TW201030060A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

This invention provides a liquid crystal display device having excellent performance in terms of retardation and flowing alignment, a liquid crystal alignment film thereof which performs the above-mentioned charactersitics, and a liquid crystal alignment agent to form the liquid crystal alignment film. The liquid crystal alignment film is formed by polyamic acid or its derivative using tetracarboxylic dianhydride and diamine as raw materials. The characteristic of the liquid crystal alignment agent is that the tetracarboxylic dianhydride contains at least one of a specified tetracarboxylic dianhydride and other tetracarboxylic dianhydride except for the specified tetracarboxylic dianhydride.

Description

[Technical Field] The present invention relates to a liquid crystal alignment agent containing polylysine or a derivative thereof, a liquid crystal alignment film formed from the liquid crystal alignment agent, and the liquid crystal alignment film Liquid crystal display element. [Prior Art] The liquid crystal display element is used for a viewfinder and projection of a video camera (vide〇camera) typified by a monitor of a personal computer or a desktop personal computer. Various liquid crystal display devices such as displays have recently been used in televisions. Further, the liquid crystal display element is also used in a photonic-related element such as an optical printer head, an optical Fourier transform device, or a light valve. Various components are known for liquid crystal display elements, but the technical development of liquid crystal display elements can be achieved not only by the driving method of the liquid crystal display element or the structure of the liquid crystal display element, but also by the composition used in the liquid crystal display element. The components are improved to achieve. In general, a liquid crystal display element has a liquid crystal alignment film for aligning a liquid crystal composition in a liquid crystal layer in a specific direction. The liquid crystal alignment film is an important factor related to the display quality of the liquid crystal display element. The function of the liquid crystal alignment film has become important year by year as the quality of the liquid crystal display element is improved. The liquid crystal alignment film is prepared from a liquid crystal alignment agent. At present, a liquid crystal alignment agent mainly used is a solution obtained by dissolving polyacrylic acid or soluble polyamidene 201030060u.doc (polyimide) in an organic solvent. After the solution is applied onto a substrate, film formation is carried out by heating or the like to form a liquid crystal alignment film. Regarding the liquid crystal alignment film, for example, a liquid crystal alignment film using diamine tetraacetic acid dianhydride is known, and the liquid crystal alignment film is improved in a super Twisted Nematic 'STN mode, an active matrix display. The voltage holding ratio in (refer to the specification of U.S. Patent No. 552〇845). Further, a method of improving crosstalk by using a liquid crystal alignment film of ethylenediaminetetraacetic acid dianhydride has been disclosed (refer to Japanese Laid-Open Patent Publication No. Hei 6-75229). Further, a liquid crystal alignment film using a copolymer of a polymer material having a photoreactive group bonded to an acid anhydride in ethylenediaminetetraacetic acid dianhydride is disclosed (refer to Japanese Laid-Open Patent Publication No. 2006-350347). The parameter O which governs the electro-optical performance (electr〇_〇phc property) of the liquid crystal display element is a retardation O (Retardatlon' R) of the liquid crystal alignment film. The higher the value of the retardation (R), the higher the uniaxial alignment of the liquid crystal alignment film, and the black display of the liquid crystal display element becomes good. Therefore, a technique of using a liquid crystal alignment film having a high uniaxial alignment property to more uniformly align liquid crystal molecules in a liquid crystal display element to enhance black display characteristics has been known (Japanese Patent Laid-Open Publication No. Hei No. 2005-258397). Further, as one type of display failure of the liquid crystal panel which is produced in the manufacturing process of the liquid crystal panel, a phenomenon in which liquid crystal molecules are fixed in the flow direction at the time of injection when liquid crystal molecules are injected into the liquid crystal panel is known. 201030060idoc That is, the flow alignment 'but as a liquid crystal display element, it is required not to generate a flow alignment. However, there is a need for a technique for further improving characteristics relating to retardation and flow alignment of liquid crystal display elements. SUMMARY OF THE INVENTION The present invention provides a liquid crystal display element having excellent performance in retardation and flow alignment, a liquid crystal alignment film in which the characteristics are exhibited in the liquid crystal display element, and a liquid crystal alignment agent which can form the liquid crystal alignment film. The present inventors have found that a composition containing polyamic acid or a derivative thereof, which is a raw material of tetracarboxylic dianhydride and tetracarboxylic acid dianhydride other than the tetracarboxylic dianhydride, is used. The liquid crystal alignment element having the liquid crystal alignment film formed by the liquid crystal alignment agent has a desired property, thereby completing the present invention. The present invention includes the following constitutions. [1] A liquid crystal alignment agent containing polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine, the liquid crystal alignment agent characterized by: One needle contains one or more kinds of tetracarboxylic dianhydride represented by the following general formula (TC-1) to formula (TC-14), and one or more kinds of other tetracarboxylic dianhydrides. 201030060 'Ai.doc

7 20103 0060.u〇c [Chemical 2]

Ad H 0 N-R1 Λ~f -r R1-N ) M O O (TC-8)

(A'L ( a2) „ (a1^ (in the general formula (TC-1), 'X is not -(CH2)m- 'two or less -CH2- can be independently 〇 _ (but Discontinuous), -s-, -COO·, -oco-, -CO-, -CONH-, -CnH2nN(CmH2mCOOH)CnH2n-, -CH(CmH2mOH)-, ·αΗ((:ηΗ2η+1)-, -CH=CH- or -OC-substituted ii.doc 201030060 (m independently represents an integer of 〇~3〇, n independently represents an integer of 1 to 3〇). Formula (TC-4) to Formula ( In TC-7), Y independently represents a single bond, _〇·, _S_, -SS-, -S〇2-, _CO_, -CONH-, -NHCO-, _NH_, •N(CH3)-(CH2) nrN(CH3)-, -C(CH3)2-, -C(CF3)2·, -(CH2)m-, -0-(CH2)m-0-, -S-(CH2)mS-(m An integer of 1 to 6 is represented. In the formula (TC-5), 'Z represents a single bond or does not exist. In the formula (tc-2) to (TC-7), it is bonded to cyclohexane (cyclohexane). The hydrogen on the ring or the benzene ring is independent and can be substituted by -F, -CH3, -CF3, -OH, -COOH, -S03H, ® -P〇3H2, in the formula (TC-3) The hydrogen bonded to the benzene ring may be substituted by benzyl. In the formula (TC-2) to the formula (TC-8), R1 independently represents -(CH2)m-, two or Two or less _ch2- can be independently -0-(but not continuous), -S_, -COO-, -OCO-, -CO-, -CONH-, -CH(CmH2mOH)-, -CH(CmH2m+1)-, -CH=CH- or -OC- is substituted (m independently represents an integer of 〇30). In the formula (TC-8), A1 is independently a carbon group having a carbon number of 1 to 10 and a carbon number of 1 to 10. Alkoxy group (alk〇Xy), acetamide, fluorine, chlorine or desert, A2 independently represents an alkylene group having 1 to 3 carbon atoms, m represents an integer of 0 to 3, and η represents 0 to 4 In the formula (TC-9), R33 and R34 each independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group. Α3 independently represents a methylene group or a phenylene group. Or a subphenyl group substituted by an alkyl group, 1 represents an integer of 1 to 6, and m represents an integer of 1 to 10. In the formula (TC-10), 'A3 represents a single bond, _〇, -COO-, -OCO- , _CO_, -CONH· or -(CH2)m, (m represents an integer of 1 ^ 6), R1 represents a group having a steroid skeleton or a group represented by the following formula (B), when bonded Two amino groups on the benzene ring (amin0) 9 201030060 "The positional relationship of doc is the alignment, and R1 further contains a carbon number of 1 to 30." In the meta position, R1 further contains a C 1 or 30 alkyl group or a phenyl group, and in the alkyl group, any -CH 2 - may be independently -CF 2 _, -CHF - 0 - (but not discontinuous) , -CH=CH- or -OC-substituted '_CHs may be substituted by -CH2F, -CHF2 or -CF3, the hydrogen of the phenyl group is independent' and may be -F, -CH3, -OCH3, -OCH2F, Replaced by -OCHF2 or -ocf3. [Chemical 3]

In the general formula (B), A4 and A5 each independently represent a single bond, (but not discontinuous), -COO-, -OCO-, -CONH., -CH=CH- or an alkenyl group having 1 to 12 carbon atoms. (alkylene), R2 and R3 each independently represent _F or heart, and ring S independently represents 1,4-phenylene, iota, 4-cyclohexylene, 1,3_ dioxins Alkano-2,5-diyl (l,3-dioxane-2,5-diyl) 'pyrimidine-2,5-diyl, pyridine-i/-diyl (pyridine_14_diyl), naphthalene -1,5-diyl (naphthalene-l, 5-diyl), naphthalene-2,7-diyl or 蒽_9,1〇-diyl (anthraCene-9,10-diyl), R4 represents Η, Ρ, an alkyl group having a carbon number i to ^, an alkyl group substituted with fluorine having 1 to 30 carbon atoms, an alkoxy group having a carbon number of 丨3 to 3, ON, -OCH2F, -〇CHF2 or -〇CF3,a And b denotes an integer of 〇~4, respectively, c, d, and e represent integers of 〇~3, respectively, and f and g are independent of u.doc 201030060, respectively, and represent an integer of 0 to 2, and c + d+e^l. In the formula (TC-ll) and the formula (TC-12), 'R5 independently represents -H or -CH3, and R6 represents -H, or a carbon number of 1 to 20 or an alkenyl group having 2 to 20 carbon atoms. A6 independently represents a single bond, -CO- or -CH2-. In the formula (TC-12), R7 and R8 each independently represent -H, an alkyl group having 1 to 20 carbon atoms or a phenyl group. In the formula (TC-13) and the formula (TC-14), A7 independently represents a -0- or a carbon number of 1 to 6. In the formula (TC-13), 'R9 represents -H or a carbon number of 1 to 30, and in the group, any -CH2· of the alkyl group having 2 to 30 carbon atoms may be -〇( (but not Continuous), ❹ -CH=CH- or -C=C- is substituted, A8 represents a single bond or an alkylene group having 1 to 3 carbon atoms, and ring T represents a 1,4-phenylene group or a 1,4-cyclohexyl group. Alkene, h represents hydrazine or 1. In the formula (TC-14), R1G represents an alkyl group having 6 to 22 carbon atoms, and R11 represents an anthracene or an alkyl group having 1 to 22 carbon atoms. [2] The liquid crystal alignment agent according to [1], wherein the other tetracarboxylic dianhydride comprises an aromatic tetracarboxylic dianhydride. [3] The liquid crystal alignment agent according to [2], wherein the aromatic tetracarboxylic dianhydride is represented by the following structural formula (1), structural formula (2), and structural formula (5) φ ～ structure At least one of the compounds represented by the formula (7), the structural formula (10), the structural formula (13) and the structural formula (14). 201030060, _____ j__j.doc [Chemical 4]

[4] The liquid crystal alignment agent according to any one of [1] to [3] wherein the tetracarboxylic dianhydride comprises an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic acid-acid One or both of the anhydrides. [5] The liquid crystal alignment agent according to [4], wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are the following structural formula (15), structural formula (16) At least one of the compounds represented by the structural formula (21) to the structural formula (25) and the structural formula (29) to the structural formula (31). 12 ir.doc 201030060

[Chemical 5]

[6] The liquid crystal alignment agent according to any one of [1] to [5] wherein the diamine further comprises a side represented by the following general formula (I) and formula (II) One or more of the diamines of the chain structure. Reference 13 201030060doc [Chemical 6] R12

(In the general formula (I) and the general formula (II), A9 independently represents _〇· or an alkylene group having 1 to 6 carbon atoms. In the formula (1), R12 represents -H or a carbon number of 1 to 3 Å. Any _CH2- of the alkyl group having a carbon number of 2 to 30 in the alkyl group may be substituted by -〇- (but discontinuous), -CH==CH- or -CSC-, and A1G represents a single bond or The alkenyl group of the carbon number of 1 to 3 represents a 1,4-phenylene group or a 1,4-cyclohexene, and h represents hydrazine or 1, and in the formula (II), R15 represents a carbon number of 6 to 22. The alkyl group, r]6 represents an alkyl group having 1 to 22 carbon atoms. [7] The liquid crystal alignment agent according to [6], wherein the diamine having a side chain structure is selected from the group consisting of the following general formula (I-1), general formula (1-2), and general formula (1) -4) and at least one of the compounds represented by the formula (1-7). 14 u.doc

201030060 (In the above formula, R13 and RM each represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms). The liquid crystal alignment agent according to any one of [1] to [7] wherein the diamine further comprises the following general formula (III) to general formula (X), and general formula (N) And a diamine having no side chain structure represented by the formula (a).

