example 17 were mixed at a weight ratio of 17PA/12A = 20/80 to prepare a solution. Polyester - polyamide acid and polyamide acid group into a liquid crystal alignment film composition. [Synthesis Example 30 to Synthesis Example 40]

The liquid crystal alignment film composition containing the polyacetal-polyamic acid and the liquid crystal alignment film composition containing polyglycine were mixed at a weight ratio shown in Table 6 to prepare a polyester-polyamide. A composition for a liquid crystal alignment film of polylysine. 90 200804517 Table 6 Composition for liquid crystal alignment film ------ Polyurethane polyester-polyglycine weight ratio Synthesis Example 29 1G 17PA 12A 17PA/12A=20/80 Synthesis Example 30 2G 18PA 12A 18PA/ 12A=20/80 Synthesis Example 31 3G 19PA 12A 19PA/12A=20/80 Synthesis Example 32 4G 20PA 12A 20PA/12A=20/80 Synthesis Example 33 5G 21PA 12A 21PA/12A=20/80 Synthesis Example 34 6G 22PA 12A 22PA/12A=20/80 Synthesis Example 35 7G 23PA 12A 23PA/12A=20/80 Synthesis Example 36 8G 24PA 12A 1 24PA/12A 2 20/80 Synthesis Example 37 9G 25PA 12A 25PA/12A=20/80 Synthesis Example 38 10G 26PA 12A 1 26PA/12A=20/80 Synthesis Example 39 11G 27PA Π 12A 27PA/12A=20/80 Synthesis Example 40 12G 28PA 12A 28PA/12A=20/80

[Example 17] The composition for liquid crystal alignment film prepared in Synthesis Example 29 was diluted with a mixed solvent of NMP/BC/GBL (=60/25/15, weight ratio) to adjust the solid content to 3 wt%/〇. As a composition for liquid crystal alignment film for coating (varnish (1 Θ)), using the above varnish 1G, the surface of the liquid crystal alignment film was observed by an optical microscope of 1 〇 0 times and 400 times by the method described in Example 1. Confirm the cutting marks and cutting debris caused by friction. This substrate was used to produce an anti-parallel cassette, and the alignment state was confirmed by a polarizing microscope. The results are shown in Table 7. [Examples 18 to 28] The compositions for liquid crystal alignment films for coating (varnishes (2G) to (12G)) were prepared using the composition for liquid crystal alignment films obtained in Synthesis Examples 30 to 40. 91 200804517 Then, a substrate for a liquid crystal display element was produced under the same conditions as in Example 17 except that the above varnish was used, and the surface of the liquid crystal alignment film was observed with an optical micromirror of 100 times and 4 times, and it was confirmed by friction. Cutting marks and cutting debris on the surface of the substrate. An antiparallel cassette was produced using this substrate, and the alignment state was confirmed by a polarizing microscope. The results are shown in Table 7. Table 7 The state of the surface of the substrate after the varnish rubbing was applied. The photobleaching of the substrate was confirmed by using a polarizing micro-if. Example 17 1G Good light non-leakage Example 18 2G Good light non-leakage Example 19 3G Good light non-leakage implementation Example 20 4G Good light is not leaked ~~ Example 21 5G Good light is not leaked Example 22 6G Good light is not leaked Example 23 7G Good light is not leaked Example 24 8G Good light is not leaked Example 25 9G Good light is not leaked ~ Example 26 10G Good light and no leakage Example 27 11G Good light is not leaked Example 28 12G Good light is not leaked (Good: no cutting marks and cutting residues caused by friction are observed.) [Synthesis Example 41] Liquid crystal Synthesis of the composition for the alignment film (1B) The composition for liquid crystal alignment film obtained in Synthesis Example 1 (1A), ruthenium, 25 g of DICEL (trademark) Celoxide (trademark) 2 (mp alicyclic epoxy) The composition (1B) for liquid crystal alignment film was prepared by mixing the resin (1.0 mmol). [Synthesis Examples 42 to 66] Synthesis of a composition for a liquid crystal alignment film, except that the polyester-polyamide was used as shown in Table 8. Liquid crystal alignment film 92 200804517 A composition for a liquid crystal alignment film containing an epoxy resin (2B) was prepared under the same conditions as in Synthesis Example 41 except that the composition, the composition for a liquid crystal alignment film of polyglycolic acid, and an epoxy resin (1.0 mmol) were used. ~(14B) and (1G)~(12G). Table 8 93 200804517