15 201030060,doc [化8] h2n—x-nh2 (III)

16 201030060 Hc _____ ^ir.doc (In the general formula (III), 'X represents _(CH2)m- (m represents an integer of 1 to 6), and the general formula (V) and the general formula (VII) to the general formula (IX) Wherein γ independently represents a single bond, _〇_, -S-, _S_S-, -S02-, -CO-, -CONH_, -NHCO-, -NH-, -N(CH3)-(CH2)mN (CH3)-, _C(CH3)2-, -C(CF3)2-, -(CH2)m-, -0-(CH2)m-0-, -S-(CH2)mS-(m denotes 1 In the formula (vil), Z represents a single bond or does not exist, and in the formula (χ), R 9&R2〇 independently represents an alkyl group or a phenyl group having 1 to 3 carbon atoms, A11 independently represents a methylene group, a sub-base group or a sub-group substituted by a mercapto group. i represents an integer of 1 to 6, and j represents an integer of 1 to 10 'general formula (IV) to formula (IX) Wherein, the bond to the cyclohexane ring or the benzene ring may be independently substituted by -F, -CH3, -CF3, -OH, -COOH, - -#2, on the benzene ring in the formula (VI) The bonded hydrogen may be substituted by a benzyl group. In the formula (Ν), Α1 independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, acetamide, fluorine, Chlorine or bromine, a2 independently represents a burning group having a carbon number of 1 to 3, m represents an integer of 0 to 3, and η represents 〇 An integer of ～4. In the formula (a), 'L1 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a styl group or a benzyl group). [9] The liquid crystal alignment agent according to [8], wherein the diamine having no side chain structure is selected from the following structural formula (VP), structural formula (VI-2), Structural formula (VI-15)~Structure formula (VI-17), Structural formula (vn_i)~Structure formula (VII-13), Structural formula (VII-32), Structural formula (νπ·34)~Structure formula (VII -36), structural formula (χι_2), structural formula (Χ-3), structural formula (ν). At least one of the compounds represented by the structural formula (Ν)-2, the structural formula (ν)-14, and the structural formula (a-1). 17 201030060 [化9] h2n

H2N-nh2 (VI-1)

(VII-4) (VII-5) (VII-6)

HO OH (VII-32) 18 201030060 , I,i^i.doc [化10] l_〇^NH2 h2n-nH^^-nh2 h2n-^^-n^v^n (VII-35) (VI1 -34)

NH, ch3 ch3 H2N-C3H6-Si-〇-Si-C3H6-NH2 CH3 ch3

〇 (X-3) ❿ )n_O~nh2

H2N—^ y-H^ , N—^ >-nh2 (N)-2 (N)-1

[10] The liquid crystal alignment agent according to any one of [6], wherein the polyamic acid or a derivative thereof comprises two polylysine or Derivatives A and B, wherein the polyaminic acid or derivative A thereof comprises the diamine having a side chain structure represented by the above-mentioned 19 201030060, the general formula (I) and the general formula (II) One or more of the polyamic acid or derivatives A and B of the tetracarboxylic dianhydride include one or both of the formula (TC-1) to the formula (TC-14) One or more of the four rebel acides of the wilderness are represented by two other needles with the other four. [11] The liquid crystal alignment agent according to any one of [1], which further comprises a nadic ylidene compound selected from an alkenyl group, having a radical polymerizable unsaturated group. One or more of a compound of a double bond, an oxazine compound, an oxazoline compound, and an epoxy compound. [12] A liquid crystal alignment film which is formed by heating a coating film of the liquid crystal alignment agent according to any one of [1] to [11]. [13] A liquid crystal display element having: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode applying a voltage to the liquid crystal layer; and a liquid crystal alignment film to cause the The liquid crystal molecules are aligned in a predetermined direction; the liquid crystal display element is characterized in that: the liquid crystal alignment film is the liquid crystal alignment film according to [12]. According to the present invention, it is possible to provide a liquid crystal display element having a desired property such as retardation and flow alignment in terms of retardation and flow alignment. The above-described features and advantages of the present invention will become more apparent from the following detailed description. [Embodiment] The liquid crystal alignment agent of the present invention contains polyamine or a derivative thereof as a product of tetracarboxylic dianhydride and diamine. The derivative of the poly-proline is dissolved in a solvent in a liquid crystal-forming agent (3) which is described later as a solvent, and is a component of the composition of the liquid crystal alignment agent. In the case of the liquid crystal alignment film, a component of a liquid crystal alignment film containing polyiminoimine as a main component can be formed. Examples of such a derivative of polyglycine are soluble polyimine and polyamic acid ester (polyamic). The acid ester) and the polyamic acidamide, etc., more specifically, 1) polyimine which is obtained by dehydration ring-closing reaction of all amino groups of a poly-proline and a carboxyl group, 2) Partial polyimine which is obtained by dehydration ring-closure reaction, 3) polyglycolate which converts carboxyl group of polyproline into ester, and acid 2 contained in tetracarboxylic acid dianhydride compound A poly-proline-polyamine copolymer obtained by replacing a part of the anhydride with an organic dicarboxylic acid, and further, 5) performing a dehydration ring closure of a part or all of the polyamido-polyamide copolymer Polyamidamine (polyami) De-imide). The polyaminic acid or a derivative thereof may be a compound ' or a compound of two or more kinds. Further, the polyamic acid or a derivative thereof may be a compound having a structure of a reaction product of a tetracarboxylic dianhydride and a diamine, and may be a tetracarboxylic dianhydride by using another raw material. A reaction product obtained by a reaction other than the reaction of a diamine. < 1. Tetracarboxylic dianhydride used in the present invention> The tetracarboxylic dianhydride (hereinafter also simply referred to as diterpenoid) used in the present invention contains the above formula (TC-1) to One or more kinds of tetracarboxylic dianhydride represented by the formula (TC-14). As the two needles of the tetracarboxylic acid represented by the formula (TC-1), it is preferred that the carbon number of the alkenyl group as the main chain of 'X in the formula is 〇 20 20, for example, it can be listed as 21 doc 201030060. The acid dianhydride represented by the structural formula. [ηη]

In the general formula, the number of carbon atoms of the alkenyl group as a main chain of R1 is preferably from 0 to 10, and is represented by the following structural formula, for example, as the tetracarboxylic dianhydride represented by the formula (TC-2). Acid dianhydride. [化 12]

The tetracarboxylic dianhydride represented by the formula (TC-3) is preferably a compound in which the number of carbon atoms of the alkenyl group as a main chain of R1 is from 0 to 10, and examples thereof include the following structural formulas. Acid dianhydride. 22 201030060 [Chem. 13]

In the general formula, the number of carbon atoms of the alkenyl group as the main chain of R1 is preferably from 0 to 10, and is represented by the following structural formula, for example, as the tetracarboxylic dianhydride represented by the formula (TC-4). Acid dianhydride. 23 201030060doc [Chem. 14]

The tetracarboxylic dianhydride represented by the formula (TC-5) is preferably a compound in which the number of carbon atoms of the alkenyl group as a main chain of R1 is from 0 to 10, and examples thereof include the following structural formulas. Acid dianhydride. [化15]

24 201030060 [Chem. 16]

φ is a tetracarboxylic dianhydride represented by the formula (TC-6), and in the formula, the number of carbon atoms of the alkenyl group as a main chain of R1 is preferably from 0 to 10, and examples thereof include the following structural formula. Indicated acid dianhydride. 25 201030060, _____ ^ __.doc [化π]

The tetracarboxylic dianhydride represented by the formula (TC-7) is preferably a compound in which the number of carbon atoms of the alkenyl group as a main chain of R1 is from 0 to 10, and examples thereof include the following structural formula. Acid dianhydride. [Chem. 18]

26 201030060iTd _____^ir.doc As the tetracarboxylic dianhydride represented by the formula (TC-8), it is preferred that in the formula, the carbon number of the alkenyl group as a main chain of R1 is 0 to 10, for example, The acid dianhydride represented by the following structural formula is listed. [Chem. 19]

27 .i.doc 201030060 [Chem. 20]

The tetracarboxylic dianhydride represented by the formula (TC-9) may, for example, be an acid dianhydride represented by the following structural formula. [Chem. 21] ch3 ch3 N—CaHe—Si—O—Si—CgHe—N / CH3 03⁄4 , 28

201030060 H. (±, it. doc) The tetracarboxylic dianhydride represented by the formula (TC-10) may, for example, be an acid dianhydride represented by the following formula or structural formula.

29 .doc 201030060 [Chem. 23] 201030060 ii.doc

31 201030060, oc (In the above formula, R23, R24, R25, and R26 each represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms). The tetracarboxylic dianhydride represented by the formula (TC-11) may, for example, be an acid dianhydride represented by the following structural formula. [Chem. 25]

The tetracarboxylic dianhydride represented by the formula (TC-12) may, for example, be an acid dianhydride represented by the following structural formula.

32 lt^doc 201030060 [Chem. 26]

33 201030060, _____ £.doc [Chem. 27]

The tetracarboxylic dianhydride represented by the formula (TC-13) may, for example, be an acid dianhydride represented by the following formula.

34 201030060 d 1 ii.doc [Chem. 28]

R29

35 _.doc 201030060 (R29 represents - an anthracene, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably an alkyl group having a hindrance of 3 to 30 or a burning oxygen having a carbon number of 3 to 30 base). The tetracarboxylic dianhydride represented by the formula (TC-14) may, for example, be an acid dianhydride represented by the following formula.

(R29 represents an alkyl group having 6 to 22 carbon atoms, more preferably an alkyl group having 6 to 10 carbon atoms. R3() represents an anthracene or an alkyl group having 1 to 22 carbon atoms, and more preferably represents -? or a carbon number of 1~ 10 alkyl). Examples of the other tetracarboxylic dianhydride include acid dianhydride represented by the following formula. 36 if.doc

201030060 (R35 and R36 each independently represent an alkyl group having 3 to 30 carbon atoms). The tetracarboxylic dianhydride which is particularly suitable for use in the present invention is a tetracarboxylic dianhydride represented by the general formula (TC-1) to the general formula (TC-7), and among them, particularly preferably represented by the following structural formula Carboxylic dianhydride.

37 201030060, [Chem. 31]

Ο In addition, from the viewpoint of exhibiting a desired retardation in the liquid crystal display element and suppressing the flow alignment of the liquid crystal display element, it is preferably contained in the acid dianhydride of the poly-proline which constitutes the liquid crystal alignment agent of the present invention. The molar ratio is from 10% to 99.5%, and the tetracarboxylic dianhydride represented by the above (TC-1) to the above (TC-14), more preferably contains 20% to 95% of the (TC) -1) ~ The tetracarboxylic dianhydride represented by (TC-14). In the present invention, as the tetracarboxylic dianhydride, in addition to the tetracarboxylic dianhydride represented by the above formula (TC-1) to formula (TC-14), other tetracarboxylic acid II is further used. anhydride. It is represented by the above formula (TC-1) to formula (TC-14).

Jtdoc 201030060 The tetracarboxylic dianhydride other than the tetracarboxylic dianhydride may be one type, or two or more types may be used to make the present poly-tantoic acid or its derivative soluble. In the case of the shape (4), it is preferable to use a tetracarboxylic dianhydride represented by the formula (like) to the formula (like 4). The juice is represented by the above-mentioned formula (TC-1) to the formula (the tetrakis(tetra) dianhydride other than the TCM acid dianhydride, and examples thereof include: lane: carboxylic acid dianhydride, aliphatic tetracarboxylic acid II Anhydride and an alicyclic acid: a family of four, using the above formula (T(M) to the formula (Τ(Μ二野° such as dianhydride and the four-cylinder dianhydride as the invention) The raw material of the poly-proline or the derivative thereof contained in the alignment agent, thereby increasing the retardation of the liquid crystal alignment and the flow distribution (4) suppression by the county civilization. As the aromatic tetracarboxylic dianhydride, for example, it is possible to The compound represented by the formula (1) to the structural formula (14). The underlying knot 39 :.doc 201030060 [Chem. 32]

(13) The aromatic tetracarboxylic dianhydride preferably has the structural formula (1), the structural formula (2), the structural formula (5) to the structural formula (7), the structural formula (10), and the structural formula (13). And a compound represented by the structural formula (14), and pyromellitic dianhydride represented by the structural formula (1) is more preferable. Examples of the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride include the compounds represented by the following structural formulae (15) to (64): 201030060 H _____ ^xt.doc [Chem. 33 ]

(24) (25) (26) (27)

(28) (29) (30)

(34) (35) (36) (37) 41 201030060 doc

42

201030060tH

^ ^ y % I ^/IX.CLOC

[化35]

The aliphatic tetraphthalic acid dianhydride and the alicyclic tetracarboxylic dianhydride preferably have the structural formula (15), the structural formula (16), the structural formula (21) to the structural formula (25), and the structural formula (29). The compound represented by the structural formula (31) is more preferably 12,3,4-cyclobutane tetracarboxylic dianhydride represented by the structural formula (15). Φ Further, in view of the fact that the poly-proline or the derivative thereof in the present invention is a polyimine which is soluble in a vehicle, the aliphatic tetracarboxylic dianhydride and the lipid bismuth tetracarboxylic acid The anhydride preferably has the structural formula (15) to the structural formula (18), the structural formula (21) to the structural formula (25), the structural formula (28) to the structural formula (3〇), and the structural formula (44) to the structural formula. (47) The compound represented. Further, the tetracarboxylic dianhydride may also contain a tetracarboxylic dianhydride having a side chain structure. The tetracarboxylic dianhydride having a side chain structure can increase the pretilt angle in the liquid crystal display 201030060, ..... ri. doc element. As the tetrareic acid dianhydride having a side bond structure, for example, the following A compound having a steroid skeleton represented by the structural formula (65) and the structural formula (66). [化36]

From the viewpoint of reducing the residual voltage in the liquid crystal display element, the above-mentioned tetracarboxylic dianhydride preferably contains the aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and alicyclic tetracarboxylic acid One or both of the anhydrides. The tetracarboxylic dianhydride also contains tetrahedoic dianhydride in various other forms, and is not limited to the tetraphthalic acid dianhydride. The tetracarboxylic dianhydride may use other various forms of tetradecanoic dianhydride within the scope of achieving the object of the present invention. It is also possible to replace a part of the tetracarboxylic dianhydride with a carboxylic anhydride 44 201030060 ---.. rll.doc (carboxylic anhydride). Replacing a part of the tetracarboxylic dianhydride with a carboxylic acid causes a termination of the polymerization reaction of the polyamic acid or its derivative, thereby suppressing further progress of the reaction, and therefore, it is easy to control the brewing. From the viewpoint of the molecular weight of the amine acid or its derivative, it is preferred. The ratio of the carboxylic acid anhydride to the tetracarboxylic dianhydride may be within a range not detracting from the effects of the present invention, and is preferably equal to or less than 10 mol% of the tetracarboxylic dianhydride. From the viewpoint of increasing the retardation value and suppressing the flow alignment, in the acid dianhydride constituting the poly-proline in the Φ liquid crystal alignment agent, the above formula (TC-1) to the formula (TC-14) The content of the tetracarboxylic acid two needles other than the tetracarboxylic dianhydride represented is preferably from 1% by weight to 9% by mole based on the molar ratio, more preferably from 1% by weight to 80% by weight, and further preferably 30% by weight. 70%. Further, the content of the aromatic tetracarboxylic dianhydride in the acid dianhydride constituting the polyamic acid in the liquid crystal alignment agent is preferably from 〇% to 80% by the molar ratio, and more preferably 〇% to 60%. % is further preferably 〜5% by weight. <2. Diamine used in the present invention> As the diamine used in the present invention, a diamine having a side chain structure represented by the following general formula (I) to formula (II) can be preferably used. (hereinafter also referred to as a side bond type diamine). 45 201030060* [化37] R12

Nh2 nh2 (I)

(ID) In the formula (I), 'R12 represents -H or an alkyl group having 1 to 30 carbon atoms. Any -CH2- of the alkyl group having a carbon number of 2 to 3 Å in the alkyl group may be independently -0- And -CH-CH- or substituted, wherein, in the alkyl group, it is not adjacent. In the formula ® and the formula ®), A9 independently represents -〇- or a carbon number of 1 to 6. In the formula (I), Αι〇 represents a single bond or a sintered group having a carbon number of i to 3. Ring represents M-human stupid or 1,4-cyclohexene. h represents 〇 or 通式 in the formula (9), R15 represents the H shown in the slits 6 to 22, H or the carbon number 丨 22 22, for example, in addition, as a side chain type represented by the above formula (I) Examples of the diamine include diamines represented by the following formulas 屮1) to (1-9).

47

201030060rH _ In the above formulas (Ι·1) and (1-2), R13 represents _H or an alkyl group having 1 to 30 carbon atoms. In the above formulas (1_4) and (1_5), rU represents _H. Or an alkyl group having a carbon number of 1 to 3 Å. Further, in the above formula (1_3), a group represented by _H or a carbon number of 1 to 3 Å is represented by the formula (1-6) to the formula (1-9), and R14 represents -H or a carbon number. 1 to 20 burnt base. As the diamine represented by the above formula (I), for example, a formula (1_1), a formula (1-2), a formula (1-4) and a formula (1-7) can be preferably used. ) the diamine represented. The side chain type diamine represented by the above formula (II) is preferably bonded to the two base groups of 镠, respectively, and the two amino groups are bonded to the meta or para position with respect to A9. The side chain type diamine represented by the above formula (Π) may, for example, be a diamine represented by the following formula (II-1) to formula (11_3). [化39]

Rt7 R18

(H-2) R1J R1® (11-1) R1 < R18 H^O^O^〇sy^-NH2 @ (H-3) In the above formula, R17 represents an alkyl group having 6 to 2 carbon atoms , indicating _H or a carbon number of l~. From the viewpoint of obtaining the alignment property of the liquid crystal display element, the second structure having the ship structure is in the form of a molar ratio of the diamine constituting the polyamic acid in the liquid crystal alignment agent of the present invention. Internal switching (In_plane 48 201030060,

In Switching, IPS), 〇%~5〇%' is more preferably 0%~20%, and in twisted nematic (TN) and STN, it is preferably 〇〇/〇~90%, more preferably 3 %~70%. Further, other diamines other than the diamines represented by the above formula (I) and formula (II) may be preferably further exemplified by the following formula (ΠΙ)~^ formula (X), formula (Ν) And a diamine (hereinafter also referred to as a linear diamine) having no side bond structure of (4) of the formula (a). The diamine having no side chain structure may be one type or two or more types. ❹

49 201030060 [化40] h2n—x-nh2 (III)

50 ii.doc 201030060 (In the formula (III), X represents -(CH2)m- (m represents an integer of 1 to 6), in the formula (V) and the formula (VII) to the formula (IX), Y independently represents a single bond, -〇-, -S-, -SS-, -S02-, -CO-, -CONH-, -NHC0-, -NH-, -N(CH3HCH2)mN(CH3)-, -C(CH3)2-, -C(CF3)2-, -(CH2)m-, -0-(CH2)m-〇-, -S-(CH2)mS- (m represents an integer of 1 to 6 In the formula (VII), Z represents a single bond or does not exist, and in the formula (X), R19 and R2〇 each independently represent an alkyl group or a phenyl group having 1 to 3 carbon atoms, and A11 independently represents a sub-group. a sub-phenyl group substituted with a subgroup or a substituent group. i represents an integer of 1 to 6, and j represents an integer of 1 to 10, and is bonded to cyclohexane in the formula (IV) to formula (IX). The hydrogen on the ring or benzene ring is independent and can be substituted by -F, -CH3, -CF3, -0H, -C00H, -SOsH, -P〇3H2, and the ring on the ring in the formula (vi) The hydrogen may be substituted by a benzyl group. In the formula (N), V independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, acetamidine, gas, chlorine or bromine. , A2 independently represents an alkyl group having a carbon number of i to 3, and m represents an integer of 〇~3' η represents 0 to 4 In the formula (a), L1 represents hydrogen, an alkyl group of 1 to 4, a phenyl group or a benzyl group. ^ ❿ As the direct bond type diamine represented by the formula (III), for example, a diamine represented by the formula (III-1) to the formula (III-3) can be used. [化41]

H2hT, NH2 (Chuan-1) Η2Ν^^^ΝΗ2 (1ΙΙ-2) Η2Ν^-s^-NHj (HI-3) As the direct bond type diamine represented by the formula (IV), for example, 51

D〇C 201030060 Diamine represented by structural formula (IV-1) and structural formula (I V-2) H2N-NH2 (IV-2) h2n -〇 nh2 (IV-1)

The linear diamine represented by the formula (V) may, for example, be a diamine represented by the structural formula (V-1) to the structural formula (V-3). Q

[化43]

The linear diamine represented by the formula (VI) may, for example, be a diamine represented by the structural formula (VI-1) to the structural formula (VI-17).

52 .i.doc 201030060 [化 44]h2n_〇^' (VI-1) •nh2

HzN-〇rNH H2N-nh2 (VI-3)

COOH

(VI-2) OH

HOOC (VI-9) -nh2 H2N v NH2 (VI-6)

H2N-^)-NH2 (VI-7)

Λ h2n-^:^vnh2 (VI-8)

, cf3 H2N~^ ^~NH2 (VI-17) The linear diamine represented by the formula (VII), for example, may be exemplified by the structural formula (VII-1) to the structural formula (VII-3 6). The diamine represented. 53 .doc 201030060 [Chem. 45]

%-nh2 H2N-~J^~m2 H2N—^ (VI1-1) (VII-2) 丨丫 NH2 H2N^j| (VII-3)

J-^2 H2N-^^〇N^j)-NH2

(VI1-12) (VII-13) h^°XXNH2 (VI1-14)

H2nm〇^0v^〇n0^nH2 H2N^Ok〇n^〇^Oknh2 (VI1-16) (VII-17) (VII-18) H2N-^^°\^n^〇^^-NH2 H2N-^ ^C (VII-19) (VII-20) h2N-^~^S~~v^~^-NH2 H2N-h^^K~S, s^~^)-nh2 (Vll-21) (VII- 22) ❹ '〇, nh2 54 201030060 ii.doc [Chem. 46] H2N^0^S^Sx&lt;Q^NH2 H2N-^0rS'^s^〇KNH2 (VII-23) (VI1-24), s ^ 〇^ΝΗζ HzN_hO^ ❹ h2n-0t-£ (VI1-25) (VI1-26) NH,

^~NH2 H2N-""-N-"--NH2 H2N-^"-N^V-N-""-NH2

OH OH

(VI1-33) (VI1-34) I (VII-35)

NH, the linear diamine represented by the formula (VIII), for example, a diamine represented by the structural formula (VIII-1) to the structural formula (VIII-6). 55 201030060, ___ .r__.doc [Chem. 47]

(VIII-5) (VIII-6) ® As the linear diamine represented by the formula (IX), for example, two represented by the structural formula (IX-1) to the structural formula (IX-16) amine.