Liquid Crystal Alignment Film Composition Liquid Crystal Alignment Film Composition (Polyester-Polyuric Acid) Liquid Crystal Alignment Film Composition (Polyuric Acid) Epoxy Resin Epoxy Resin Addition Example 41 1B 1A (100 Magic See SE2021P 1 .Ommol Synthesis Example 42 2B 1A (War) - TGDDM 1 .Ommol Synthesis Example 43 3B 11A (100 Magic - SE2021P 1 .Ommol Synthesis Example 44 4B 11A (l〇〇R) - CY177 1 .Ommol Synthesis Example 45 5B 11A (I00g) - TGDDM ]. Ommol Synthesis Example 46 6B 13A (I00g) - SE2021P 1 .Ommol Synthesis Example 47 7B 13A (100 g) - CY177 1 .Ommol Synthesis Example 48 8B 13A (100 g) - TGDDM 1 .Ommol Synthesis Example 49 9B 14A (100 g) - SE2021P 1 .Ommol Synthesis Example 50 10B I4A d〇〇R) - CY177 1 .Ommol Synthesis Example 51 11B 14A (l〇〇g) - TGDDM 1 .Ommol Synthesis Example 52 12B 16A (War - SE2021P 1 .Ommol Synthesis Example 53 13B 16A d〇〇g) - CY177 1.Ommol Synthesis Example 54 14B 16A (Chi) - TGDDM 1.Ommol Synthesis Example 55 1G 12A (8〇g) 17PA (2〇g) TGDDM 1 .Ommol Synthesis Example 56 2G 12A (80 g) I8PA (2〇g) TGDDM 1 .Ommol Synthesis Example 57 3G 12A (8〇R) 19PA (2〇R) TGDDM 1 .Ommol Synthesis Example 58 4G 1 2A (8〇g) 20PA (2〇g) TGDDM 1 .Ommol Synthesis Example 59 5G 12A (80 Magic 21PA (2〇R) TGDDM 1 .Ommol Synthesis Example 60 6G 12A (8〇R) 22PA (2〇R) TGDDM 1 .Ommol Synthesis Example 61 7G 12A (8〇g) 2 3 PA (20 Magic TGDDM 1 .Ommo) Synthesis Example 62 8G 12A (80^) 24PA (2〇g) TGDDM 1 .Ommol Synthesis Example 63 9G 12A ( 80 g) 25PA (20 g) TGDDM]. Ommol Synthesis Example 64 10G 12A (8〇g) 26PA (2〇g) TGDDM 1 .Ommol Synthesis Example 65 11G 12A (8〇g) 27PA (2〇R) .TGDDM 1 . Ommol Synthesis Example 66 12G 12A (80 g) 28PA (20 g) TGDDM 1.Ommol 94 200804517 [Example 29] The liquid crystal alignment film composition (1B) prepared in Example 41 was used for 酉曰|1 stomach amine 1 and ring The total solid content of the oxygen resin was adjusted to 3% by weight to prepare a varnish (1 Å).

Using the above varnish (IB), the surface of the liquid crystal alignment film was observed with an optical microscope of 1 倍 and 400 times in the same manner as in the Example, and the cutting marks and the cutting residue which were picked up by the friction were confirmed. This substrate was used to produce an anti-parallel cassette, and a alignment microscope was used to confirm the alignment state. The results are shown in Table 9. [Example 30 to Example 54] A varnish was prepared under the same conditions as in Example 29 except that the composition for a liquid crystal alignment film prepared in Synthesis Examples 42 to 66 was used. Using the above varnish, the surface of the liquid crystal alignment film was observed by optical microscopy at 1 〇〇 and 4 〇〇 times in accordance with the method described in Example 1, and the cutting marks and cutting residues from the smear were confirmed. This substrate was used to produce antiparallel, and the alignment state was confirmed by a polarizing microscope. 95 200804517 Table 9

EXAMPLES Varnishes Defects on the surface of the substrate by 顕 micromirror The light leakage of the cell was confirmed by a polarizing micromirror. Example 29 1B Good light is not leaked. Example 30 2B Good light is not shallow. Example 31 3B Good light is not bubbled Example 32 4B Good light is not leaked Example 33 5B Good light is not leaked Example 34 6B Good light is not leaked Example 35 7B Good light is not bubbled Example 36 8B Good light is not; Leakage Example 37 9B Good light: 3⁄4漏 embodiment 38 10B good light leaking embodiment 39 11B good light not: 3⁄4 drain embodiment 40 12B good light non-foaming embodiment 41 13B good light non-leakage embodiment 42 14B good light non-leakage embodiment 43 1G Good light: 3⁄4 leaking Example 44 2G Good light non-foaming Example 45 3G Good light non-steam leakage Example 46 4G Good light non-steam leakage Example 47 5G Good light non-foaming Example 48 6G Good light: 3⁄4漏实施例 49 7G Good • Light is not leaked Example 50 8G Good light: 3⁄4 Leakage Example 51 9G Good light: 3⁄4 Leakage Example 52 10G Good light non-foaming Example 53 11G Good light Non-steam leakage Example 54 12G Good light non-foaming (good: no cutting marks and cutting residues due to friction were observed.) [Comparative Example 1] 200 ml four equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet The neck flask was charged with 4.00 g of APE (20 mmol) and 84.7 g of dehydrated NMP, and stirred and dissolved under a dry nitrogen stream. While maintaining the temperature of 96 200804517 of the reaction system at 25 C, l_96 g of CBDA (10 mmol) and 2.18 g of PMDA (10 mmol) were slowly added, and reacted under a dry nitrogen stream for 30 hours, after which 38.7 g of BC and 23.1 g of GBL were added. The temperature was raised to 50 ° C and stirring was continued. When the viscosity of the varnish reached 30 to 35 mPa·s (the reaction was terminated using an E-type viscometer, 25. 〇, a polyamine composition having a solid content of 5% by weight (29PA) was obtained. The weight average molecular weight of the obtained composition was 29, 〇〇〇.