56 201030060 d x u.doc

Nh2h2n- (IX-1) (Xi-2) H2n-Ok^^j^ch2)tO^HI)_nH2 HzN'H0/v^3^CH2)r0^0~NH2 (IX-3) (IX-4 ) h3c .ch3 (IX-5) (IX-6) _f3c,;f3 — — 9 — -S'

/-NH2 (IX-8) NH2 H2N^r〇-Q-(cH2)rQ^〇-&lt;Q^NH2 ❹ (IX*7)

(IX-10)

-NHZ H2N-〇^°^Q^-(CH2)j^-〇-QkNH2 H2N-Q-°^Qh-(cH2^, 0Χ-Ί1) (1X-12) h3c ch3 η2ν^Ο^ (IX- 13) J3C. &gt;CF3 (IX-14) - ^3G CF3^ 〇 (4) Let h2N_q^k! Order (IX-15) (IX-16) Among these diamines, as a more preferable linear diamine, The formula (VI-1), the structural formula (VI_2), the structural formula (VI_15) to the structural formula (VI-17), the structural formula (VII-1) to the structural formula (VII-13), The formula (VII-32), the crucible formula (VII-34) to the structural formula (VII_36), and the amine (represented by the structural formula (ι__2)) are further preferred as the linear amine diamine. The diamine represented by the formula (vi-i), the structural formula (VI-15), the structural formula (VI_16), the structural formula (vw), and the structural formula (VII-7). 57

201030060H The diamine represented by the above formula (X) is, for example, a diamine represented by the following structural formula (X-1) to structural formula (X-7). Among these diamines, a diamine represented by the following structural formula (X-3) is particularly preferably used. CH3 ch3 H2N-CH2-Si-〇-Si-CH2-NH2 CH3 ch3 (X-1) ch3 ch3 H2N-C3H6-Si-〇-Si-C3H6-NH2 ch3 ch3 ch3 ch3 l. !. H2N —C2H4—0 〇—from C2H4—ΝΗ2 ch3 ch3 (X-2) ch3 ch3 H2N-C4H8-Si-〇-Si-C4H8-NH2 CH3 ch3

(X-3) CH3 CH3 CH3 H2N-C3H6-Si-〇-S 〇-Si-C3H6-NH2 CH3 ch3 ch3 (X-4) C2H5 c2h5 H2N-C3He~Si~0-Si-C3H6-NH2 C2H5 c2h5 (X-5) O3H7 C3H7 (X-6) H2N-C3H6-Si-0-Si-C3H6-NH2 C3H7 C3H7 (X-7) As the diamine represented by the above formula (N), for example, The following structural formula (N)-1, structural formula (N)-2, structural formula (Ν)·5~ structural formula (N)-7, structural formula (N)-9, structural formula (N)-10, Structural formula (N)-14, structural formula (N)-17, structural formula (N)-18, structural formula (N)-21~structural formula (N)-23, structural formula (N)-26, structural formula The diamine represented by (N)-28. Among these diamines, a diamine represented by the following structural formula (N)-1, structural formula (N)-2, and structural formula (N)-14 is particularly preferably used. 58 u.doc 201030060 Λ.

[化 50]

(N)-1

(N)-6

(N)-10 (N)-14

(N)-21 (N)-22

(N)-23

(N)-26

(N)-28 The diamine represented by the above formula (a) may, for example, be a diamine represented by the following structural formula (a-Ι) to structural formula (a-3). Among these diamines, a diamine represented by the following structural formula (a-Ι) is particularly preferably used. 59 _i.doc 201030060 [Chem. 51]

From the viewpoint of obtaining an appropriate orientation when the liquid crystal display element is formed, the molar ratio of the linear diamine to the diamine constituting the poly-proline of the present invention is in 〖ps It is preferably from 5% to 1% by weight, more preferably from 80% to 100%. It is preferably from 1% to 100% in TN and STN. More preferably, it is 30% to 97%. In addition, the other diamine is not particularly limited, and examples thereof include diamines represented by the following formula (丨) to (8). [化52]

60 n.doc 201030060 / Wire 1 independently showing carbon number 3 to 30 In the general formulas (4), (6) and (8,), R22 represents a carbon group having a carbon number of 3 to 30. In the liquid crystal alignment agent constituting the present invention, the degree of the effect of the present invention is not detrimental to the extent of the effect of the present invention. For the second filament, it can be compared with each of the diamines (m〇n〇amine). The ratio of diamine is less than or equal to * =

The inner portion replaces the -diamine moiety with a monoamine. This can be done in step-by-step. Therefore, by such substitution, the molecular weight of the desired polymerization (polylysine or its derivative), such as; and the coating of the present invention, improves the coating properties of the liquid crystal. = and the effect of the present invention 'The diamines which are then substituted with a monoamine may be two kinds, and may be two or more kinds. As the monoamine, for example, aniline (4-hydroxyaniline) (cyclohexylamine), n-butylamine (n-butylamamine, n-heptylamine, n-octylamine, n-decylamine, n-nonylamine, n-di-amine, n-Dodecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptaamine, n-octadecylamine, and n-dodecylamine. Among the monomers of polylysine or its derivatives (_〇 Bribes can also include a monoisoocyanate compound. The mono-ocyanate compound is contained in the body, and the end of the polypyrene or its derivative is obtained, and the molecular weight is obtained. The _ terminal dance type polyaminic acid or a derivative thereof can be used, for example, without impairing the effects of the present invention.

201030060.J〇C Improves the coating properties of liquid crystal alignment agents. From the above viewpoints, the content of the monoisocyanate compound in the monomer is preferably i mole % to 10 mol% relative to the total amount of the diamine and the tetrahedral liver in the monomer. Examples of the monoisocyanate compound include phenylis〇cyanate and naphthyl isocyanate. In the present invention, in the range which does not impair the effects of the present invention, The diamine other than the diamine represented by the general formula (III) to the general formula (X) and the general formula (N) may be a diamine having a side bond structure as described below (hereinafter also referred to as a side chain type II). (Amine). As such a diamine having a side chain structure, for example, a diamine having a side chain structure represented by the following general formula (XD, general formula (xm), and general formula (χιν)) may be mentioned. The diamine of the chain structure may be one type or two or more types. [Chem. 53] R27 Λ (Χ0 h2nt^J-nh2 ❹ In the formula (XI), A12 represents a single bond, _〇_, _c 〇〇...〇c〇-, -CO-, -C0NH_4-(CH2)m- (m represents an integer of 1 to )), and R27 represents a group having a steroid skeleton, and a group represented by the following formula (XII), In addition, when the positional relationship of the two amino groups bonded to the stupid ring is para-position, R27 further contains an alkyl group having a carbon number of 1 to 30, when the positional relationship is between In the case of R27, R27 further contains an alkyl group having 1 to 30 carbon atoms or a phenyl group. In the alkyl group, any 'independent' can be -CFr, -CHF-, -〇- (but not continuous), _CH =CH- or 62 201030060u.doc ^«Just substituted, _CH3 can be substituted by -CH#, -CHF2 or -CF3. In addition, the hydrogen of the phenyl group is independent and can be _F, _CH3, _0CH3, -OCH2F , -〇CHF2 or -ocf3 is replaced.

In the general formula (XII), 'A13 and A14 each independently represent a single bond, -0_ (but not continuous), -COO-, -0C0-, -CONH-, -CH=CH- or an alkane having 1 to 12 carbon atoms. Alkenyl 'r3〇 and r31 each independently represent -F or -CH3, and ring S independently represents M-phenylene, M-cyclohexene, dioxo-2,5-diyl, pyrimidine-2,5 -diyl, pyridine-fluorene-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or fluoren-9,l-diyl, R32 represents -H, _F, carbon number 1~ An alkyl group of 30, an alkyl group substituted with fluorine having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -C=N, •OCH2F, _〇CHF2 or _OCF3, a and b respectively represent 0~ An integer of 4, c, d, and e respectively represent integers 0 to 3 'f and g respectively represent integers of 0 to 2, respectively, and c + d + eg Bu. In addition, when c + d + e = 1, R4 An alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. 63 201030060-

(ΧΠΙ) (XIV) In the formula (XIII), hydrogen bonded to the carbon forming the steroid skeleton is independent and can be substituted by _ch3. In the formula (xm) and the formula (?), R37 each independently represents -H or -CH3'. R38 represents -H or a carbon group of 1 to 20 or an alkenyl group having 2 to 20 carbon atoms. A15 independently represents a single bond, _c〇_ or -CHr·. In the formula (XIV), 'R39&amp;R4g each independently represents an ugly, alkyl group having 1 to 20 carbon atoms or a phenyl group. In the case of a side-chain type diamine represented by the formula (XI), two kinds of diamines represented by the formula (XI), For example, a diamine oxime represented by the following formula (XI-1) to formula (XI-9) can be cited as 201〇3〇〇6〇".

(XM) (XI-3) (XI-2) h2n Ming h2n

(XI-9) In the above formula (XI-1), formula (XI-2), formula (XI-5) and formula (XI-6), 'R41 represents an alkyl group having 1 to 30 carbon atoms. Or an alkoxy fluorenyl group having 1 to 30 carbon atoms, preferably an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, more preferably an alkyl group having 5 to 25 carbon atoms or a carbon number of 5 to 25 Alkoxy group. Further, in the above formula (XI-3), formula (XI-4), and formula (XI-7) to formula (XI-9), 'R42 represents an alkyl group or a carbon number of 1 to 30 carbon atoms. The alkoxy group of 1 to 30 is more preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. In addition, examples of the side chain type diamine represented by the above formula (XI) include the amines represented by the following formula (XI_10) to (XH5). ', one of 65 20103 0060.a〇c [57]

(XI-14) (XI-15) In the above formula (XI-10) to formula (XI-13), R43 represents an alkyl group having 4 to 30 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms. . In the above formula (XI-14) and formula (XI-15), R44 represents an alkyl group having 6 to 30 carbon atoms, preferably an alkyl group having 8 to 25 carbon atoms. In addition, examples of the side chain type diamine represented by the above formula (XI) include diamines represented by the following formula (XI-16) to formula (XI-36).

66 201030060 i.doc [Chem. 58]

H2n h2n^^ h2n H2N νι H2N /V| h«7\ H2N (XI-16) h2n h2n (XM7) h2n h2n (XI-18) h2n h2^ h2n ^0^r45 0^°^OR45 ^°^^ -R46 h2n /V1 h2n , V1 h2n , VI OH, h2n h2n (XI-19) ❹ h2n h2n

(XI-20) h2n r°^&gt;' o (XI-22)

R45 h2n h2n (XI-23) (XI-21) -R45 r46

H2n (XI-24) (XI-25) N

(XI-28) (XI-29) ❹ 67 201030060idoc [Chem. 59]

The general formula (XI-16), the general formula (XI-17), the general formula (χι_2〇), the general formula (ΧΙ-22), the general formula (ΧΙ-23), the general formula (ΧΙ-26), In the formula (χι_28), the formula (ΧΙ-29), the formula (ΧΙ-34), and the formula (XI-35), R45 represents a thio group having a carbon number of i to 30 or an alkoxy group having a carbon number of from 1 to 30. More preferably, it is an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. The general formula (XI-18), the general formula (XI-19), the general formula (XI-21), the general formula (XI-24), the general formula (XI-25), the general formula (XI-27), In the formula (χι_30) to the formula XI (XI-33) and the formula (XU6), 'R46 represents -H, -F, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having a number of 1 to 3 Å, -ON, -〇CH2F, -〇CHF2 or -〇CF3, preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. In the above formula (XI-31) and formula (XI-32), A16 represents an alkenyl group having 1 to 20 carbon atoms. In addition, as the side chain type diamine represented by the above formula (X), for example, 68 20103006 (Ldoc diamine) represented by the following structural formula (XI-37) to structural formula (ΧΙ·46) can be used. .

[60]

69 201030060^ [Chem. 61]

H2n

(XI-45)

Preferably, the one-bonded diamine represented by the formula or the general formula ρα.4) is a one-bonded diamine represented by the formula (xm), preferably one of the two NH^Ph-A1 It is attached to the 3 position of the steroid core, and the other is bonded to the 6 position. Further, the two amino groups respectively bonded to the two stupid groups are preferably bonded to the meta or para position with respect to the bonding position of A15. The side chain type diamine represented by the above formula (ΧΙΠ) may, for example, be a diamine represented by the following structural formula (ΧΠΙ-1) to structural formula (ΧΙΙΙ-4). 70 201030060iidoc [Chem. 62]

Κϋί means that two of the lysine-type diamines are on the phenyl carbon, but it is preferred that the carbon of the phenyl t bonded by the nucleus is bonded to the meta position, and the phenyl group is difficult to bond. (4) The pure base axis is bonded to the meta or para position for the 鏠 junction position of A 〖5. Examples of the side chain type diamine represented by the above formula (XIV) include _71 represented by the following structural formula (XIV-1) to structural formula (XIV-8).

20103 0060JOC

[化63]

(XIV-1) ο

(XlV-2) 0 NH2

Nh2

(XIV-5) 0

Nh2

(XIV-8) ^CS0-NH2 ❹ From the viewpoint of obtaining an appropriate alignment property in forming a liquid crystal display element, the above-mentioned diamine has the above formula (XI), formula (XIII) and formula The molar ratio of the diamine having a side chain structure represented by (XIV) to all the diamines constituting the polyalkenic acid in the 72 201030060idoc liquid turbidity agent of the present invention is preferably 0% to 50% in milk. More preferably, it is 〇%~, and it is selected from 0% to 90% in tn and st, and more preferably 3% to 7%. The poly-proline or a derivative thereof can be used in combination with the tetracarboxylic dianhydride represented by the formula (TC-1) to the formula (TC 14) and other tetrahydro acid dianhydrides. (A) The well-known polyacrylic acid or a derivative thereof is produced in the same manner. Excellent total addition of acid dianhydride

The total number of moles selected from the diamine is approximately mol (the molar ratio is about Q9 to n), and the molecular weight of the polyamic acid or its derivative is a polystyrene-reduced weight average molecular weight (Mw Preferably, it is from 10,000 to 500,000, more preferably from 20,000 to 200, 〇〇〇. The molecular weight of the polyaminic acid or its derivative can be determined by using gel permeation chromatography (Gel)

The Permeation Chromatography (GPC) method was measured and determined. The polyaminic acid or a derivative thereof can be confirmed by the following method: that is, by infrared spectroscopy (IR), nuclear magnetic resonance (NMR), and precipitation using a large amount of poor solvent. The solid components were analyzed. In addition, gas chromatography (GC), high performance liquid chromatography (Gas Chromatography, GC) can be performed on an extract of an organic solvent of a decomposition product of the polyaminic acid or a derivative thereof with a strong aqueous solution such as KOH or NaOH. High Performance Liquid Chromatography (HPLC) or Gas Chromatograph-Mass Spectrometer (GC-MS) analysis was performed to confirm the monomers used. 73 201030060.doc The liquid crystal alignment agent of the present invention may further contain other components than the polyamic acid or a derivative thereof. The other ingredients may be one type or two or more types. For example, the liquid crystal alignment agent of the present invention may further contain an alkenyl substituted imine compound substituted with an alkenyl group from the viewpoint of stabilizing the electrical properties of the liquid crystal display device for a long period of time. The alkenyl iodide compound substituted with an alkenyl group may be one compound or a combination of two or more compounds. From the viewpoint of the above, the content of the alkenyl substituted imine compound substituted by the alkenyl group is preferably 0.01 to 1.00 by weight based on the weight ratio of the poly-artisic acid or the derivative thereof in the liquid crystal alignment agent. More preferably, it is 0.01 to 0.70, and further preferably 0.01 to 0.50. The naphthylamine compound substituted with an alkenyl group is preferably a compound which can be dissolved in a solvent which dissolves the polyaminic acid or a derivative thereof used in the present invention. Examples of such an alkenylimine compound substituted with an alkenyl group include compounds represented by the following formula (Ina). [Chem. 64] Corrected the general formula.