The weight average molecular weight was measured at a column temperature of 50 °C using a GpC measuring device manufactured by Shimadzu Corporation. The composition (29PA) obtained as above was diluted with a mixed solvent of NMp/BC/GBL (=60/25/15, weight ratio), and the solid content was adjusted to 3% by weight to prepare a varnish as a coating composition. (29pA). A liquid crystal alignment film, a liquid crystal display element substrate, and a liquid crystal display element were prepared in the same manner as in Example except that varnish (29PA) was used. The silk surface, > month § § endures the cutting marks and cutting debris caused by friction. Using a polarizing microscope, no electricity was applied at room temperature: the alignment of the liquid crystal display element was poor. When the box is rotated, the stone is confirmed to be light that is not picked up by the alignment in the state of 1 (4). In the darkness of the present invention, a substrate for a device and a liquid crystal display device can be cited. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The scope of the spirit is defined by the scope of the appended patent application = Protection of the invention 97 200804517 Ζ 441〇ρΐΙ [Simple description of the diagram] No [Major component symbol description] None

Claims (1)

200804517 24416pit X. Patent Application Range: A composition for a crystal compound, including a polymer A, a polymer A, a polyacetate-polyacid having a constituent unit represented by U and (d), and including the following formula (3) and the following formula (4) The constituent elements of the group, or the species or groups of the group consisting of imines (A2), where 3: the dotted line indicates the linking sites, Rll, R12, R21, R22, R31, & 32 and R independently represents an organic group having a carbon number of (10). 〇 〇 II II -...C\ /C-NH-RtNH 'R11 HOO^ XCOOH (1) 〇 〇 (2-1) cv ; 〇 r r22—〇 V1 HOOc/ XC〇〇H 2. A liquid crystal alignment film composition comprising a polymer a, the polymer a comprising a group selected from the group consisting of polyester-polyglycine (A1) and polyester-polyimine (A2) Or one or more, the polyester-polylysine (A1) includes a constituent unit represented by the following formula: and one or more constituent units selected from the following formula (2-21) and the following formula (2-22) represents 99 200804517 24436ριί The constituent unit 'polyester-polyimine (A2) includes a constituent unit represented by the following formula (3) and a species or more selected from the following formula (2_21) The constituent unit and the following formula (2-22) represent the constituent units of the rotation of the single handle (four), and the dotted line indicates the joint portion, and the ruler 1, 1, 1112, 1121, 1^31^4 & An organic group representing the number of carbon atoms _ 2~. , 0 II C 〇II /0—NH- >12 R 11 -NH- (1) HOOC C00H 〇=C1 , c=o 2 \ R onnc\ /ennoIo 〇3* ό—R2 ο ο -2 ( 2- Φ o=c1 c=〇/2 \ R 〇=c /0=〇io ο ο II丨t 9 2) -2 (2- OH one HOOC OHQ R' 33 COOH (3) 100 0 200804517 2441bpil 3 - A composition for a liquid crystal alignment film comprising a polymer A comprising a polymer selected from the group consisting of polyester-polyglycine (A1) and polyester-polyamide One or more kinds of the group consisting of the amine (A2), the polyester-polyaminic acid (A1) includes a constituent unit represented by the following formula (1) and one or more constituents selected from the group consisting of the following formula (2-31) The constituent unit of the group consisting of the constituent unit represented by the following formula (2-32) and the constituent unit represented by the following formula (2-33), the polyester-polyimine (A2) includes the following formula (3) The constituent unit represented by the constituent unit represented by the following formula (2-32) and the constituent unit represented by the following formula (2-33) and one or more constituent units represented by the following formula (2-31) A constituent unit of a group in which a broken line indicates a linking site, and R11, r12, r21, R25, R26, R27, R31, Rj, and R33 each independently represent an organic group having 2 to 1 carbon atoms. 