In the alkyl group and the carbon number formula (Ina), L and L2 each independently represent hydrogen, carbon number ^~^ group, carbon number 3 to 6 alkenyl group, and carbon number 5 to 8 cycloalkyl group 74 201030060 Cycloalkyl, aryi or benzyl, n represents 1 or 2. When 1 o', W represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, a sulfhydryl group, and a ruthenium group. Ννβονζ3·!^1, Z2 and Z3 independently represent a carbon number of 6 sinter, q represents 0 or 1, and Γ represents an integer represented by 1 to 3 )), and -(Z4)SB-Z5 -H (Z4 and Z5 independently represent an alkylene group having a carbon number of i to 4 or a badly burned base having a carbon number of 5 to 8, B represents a subphenyl group, and s represents a group represented by hydrazine or 1), and is represented by a phenyl group, and τ represents a group represented by -CH2_, -C(CH3)2-, -0-, -CO-, -S- or S02-), or one to three of these groups. A group substituted by a hydroxyl group. In this case, preferred W is a carbon group having 1 to 8 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a group having an alkyl group, and a poly(ethyleneoxy group) having a carbon number of 4 to 1 Å. Ethyl (poly(ethyleneoxy)ethyl), phenyloxy phenyl, phenyl methyi phenyl, phenyl isopropylidene phenyl, and these groups One or two hydrogen-substituted groups. n When n=2 in the general formula (Ina), W represents a basic group having 2 to 20 carbon atoms, a cycloalkenyl group having 5 to 8 carbon atoms, and an arylene group having 6 to 12 carbon atoms. a group represented by -zLcKzhvz^z1 to Z3 and r as described above), a group represented by -Z4-BZ - (the meanings of Z, Z, and B are as described above), and -B-(0- B) s-T_(B-0)sB-(B represents a subphenyl group, τ represents a base of carbon number 1 to 3, -0- or -SCV 's represents a group represented by hydrazine or 1), or One to three quinones of these groups are substituted by a radical. In this case, preferred W is an alkenyl group having 2 to 12 carbon atoms, cyclohexanyl, 75 201030060.a〇c phenyl, tolylene, stupid dimethyl (tetra) plus e), 〇3Η6-0-(Ζ2·〇)γ-〇·(:3Η6-(Ζ2 represents an alkyl group having 2 to 6 carbon atoms, Γ is not 1 or 2), and _Β·Τ-Β_ (Β represents a subphenyl group, and Τ represents a group represented by -CHr, _〇- or -S(V), and a group represented by -bob-C3H6_b-o-b_(b represents a substitutable group), and these groups One or two hydrogen-substituted groups are substituted by a group. • Such a nadic-ylidene compound substituted with an alkenyl group can be used, for example, as described in Japanese Patent No. 2729565, by being substituted by an alkenyl group. The nadic anhydride derivative and the diamine are obtained by synthesizing a compound obtained by synthesizing G. 5 hours to 2 Gh at a temperature of ❹ at a temperature of 8 〜. Specific examples of the substituted Nadick-bromide compound include the compounds shown below. N-methylpropylpropyl bicyclo [2.2.lm_542, 3_di-supplemental enamine (N-methyl-allylbicyclo[2.2j] ]hept-5-ene-2,3-dicarbox Yimide), N-methylallylhydrazinobicyclo[2 2 ·_5|2,3-di-restrobinium imine, Ν-methyl·methallylbicyclo[2 21]hept-5-ene '3_Dicarboxy quinone imine, Ν_曱-yl-hydrazinylpropylbicyclo[2 2]]heptane-5_ roasted_2,3_di-filariaimine, Ν-(2-ethyl Hexyl)-propylidene bicyclo[2 2 hept·5_wo-2,3_diindole carboxy quinone imine, 'mono-(2-ethylhexyl)-allyl (methyl)bicyclo[2 21 Geng_5_ene_2,3_dicarboxy quinone imine, Ν-allyl-allyl bicyclo[2·2 ηhept_5_enyihong carboxy quinone imine, Ν-allyl-ene Propylmethylbicyclo[2 2...heptyl- 2,3-dicarboxyindenine, fluorenyl-allyl-mercaptopropylbicyclo[2·2^hept.·ene-2,3- Dicarboxy quinone imine, isopropenyl-allyl bicyclo quinone·2· η g _5_ 76 u.doc 201030060 olefin-sodium sulfoximine, N-isopropyl-allyl (methyl) bicyclic ring pH]hept-5-ene-2,3-dicarboxyarminemine, N_isopropenyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3·dicarboxyarmine 'N_Cyclohexyl-allylbicyclo[2.2^]hept-5-rare-2,3-dicarboxyindolimine, N_cyclohexyl-allyl (methyl) double %P.2.1]g- 5-ene-2,3 -Dicarboxy quinone imine, N-cyclohexyl-mercaptopropyl bicyclo [2.2.1] hept-5 · dilute 2,3-dicarboxy acid imide, ν·phenyl-allyl (tetra) ring [2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine, 〇m N-phenyl-allyl (methyl)bicyclo ρ.2.1]hept-5-ene-2,3-dicarboxyl Imine, N-nodal, propyl propyl bicyclo [2 21] g _5 _ _2, 3 _ double tendon lead two counts = N 呷 呷 稀 稀 dipropyl bicyclo [2 21] G · 5_ Alkene ST is called dipropyl bicyclo [2.2.1] gemylamine (2_ylidylethyl)-allyl (methyl)bicyclo[Z2.1]hept-5-ene^) 2.lm_5.m silk imine, post 3 propyl ^===methyl __] g _ 5 life 2,3-dimercapto _ (3 hydroxy-1-propenyl)-allyl bicyclo fluorene 2·1]g _5_ene [such as] G. 5 - Rare aryl iranine, anthracycline (4-phenylphenyl) _allyl bicyclo [221] G _ 5 _ -2, 3_二丝77 jt.doc 201030060 Imine imine, N~(4-hydroxyphenyl)-dilyl (methyl)bicyclo[2.2.1]g _5-diluted _2,3_- Amine, N-(4-p-phenylphenyl)-methylindolediylbicyclo[2 2 1]hept-5-ene-2,3-dicarboxyindenine, N_(4-hydroxyphenyl)_曱Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di-resinimide, N-(3-carbyl) ()) allyl bicyclo [2.2.1] hept-5-ene · 2,3-dicarboxy quinone imine, N_(3-hydroxyphenyl)-allyl (methyl) bicyclo [2.2·_5 Lu 2,3_二县醯亚ς, Ν-(to the base group) _ propyl propyl p21] g y _2, 3 _ _ _ _ _ _ _ _ _ _ _ _ }_稀稀双环似---2,3-二缓基丑胺胺, η:故基ethoxy)ethyl}_propyl (indenyl)bicyclo (2.2.1) g-5-ru 3· 二县醯iimine, N_{2_(2嚷基(四)丙庚倾·2,3•Reading m Methyl propylmethyl double dimer 2.1] Geng 2 4 slope r preparatory slope, heptene-2 , 3-di-rebelletic imine, team [2-{2-(2-Hoxy}ethyl-propyl(indenyl)bicyclo[2.2.1]heptyl], township (2·woven ethoxylate) Ethyl diethylidene diyl) stupyl bis. T N_{4-(4-pyridyl isopropylidene di N- {4-(4-hydroxyxin: 2. -5· olefin·2,3·dicarboxy quinone imine, NN,i imine, and their oligomers, bis-di-gly-bis-bis. 2.η-g- 5·ene-2,3.二丝78 201030060iidoc ^)(N,N'-ethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicar boxyimide)), N,N'-ethylidene-bis(phosphorus Bismuthyl double ring [2 2 ^g·5_ ene-2,3- a few醯imino), N,N'-ethylidene-bis(methyldipylbicyclo[2.2.1]hept-5-ene-2,3-di-redecylimine), ν,Ν'- Wang 曱 --bis (dilyl bis-bicyclo[2.2.1]hept-5-ene-2,3-disulfhydrylimine), ν, ν'-hexamethylene _ bis (dilyl propyl bicyclic [2.2 .1]hept-5-female-2,3·dicarboxyindolimine), ν,ν,α methylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2, 3-di-supplemental-based amines, anthracene, oxime--dodecyl-bis(dipropylbicyclo[2.2.lm_5_ene_1,3-diaminofuranimine), N,N '-Eleven methylene-bis(l-propyldecylbicyclo[22 1]hept-5-ene-2,3-dicarboxyanimine), N,N'-cyclohexene_bis(allyl Bicyclo[2.2.1] hept-5-rare-2,3--rebornyl imine), N,N'·cyclohexene-bis(l-propyl decylbicyclo[2.2.1]g·5 · enedicarboxyimine), 1,2-bis{3'·bromopropylbicyclo[2.2.1]hept-5-ene·2,3-dicarboxyarenimine) propoxy}ethane l,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimid φ e)propoxy } ethane), 1,2_double {3'-dilyl fluorenyl double ring [2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) propoxy } ethane, 1,2-double {3,···yl propyl propyl bis-[2.2.1]hept-5-lean-2,3-di-rebasic imine) propoxy} Bis[2'·{3'-allylbicyclic P.2.1]hept-5-ene-2,3-dihydroxyinlimine)propoxy}ethyl]ether (bis[2'-{3' -(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide )propoxy}ethyl]ether), bis[2'-{3'-allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine) propoxy}ethyl]ether, 1,4-double {3'-dilylpropyl 79 201030060 _____Γ—·α&lt;χ; bicyclo[2.2.1]g -5-ene-2,3-di-reactive iodide)propoxy} butyl (1,4-bis{3 -(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimid e )propoxy}butane), 1,4-bis{3'-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}butane, N , N'-p-phenylene-bis(allylbicyclop.2.1)hept-5-ene-2,3-dicarboxyanimine XNW-p-phenylene-bisQllylbicyclol^ll^ept-S-eneJj- Dicarboxyimide;)), Ν, Ν'-p-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), Ν,Ν'- Meta-phenyl-bis(allylbicyclo® [2.2.1] H,5-ene-2,3-dicarboxyimine) (N,N'_m-phenylene_bis (allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)), N,N'- Meta-phenyl-bis(distypropylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), wind 1^-{(1-methyl)-2,4 -N-phenyl}-bis(allylbicyclo P.2.1]hept-5-ene-2,3-dicarboxyindolimine)(N,N'-{(l-methyl)-2,4-phenylene }-_bis(allylbicyclo[2.2.1] hept-5-ene-2,3-dicarboxyimide), N,N'-p-diphenylene-bis(allylbicyclo[2.2.1]hept-5- Alkenyl-2,3-dicarboxyindenylamine XN'N'-p-xylylene-bisfallylbicycloP.〗 l]hept,5-ene-2,3-di carboxyimide)), N,N·-pair Phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), hydrazine, Ν'-m-phenylenedifluoryl-bis(allylbicyclo) [2.2.1] H-5-ene-2,3-dicarboxy quinone imine) (N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboximide)), N, NL meta-benzoic acid-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), 80 201030060idoc 2,2_double [4·{4·(propylpropyl bicyclo[2.2.1]hept-5-ene-2,3-di 2,2-bis(4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyim ide)phenoxy}phenyl] Propane), 2,2·bis[4-{4-(allylmethylbicyclo[2.2.1]heptene·2,3-dicarboxyindolimide) phenyloxy}phenyl]propane, 2, 2-Bis[4-{4-(decyl-dipylbicyclo[2.2.1]hept-5-ene-2,3-dioxalimine)phenoxy}phenyl]propane, double { 4-(Dilyl-propylbicyclo[2.2.1]hept-5-ene-2,3-bis-destrobin iodide) stupid base}曱(©(bisl4-(allylbicyclo[2.2.1]hept-5) -ene-2,3-dicarboxyimide)ph enyl}methane), bis{4-(allylhydrazinobicyclo[2.2.1]hept-5-diluted_2,3-dicarboxyarmineimine)phenyl}methane , double {4-(mercaptopropylidene bicyclo[2.2.1]hept-5-lean-2,3-disulfhydrylimine)phenyl}methane, double {4-(mercaptopropylallyl) Bicyclo[2.2.1]hept-5-ene•2,3-di-rebasic imine)phenyl}zepine, bis{4-(allylbicyclo[2.2.1]hept-5-ene- 2,3-dicarboxy quinone imine) bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)ph ❹ enyl}ether), double {4_(ene Propyl fluorenylbicyclo[2.2.1]hept-5-thin-2,3-di-resinimide)phenyl}ether Double {4-(methylallylbicyclo[2.2,1]heptene 2,3-dicarboxyindolimine)phenyl} shouting, double {4_(dilylpropylcyclo[221]hept-5-ene-2 , 3-dicarboxy quinoid imine) bis{4-(allylbicycl〇t2.2.1]hept-5-ene-2,3-dicarboxyimide)ph enyl}sulfone), double {4-(allyl Methylbicyclo[m]hepta-5-indenyl-2,3-dicarboxyarsenazo)phenyl}milled, double {4-(mercaptopropylbicyclo[2.2.1]hept-5-thin- 2,3-two-wound base Ya 81 201030060 Joc amine) phenyl} 飒, 1,6 bis (allyl bicyclo [2.2.1] g _5 _ _2, 3 _ bis ribitol )-3-,6-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide)-3-hydroxy-hexane), 1,12-bis(methyl) Allyl bicyclo [2 2 ^heptene:ene 2,3·di-rebasic imine)-3,6-di-perylene-dodecyl, 1,3_bis (propylpropyl bicyclo [2.2.1] Hg-5-rare-2,3-dicarboxy-bromoimine)_5-radio-cyclohexene, 1,5·bis{3'-allylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxyindolimine)propoxy}-3-hydroxy-pentane, 1,4-bis(allylbicyclo[2.2.1]hept-5-ene-2,3.dicarboxyfluorene Amine)-2-hydroxy-benzene, 'M-bis(allylmethylbicyclic P.2.1)hept-5-ene_2,3- Dimercaptopurine)-2,5-dihydroxy-benzene, N,N'-p-(2-hydroxy)benzodiazepine_bis(allylbicyclo[2.2.1]hept-5-ene_ 2,3-Dicarboxy 醯 ^ ^ ) C ^, N p-(2~hydroxy) xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide), N,N'- (2-hydroxy)benzodiazepine-bis(allylmethylcyclo[2.2.1]hept-5-ene-2,3-disulfhydrylimine), n,N'-inter (2 -hydroxy)phenylenedonyl·bis(allylbicyclo ρ.2 ηhept-5-ene'孓dicarboxy quinazomine), hydrazine, hydrazine, -m-(2.hydroxyl)-p-dimethyl- _ Mercaptopropyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), ]^, :^, _ p-(2,3-dihydroxy)benzene-methyl-double (allylbicyclo[2.2.1]hept-5-ene-2,3-di-protective imine), 2,2-bis[4-{4-(allylbicyclo[2 21]hept_ 5-ene-2-,3-dicarboxyarsenine)-2-hydroxy-phenoxy}phenyl]propane, bis{4_(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinoid imine) 2 -hydroxy-phenyl decane, bis {3-(allylbicyclo[2.2.1]hept-5-ene·2,3_di-rebasic imine) Bucket base _ phenyl} ether, double {Η methallyl double ring [2.2 η g du d 2,3_ dimercapto 82 201 030060^ 醯imino)-5-hydroxy-phenyl}indole, tris{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-diindenylimine)} Phenoxymethylpropane, N,N',N"s (hypoethyl methallylbicyclo[2.2.1]hept-5-ene-2,3-dioxalimine) isocyanide Uric acid esters, and oligomers thereof and the like. Further, the alkenylimine compound substituted with an alkenyl group used in the present invention may be an asymmetric compound containing an alkenyl group or a phenylene group represented by the following structural formula. ❹ [Chem. 65]

83 • doc 201030060 中优ΐΧΓ Γ N 被 被 被 被 被 被 被 被 N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N 5 base susceptor 2 Yaguang, -ethylidene, methyl propyl bicyclo guanidine bis (dilyl propyl ring called Geng ^ thin ^ sub-amine), N, N, _ hexamethylene _ methylene - bis (dilylmethyl bis-bis-silk imine), N, N, · six ^, n, n, - dodecamethylene _ bis (female carboxy quinone imine), N, N, - Twelve Asians. 1] Geng _5 2, 3- 2 Gina 2, 3 · 2 County Stuffed A ^ ^ C ^ base double egg Zhen ^ 2 · 2.1, 2, 3- dicarboxy ^, the second Benji-double (female c 9 ng &lt; quinone imine), p-benzene benzene 1 ^ = · ^ like 3- dicarboxy hydrazine [2.2 · υ -5 -5 养 2, 3 _ Two-base bicyclic (four) double-ruple..5==:_yl_double (sweet propylene (allyl:imine), hydrazine, π-diphenylene, (allyc = j imine), take, · pair Dimethyl stupyl-propyl A double-produced l^-2,3-di-succinimide), N,N,-m-phenylene smectite 基J base double though 2. purchase · (four) ·: silk 醯 butterfly 84 201030060iidoc Base-bis (l-propyl decyl bicyclic P.2.1] hept-5-ene-2,3-dicarboxy quinone imine), 2,2-double [4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-diindenylimine) oxy}benzin]propane, 2,2-bis[4- {4-(Baked propyl fluorenylbicyclo[22 1]hept-5-ene-2,3-dicarboxy quinazomine)phenoxy} stupyl]propane, 2,2_bis[4-{4- (Methylallylbicyclo ρ·2.1]hept-5-ene-2,3-dicarboxy quinone imine) phenoxy}phenyl]propane, bis{4_(allylbicyclo[2.2.1]g _5_稀_23_ Dicarboxy quinone imine) phenyl} decane, bis {4-(allylmethyl bicyclo [22 q hept-5 · dilute-2,3-dicarboxy quinone imine) phenyl }methane, ·. ® double {4·(methylallylbicyclo P.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}decane, double {4-(methyl Allylmethylbicyclic hydrazone 21]^_5-ene 2,3-dicarboxy quinone imine) phenyl}methane, double {4-(dipropyl biscyclo[2.2.1]hept-5-women_2 , 3-dimercaptoindole) phenyl}ether, bis(allylmethylbicyclo[2.2.1]hept-5-lean-2,3-a sulphonyl imine)phenyl} mystery, double _j4_(曱基归propyl double bad [2.2.1]g _5-埽_2,3-dicarboxy quinone imine) phenyl} 趟, double {4_(dilyl bisbicyclo[2.2.1]g -5·ene-2,3_di-supplemental imine)phenyl ice, double {heart (allyl methyl double ring called士 办 办 酿 酿 酿 酿 酿 酿 { 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 difficult. The more preferred dipyridinium compound substituted by a dilute group, Ν'_ethylidene-bis(allylbicycloindole.2.1)hept-5-ene·2,3_dicarboxyindole Imine), hydrazine, hydrazine, · ethethyl-bis(allylhydrylbicyclo[2.2.1]hept-5-phetamine), N, NL-ethylidene-bis (methyl propyl) Bicyclic P.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N,_trimethylene-bis(slightly propyl 85 l.Joc 201030060 bisbicyclo[2.2.1]hept-5 - dilute-2,3-disyl iodide), n, n, hexamethylene-bis (dilyl propyl bicyclo [2·2.1] g _5_ dilute _2,3-didecyl fluorene Amine, N,N,_hexamethylene-bis(trimylmethylbicyclo[2.2.1]hept-5_埽_2,3-dicarboxyindenine), N,N,-Twelve Methylene bis (dipropyl bicyclo [2 2 ^heptyl] carboxy quinone imine), N, N, - dodecamethylene bis (allyl methyl bicyclo [2.2.1] g -5-ene-2,3-dicarboxy quinone imine), N,N,-cyclohexene_bis(allylbicyclo[2.2.1]hept-5-ene-2,3-indole carboxy fluorene Amine, N,N,-cyclohexene-bis(distypropylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'_p-phenylene Base-double Propylbicyclo[2.2.1]hept-5-rare-2,3-dicarboxyindolimine), N,Nf-p-phenylene-bis(allylmethylbiscycloalkenene-2,3-dicarboxyl醯imino), N,N,_m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,n,4b1 benzene Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-didecylimine), N,N'-{(1-methyl)-2,4-time Phenyl bis(allylbicyclop.2 l)hept-5-ene-2, '3-dicarboxyanimine), N,N,-p-xylyl-bis(propylpropyl bicyclo[2.2 .1]g_5_Bound-2,3-dicarboxyanimine), N,N'_p-xylylene_bis(propylpropylmethylbicyclo[2.2.1]g-5-dilution_2 , 3_dextrin imine), taken, _m-xylylene: propyl bicyclo [2.2.1] g _5_埽_2,3-di-reindolimine); Dimethyl-bis(trimylmethylbicyclic P.2.1]hept-5-indole-2,3-dioxazolidine 2,2-bis[4-{4-(allyl bicycloglycone 2 , 3_2 =) phenoxy} stupyl] propane, 2,2_bis[4♦(allylhydrylbicyclo.2.1)hept-5-ene_2,3-dicarboxyarlimine) Phenoxyindole phenyl]propane, bis-cyclobutanosyloxy}phenyl]propane 6, double {4_(dilyl propyl double [22^庚士灿-^ 86 201030060idoc II slow-base brewed imine) phenyl} methyl, double {4_(dilylmethylbicyclo[2 2 j] hept-5-rare-2,3- a slow Phenylimine) phenyl}methyl, double {4-(nonyl propyl propyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) {4_(Methylallylmethylbicyclo[2.2.1]hept-5-resin 2,3·di-succinyl iodide)phenyl}-methyl. Further, as a particularly preferred nadicyl imine compound substituted with a hydrazide, a bis(4-(allylbicyclo[2.2.1]g) represented by the structural formula (^^) can be cited as shown below. -5-ene-2,3-dicarboxy quinone imine)phenyl}decane, ν,ν,-m-xylylene-bis(allylbicyclo) represented by the structural formula (Ina-2) 2.2.1] hept-5-ene-2,3-dicarboxyindenine), and ν,Ν'-hexamethylene-bis(allylbicyclo) represented by the structural formula (Ina-3) 2 2 丨]g _5_ ene-2,3-dicarboxy quinone imine). [化66]

(I na-3) 87 20103 0060.ioc Further, for example, in order to stabilize the electrical properties of the liquid crystal display element for a long period of time, the liquid crystal alignment agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond. The compound having a radical polymerizable unsaturated double bond may be one compound or two or more compounds. Further, the naphthylamine compound substituted with an alkenyl group is not included in the compound having a radical polymerizable unsaturated double bond. From the viewpoint of the above, the content of the compound having a radical polymerizable unsaturated double bond is preferably 0.01 to 1.00, more preferably 0.01 to 0.70 by weight based on the weight ratio of the polyaminic acid or its derivative. Further preferably, ❹ is from 0.01 to 0.50. Further, in terms of reducing the ion density of the liquid crystal display element, suppressing an increase in ion density with time, and further suppressing the afterimage, a compound having a radical polymerizable unsaturated double bond is substituted with an alkenyl group. The ratio of the diclosan compound is preferably from 1 to 10, more preferably from 0.5 to 5, by weight. Examples of the compound having a radically polymerizable unsaturated double bond include (meth)acrylic acid (meth)acrylic acid ester (meth)acrylic acid amide, (meth)acrylic acid amide, and the like. (Meth)acrylic acid derivative © and bismaleimide. The compound having a radical polymerizable unsaturated double bond is more preferably a (mercapto)acrylic acid derivative having two or more radically polymerizable unsaturated double bonds. Specific examples of the (meth) acetoacetate include, for example, cyclohexyl (meth)acrylate, 2-mercaptocyclohexyl (meth) acrylate, and dicyclopentanyl (mercapto) acrylate. Dicyclopentyloxyethyl (meth)acrylate, (meth)acrylic acid 88 201030060^ Isobornyl ester, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyl (meth) acrylate Ethyl ester and 2-hydroxypropyl (meth)acrylate. Specific examples of the difunctional (fluorenyl) acrylate include, for example, ethylene diacrylate, East Asian synthetic products Aronix M-210, Aronix M-240, and Aronix M-6200, Nippon Chemical Co., Ltd. Products KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, products of Osaka Organic Chemical Industry Co., Ltd. V260, V312 and V335HP, and products of Kyoritsu Chemical Co., Ltd. Light ® Acrylate BA- 4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA. Specific examples of the trifunctional or trifunctional or higher polyfunctional (meth) acrylate include, for example, 4,4'-methylenebis(N,N-dihydroxyethylene phenyl aniline), Aronix M -400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 φ and VGPT of Osaka Organic Chemical Industry Co., Ltd. Specific examples of the (fluorenyl) acrylamide derivative include, for example, N-isopropyl acrylamide, N-isopropyl decyl acrylamide, and N-n-propyl propyl. Glucosamine, N-n-propyl methacrylamide, N-cyclopropyl acrylamide, N-cyclopropyl methacrylamide, N-ethoxyethyl acrylamide, N-ethoxy Ethyl ethyl acrylamide, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl decyl acrylamide, N-ethyl acrylamide, N-ethyl-N-methyl propylene Indoleamine, N,N-diethyl acrylamide, N-89 201030060u〇c fluorenyl _N• n-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N_ propylene Base absorbing, N-propyl thiopyrrolidone, N, N,- fluorenyl propylamine, n, n'-ethylidene bis decylamine, N, N, _: hydroxyethylidene double Acrylamide, N-(4-hydroxyphenyl)methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N_(isobutoxymethyl)methacrylate Amine, Ν_[2-(Ν,Ν·dimethylamino)ethyl]methacrylamide, wind dimethyl methacrylamide, Ν-[3-(Dimethylamino)propyl]decyl acrylamide, Ν_(decyloxymethyl)methacrylamide, Ν-(hydroxymethyl)_2-mercaptopropenylamine, hydrazine- Benzyl-2-methylpropenylamine and hydrazine, hydrazine, -methylene bis methacrylamide. Among the (mercapto)acrylic acid derivatives, particularly preferred are hydrazine, hydrazine, -merylene bis acrylamide, hydrazine, Ν'-dihydroxyethenyl-bispropenylamine, ethylene diacrylate. And 4,4'-methylenebis(indole, fluorene-dihydroxyethylene phenyl aniline). Examples of the bismaleimide include BMI-70 and BMI-80 manufactured by INDUSTRY CHEMICAL INDUSTRY, and BMI-1000, BMI-3000, BMI-4000, and BMI manufactured by Daiwa Kasei Kogyo Co., Ltd. -5000 and BMI-7000. Further, the liquid crystal alignment agent of the present invention may further contain an oxazine compound from the viewpoint of long-term stability of electrical properties in the liquid crystal display element. The agonizing compound may be a compound. It may also be a compound of two or more kinds. From the viewpoint of the above, the content of the oxazine compound is preferably 0.1% by weight to 50% by weight, more preferably 1%, based on the polyamic acid or a derivative thereof. %~40 wt%, step into 201030060udoc is preferably 1 wt% to 20 wt%. The oxazine compound is preferably soluble in a solvent which dissolves polylysine or a derivative thereof and has a ring-opening polymerizable oxazine compound. Further, the number of the oxazine structure in the oxazine compound is not particularly limited. ...', the structure of the oxazine is known to have various structures. In the present invention, the structure of the oxazine is not particularly limited, and the oxazine structure in the oxazine compound may include a benzoxazine or a naphthoxazine having a condensed polycyclic aromatic group. The structure of the aromatic-based oxazine. 'As the oxazine compound', for example, a compound represented by the following formula (a) to the formula (ί) can be mentioned. Further, in the following formula, a bond shown toward the center of the ring ^ represents a bond which is bonded to a constituent ring and which may bond a substituent - [Chem. 67]

201030060# In the above formula (a) to formula (c), R1 and R2 represent a carbon number of 16 to, for example, an organic group. Further, in the above formula (4) to the formula (0, R3S R represents a nitrogen group or a hydrocarbon group having 1 to 6 carbon atoms. Further, in the above formula (c), formula (d) and formula (f) , X represents a single bond, -〇-, each, -8, -8〇2-, 七--, 七--, -NHCO-, _C(CH3)2-, -C(CF3)2-, -(CH2)m, _〇_(CH2)m〇-, -S-(CH2)mS-. Here, m is an integer of 1 to 6. Further, the above formula (e) and formula (f) Wherein 'Y independently represents a single bond, -〇-, -S-, -CO-, -C(CH3)2-, -C(CF3)2- or an alkenyl group having 1 to 3 carbon atoms. The bond in Y is independently bonded to the hydrogen on the benzene ring and the naphthalene ring, and may be substituted by _CH3, _〇H, -COOH, -S03H, -Ρ03Η2. In addition, the oxazine compound includes a side chain having a wickiness. An oligomer or a polymer having a azine structure (a ymer) or an oligomer or a polymer having an oxazine structure in the primary bond. The oxazine compound represented by the formula (4) is exemplified by the following oxazine compound. 68]

(a«1)

(a-2)

More preferably, the carbon number is 1 to 2, and in the formula, R1 is preferably an alkyl group having 1 to 30 carbon atoms. 92 201030060 „.doc As the agonizing compound represented by the formula (b), for example, the following oxazine compounds can be exemplified.

Φ-9) (b-10) 93 201030060 icc In the formula, R1 is preferably an alkyl group having 1 to 30 carbon atoms, more preferably a carbon group having 1 to 20 carbon atoms. The oxazine compound represented by the formula (c) includes a agonizing compound represented by the following formula (c-I). [化70]

(c-I)

In the above formula (cI), R1 and R2 represent an organic group having 1 to 30 carbon atoms, R3 to R6 represent an argon or a hydrocarbon group having 1 to 6 carbon atoms, and X represents a single bond, -CH2-, -C(CH3) 2-, -CO-, -Ο-, -S02- or -C(CF3)2-. As the agonizing compound represented by the above formula (c-I), for example, the following oxime compound can be mentioned.