〇 〇 .........C\ <C-NHsR12~NH......- (1) / \ HOOC COOH 101 200804517 ^44i〇piT 〇 Ο II l25 c—〇一r25—〇 21 I \ 9 c—OH : il i 〇 ; (2-31) Ο O OH ,C—O—R26 - O (2-32) C-OH II 〇 OH C—〇—R 27_ R 21 OH H〇一 CI! 〇 C 一〇H (2-33) 102 200804517 2441bpil 4. A liquid crystal alignment film composition comprising a polymer A comprising a polymer selected from the group consisting of poly-proline (A1) and a polyester-poly-proline (A1) ruthenium. One or more than one group consisting of polyester-polyimine (A2), polyester polyamic acid (A1) is at least using a polyvalent hydroxy compound (al), a diamine (a2) and including 2 One or two or more acid anhydride-based compounds (8)). 5. The liquid crystal alignment film composition according to claim 4, wherein the polyvalent hydroxy compound (al) is a diol represented by the following formula (5_1}, wherein 'R51 is a carbon number of 2 to 1 〇 The liquid crystal alignment film composition according to claim 5, wherein the polyester_polyglycine (A1) comprises the following formula: (1) the constituent unit represented by the formula and the constituent unit represented by the formula (2_1), the polycarbo-imine (A2) includes the constituent unit shown below and the constituent unit represented by the following formula (2_1}, where $( ) indicates the linking site, R11, R12, R2, R22, R31, R32, and r33. The green group is independent of an organic group having 2 to 1 carbon atoms. Knife 103 103045045 Z^+HlOpii 〇Ο... .../-nh-r12-NH......- (1) /R\ H〇〇CC〇〇H 〇〇II II π ..........Cx/-〇-R -°·-. ...(2-1) / \ HOOC C〇〇H _ 〇〇〇o II II II II — ..., /c\ /c\ /C—....... /Rl /N - R32 - N \ X (3) HOOC C c COOH li II 0 〇 7. The liquid crystal alignment mold according to claim 4, wherein the polybasic grouping The compound (al) is a three-second formula represented by the following formula (5-2), and R52 represents an organic group having 2 to 100 carbon atoms. % alcohol 'OH HO - R52-OH (5_2) 8 The liquid crystal alignment film according to claim 7, wherein the polyester-polylysine (A1) comprises a constituent stage represented by the following formula (1) and one or more selected from the group consisting of the following formula (2-21) The constituent unit of the group consisting of the constituent units represented by the structural unit (2-22), the polyamicimine (A2) includes the constituent unit represented by the following formula (3), and one or more selected from the following formula (2-21) The constituent unit represented by the following formula and the composition of the group consisting of 104 200804517 represented by the following formula (2_22), Rn, Rl2, and the organic groups having 2 to 1 carbon atoms are respectively independent groups. II C 〇II R 11 C—NH—R12—NH— (1) HOOC COOH Ho 〇=c/21\c=〇R2〇=c\/c=〇9 3 6——R2 - ο OH -2 ( 2- Φ Ho 〇=C3,1 c=o r2\〇=c\/c=〇ο £ 2) -2 (2 OH 〇II c 〇II.co It R 31 , 'N-R32——NR: 33 (3) HOOC COOH Composition 105 200804517 弋 indicates that the rabbit atomic number is 2~lo o The organic group OH HO· R53 ～OH OH (5-3) is a group of constituent units represented by the constituent units of the group of 冓 冓 早 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 Formula (3) is expressed as 7L in the morning and - or more than one or more selected from the following formula (2 = subordinate (4) table constituent unit and the following formula (2·33) indicates = = kg composed of the constituent units of the group, In the formula, the dummy positions 'Rll, Rl2, R2I, R25, R26, R27, R3i, R, and Ri^ independently represent an organic group having 2 to 1 carbon atoms. 〇II -CR 11 ,C—NH—R12—NH (1) H〇〇(/ C〇〇H 106 200804517 Ζ,ΗΗ 1 υριι C—0——R25—〇R 21 HO-CII 〇c—OHI !〇(2-31) OH /C—〇一R26—〇 521 HO-CII 〇 c—OH (2-32) Ο O OH /C——0—R27—O 21 I \ OH , C-〇HII 〇 (2-33) 107 (3) 200804517 H_T JL v/pxi The liquid crystal alignment film composition according to any one of claims 4 to 10, wherein the polybasic compound (al) is one or a group selected from the group consisting of the following compounds; the above, HO—'\厂 OH OH 丄 V -Υ HO^ ΗΟ^ ~〇H HO—丨 \—OH OH OH OH 108 200804517 The diamine (a2) is one or more selected from the group consisting of the following compounds. H2i NH !2 (ch2)3\ />-nh2 H2n NHo H2N-i /-s-(ch2)4-s -V /-nh2 h2n NH 2 H2N NH 2 h2n NH 2 -NH 2 um3 /-NH2 h2^〇〇H-〇-o^nh2 cf3 h2nh〇-0-(ch2)4-0~^-nh2 109 200804517 ZH·外丄 0|Jii ?H3 110 200804517 The compound (a3) comprising two or more acid anhydride groups is one or more selected from the group consisting of the compounds described above. The composition for a liquid crystal alignment film according to any one of claims 1 to 3, wherein the polyester-polyamic acid (A) or the poly-acetamide (A2) Is a compound of the diamine (a2) having a 〇·5 to 19 molar amino group, including two or more acid anhydride groups (0. 5 〜 2 〇 molar anhydrate and a polyvalent hydroxy compound (al) The composition of the liquid crystal alignment film according to any one of claims 1 to 1 further includes a polymer field, and the polymer '(B) includes One selected from the group consisting of polylysine (B1) and polyimine (B2) And R and the counter 42 each independently represent an organic group having a carbon number of 2 to 100. 111 200804517 Z,*+^lUUii Ο Ο ...-c\ —ΝΗ-r12—ΝΗ......- (1) R11 • / \ , HOOC COOH 〇 O The composition for liquid crystal alignment film according to any one of claims 1 to 10, further comprising a polymer (B) comprising a polymer selected from the group consisting of polyacrylic acid (B1) One or more groups consisting of polyimine (B2) obtained by imidating poly(protonic acid) (B1) with polyamine (B1) using at least diamine (a2) and A compound (a3) comprising two or more acid anhydride groups. 15. The composition of the liquid crystal alignment film as described in the above patent application scope 112 200804517 I UJJIJl η2ν· S—(CH2)4-S. α H2n /-nh2 h2ish^^~〇-(ch2)4-o~^^h NH, h2n-(^o-^} NH 丨2 113 200804517 ZHH 1 Upil o 16. The liquid crystal alignment film composition as described in claim 14, wherein the polyaminic acid (B1) comprises a constituent unit represented by the following formula (1), and the polyamic acid imide includes the composition represented by the following formula (4). In the unit, in the formula, the imaginary line indicates that the joint portion '^^(10) independently represents the organic group of 绿子连~100. 〇〇II II -C /C—NH—R12—NH_ 11 R / \ HOOC COOH 〇〇(1) , Ν R42—Ν •C II 〇CI 〇114 (4) 200804517 17·If you apply for the patent scope, item 13 The composition for a liquid crystal alignment film includes a polyamine acid (B1) and a polyimine (B2) in an amount of 1 to 50% by weight of ruthenium/iridium relative to the composition for a liquid crystal alignment film. 18. The composition for a liquid crystal alignment film according to claim 12, further comprising an epoxy compound (c). The composition (C) for a liquid crystal alignment film according to claim 18 is a compound species selected from the group consisting of the following formulas (C1) to (C5) or more than one, wherein 'η is 〇~1〇 115 200804517 benefit (C3) (C4) 116 200804517 The composition for a liquid crystal alignment film according to claim 18, wherein the composition for the liquid crystal alignment film comprises from 1 to 40% by weight of the epoxy compound (C). A liquid crystal alignment film is obtained by using a composition for a liquid crystal alignment film according to the first aspect of the patent application. A liquid crystal display element comprising the liquid crystal alignment film according to claim 21 of the patent application. Μ 117 200804517 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 0 〇I! 丨丨19 ----------C /C—NH—R12—NH------ ---- (1) V / \ HOOC COOH 〇〇 II II 99 C / C 〇 R R22 - Ο \r21 / \ HOOC COOH 〇〇 II II 〇 II i! II R31 XN II c 32 / \ - R32 —N 〇II CR 33 HOOC (2-1) COOH (3)