94 201030060udoc [化71] c

95 201030060doc 72]

(c-15)

In the formula, R1 is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms. As the oxime compound represented by the formula (d), for example, an oxazine compound of 96 ii.doc 201030060 can be cited.

The oxazine compound represented by the formula (e) is exemplified by the following acetonide compound. 97 20103 0060. Joc [化74]

The oxazine compound represented by the formula (f) may, for example, be an oxindole compound. 98 201030060* [化 75]

99 201030060ldoc [Chem. 76]

(M1)

Among these oxazine compounds, '(3), (c-5), (C-7), (9), and V) are the formula (c), The oxazide compound can be produced by the same method as that described in the Japanese Patent Laid-Open Publication No. Hei. No. Hei.

For example, the oxazine compound represented by the formula (a) can be obtained by reacting a phenol compound, a primary amine, and an aldehyde (refer to International Publication No. 2004/009708). ~

Further, the oleophobic compound represented by the formula (b) can be obtained by adding a primary amine to the formaldehyde, and then adding the naphthol (naPhtho1) system after the reaction. The hydroxy compound is reacted (refer to International Publication No. 2004/009708, manual V. Further, the oxazine compound represented by the formula (c) can be obtained by the following formula 100 201030060*, that is, in an organic solvent, 1 mol a phenolic compound, an aldehyde of at least 2 moles or more with respect to one of its phenolic hydroxyl groups, and 1 mole of primary amine in an aliphatic secondary amines, auphatic tertiary amines The reaction is carried out in the presence of a nitrogen-containing heterocyclic compound (refer to the International Publication No. 2004/009708 and the Japanese Patent Laid-Open No. Hei 11-12258). Further, 'is represented by the general formula (d) to the general formula (f) The oxime compound can be obtained by using a diamine having a plurality of benzene rings and an organic group bonded to the benzene rings, such as 4,4,-diaminodiphenylmethane or the like, in n-butanol. Aldehydes such as formalin and Phenol is subjected to a dehydration condensation reaction at a temperature of 901 or 90 ° C or higher (refer to Japanese Laid-Open Patent Publication No. 2004-352670). Further, 'for example, from the viewpoint of long-term stability of electrical properties in a liquid crystal display element' The liquid crystal alignment agent may further contain a oxethin compound, which is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. In view of the above, the content of the smectite compound is preferably 0.1 Wt 〇 〇 50 W t%, more preferably 1 wt% 〜 40 Wt% with respect to the polyaminic acid or its derivative. Further, it is preferably from 1 wt% to 20 wt%. Or, from the viewpoint of the above, the content of the oxazoline compound is preferably when the oxazoline structure in the oxazoline compound is converted to an oxazoline. The oxaporphyrin compound may have only one oxazoline structure in one compound or may be in one compound, relative to the poly-proline or its derivative. 丨.丨^^%~4〇wt% 0 Have two or more types 1 01 201030060 The oxazoline structure of uoc. In addition, the oxazoline compound may have one or more of the oxazoline structures in one compound, but preferably has two or more oxazoline structures. Further, the oxazoline compound may be a polymer having an oxazoline ring structure in a side chain, or may be a copolymer. A polymer having an oxazoline structure in a side chain may have an oxazoline structure on a side chain. The homopolymer of the monomer may also be a copolymer of a monomer having an oxazoline structure in a side chain and a monomer having no oxazole structure. There is evil on the side chain. The copolymer of the pendant structure may be a copolymer of two or more kinds of monomers having an oxazoline structure in a side chain, or two or more kinds of oxazoline structures having a oxazoline structure in a side chain. a copolymer of a monomer and a monomer having no oxazoline structure. The oxazoline structure is preferably a structure in which one or both of oxygen and nitrogen in the oxazoline structure are allowed to react with a carbaryl group of the poly-aracine. Examples of the oxazoline compound include 2,2f-bis(2-oxazoline), 1,2,4-tri-(2-oxo). Isozoline-2)-benzene (1,2,4-tris-(2-oxazolinyl-2)-benzene), 4-°fusin-2-ylmethylene-2· phenylene-4H- 4-furan-2-yl methylene-2-phenyl-4H, oxazole-5-one, 1,4-bis(4,5-dihydro-2-oxasinyl)benzene , 4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3,bis(4,5-dihydro-2-oxazolyl)benzene, 2,3-bis(4-isopropenyl) -2-oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2-oxazoline, 2,6-bis(isopropyl-2-oxazole-15 Pyridine, 2,2'-isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2,-isopropylidene bis(4-indolyl-2-oxazoline) 2,2'-methylenebis(4-tert-butyl-2-oxazole 102 201030060 =) private and 2,2-methylenebis(4-phenyl-2-oxo 0 sitting). In addition to these evil salivas, it is also possible to cite, for example, Epocros (trade name, Japanese touch, or (4)-based polymer or oligomer. These two are more preferably 1,3_double (4,5). _Dihydro-2-oxazolyl) benzene. The second example of the observation of the electrical properties of the liquid crystal display elements

The liquid crystal alignment agent of the invention may further contain an epoxidized material. The epoxy compound may be one compound or two or more compounds. In view of the above, the content of the epoxy compound is preferably ag wt &amp; 〜50 Wt 〇 / 〇, more preferably 1 wt% 〜 40 wt%, with respect to the polyamic acid or a derivative thereof. The further step is preferably i wt%. As the epoxy compound, various compounds having one or two or more epoxy rings in the molecule can be cited. Examples of the compound having an epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, and 3,3,3-trifluorodecyl propylene oxide (3, 3, 3-tnfluoro propylene oxide, styrene oxide, hexamethylene propylene oxide, cyclohexene oxide, 3-glycidoxypropyltrimethoxy chopping (3_giyCid〇Xy propyl) 11^11(^丫3 such as 1^), 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, N-glycidyl phthalimide , (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidol, epichlorohydrin, epibromohydrin, N, N- Diglycidyl aniline and 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane. 103 201030060, A i.doc is a compound having two epoxy rings in the knife, for example · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Equine Shrinking sweet (10), glycerol digoxime: = 曱 环 环 ^ 一 一 二 ( ( ( ( ( ( ( ( ( ( ( ( ( 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 [ [ [ [ [ [ [ [ [ [ 4-([2,3-epoxypropane VG3101L", Mitsui & Co., Ltd. (trade name "Techmore has four epoxy lifts in the molecule: U, 5, 6w glycidyl group _24_H chemical, for example, can be listed Baked, windy, tetraglycidyl _44, __ butyl hydrazine and hydrazyl allyl-N-glycidyl) amino two groups ^^ = In addition to the compound, as a molecule called a ring Examples of the compound of the oxygen ring ' can also be used to exemplify a monomer having an epoxy ring with an epoxy group, and examples thereof include: glycidyl (meth) a Crylate, (methylated 4 4 cyclic ester of women's acid and ( Methyl) decyl glycidol vinegar. 'As another monomer copolymerized with a monomer having an epoxy ring, for example, (meth)acrylic acid, (methyl) dicarboxylic acid methyl vinegar (methyi 104 201030060) Meth (meth)acrylate), (mercapto)ethyl acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate Ester, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Styrene, methyl styrene, chloromethyl styrene, (3-ethyl-3-epoxypropenyl) decyl (meth) acrylate, N-cyclohexyl maleimide, and N- Phenyl maleate. Preferable specific examples of the polymer of the monomer having an epoxy ring include polyglycidyl methacrylate and the like. Further, preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenylmaleimide-glycidyl methacrylate copolymer and N-cyclohexyl horse.醯imino-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate/glycidyl methacrylate copolymer, 2-hydroxyl methacrylate Ethyl ester-glycidyl methacrylate copolymer, methacrylic acid (3_ethyl_3_epoxypropenyl) phthalic acid methyl acrylate glycidyl ester copolymer and styrene bromide Glycidyl ester copolymer. Among these examples, N,N,N,,N,_tetraglycidyl-isophthalamide, 1,3-bis(N,N-diglycidylaminodecyl)cyclohexane, N is particularly preferred. , N, N', N'-tetraglycidyl_4,4, diaminodiphenyl decane, trade name "Techmore VG3101L", 3,4-epoxycyclohexyl fluorenyl _3, , 4,-epoxycyclohexanecarboxylic acid vinegar, N-phenylmaleimide-glycidyl methacrylate copolymer and 2-(3,4-epoxycyclohexyl)ethyltrimethoxyl Brothel. More systematically, as the epoxy compound, for example, it can be listed 105

,.d〇C 201030060 举: glycidol mystery, glycidyl ester, glycidyl amine, epoxy-containing acrylic resin, glycidyl amide, glycidyl A giycidyl isocyanurate, a chain aliphatic epoxide, and a cyclic aliphatic epoxide. Further, the 'epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group. Examples of the glycidyl ether include a bisPhen〇l A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a bisphenol type epoxy compound, and a hydrogenation double Phenol_A type epoxy compound, hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol_s type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol type A epoxy compound, brominated double Phenol-F type epoxy compound, phenol novolac (phen 〇 η 请 (4) type epoxy compound, 甲 _ _ _ _ _ _ 面 〇 〇 〇 〇 环氧 环氧 环氧 、 、 _ _ _ _ _ _ _ _ 氧 氧 氧 氧甲甲〇ΪΪ 〇ΪΪ ΐ epoxy compound, Wei A _ varnish type Wei compound, epoxy compound, aromatic polyglycidyl ether compound, diepoxide, alicyclic dimethyl sulphate compound, titan _ compound, Polysulfide (iv) secret e) diglycidyl ether compound and biphenol type epoxy compound. As the glycidol vinegar, for example, a condensable compound and a glycidol-based epoxy compound. The glycidol compound is, for example, the glycidylamine. The amination of polyglycidyl glycerol, for example, can be listed as the homopolymer and copolymer of the monomer containing oxiranyl, 106. As the glycidylamine, for example, a glycidylamine type oxygenated compound can be mentioned. The chain aliphatic epoxy compound may, for example, be a ring-containing compound obtained by oxidizing a carbon-carbon double bond of an alkene compound. ^As the cyclic aliphatic epoxy compound, for example,

An epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a cycloolefin compound. Examples of the double-type A-type epoxy compound include: 828, l〇 (U, 1002, 1〇〇3, 1〇〇4, 1007, 1〇1〇 (all Japanese epoxy resins (Japan Epoxy) Resins), Ep〇t〇ht〇YD128 (made by Toho Chemical Co., Ltd.) 'DER-331, DER-332, DER-324 (all manufactured by Dow Chemical Japan), Epicl〇n840 , Epicl〇n85〇, EPicl〇nl〇5〇 (all manufactured by DIC), Ep〇mic R_14〇, Ep〇mie R-301 and Ep〇micR_3〇4 (both manufactured by Mitsui Chemicals Co., Ltd.) Examples of the bisphenol F-type epoxy compound include: 8〇6, 8〇7, and _4P (all manufactured by Japan Epoxy Resin Co., Ltd.), Ep〇t〇ht〇YDF-170, and Epotohto YDF. -175S, Epotohto YDF-2001 (all manufactured by Tohto Kasei Co., Ltd.), DER-354 (manufactured by D〇w Chemical Japan Co., Ltd.), Epiclon 830 and Epiclon 835 (both manufactured by DIC). Examples of the phenol type epoxy compound include an epoxide of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane as the hydrogenated bisphenol-A. Examples of the epoxy compound include, for example: 107 201030060 Joc

Suntohto ST_3000 (manufactured by Tohto Kasei Co., Ltd.), de-(10) fine HBE-100 (manufactured by Shin-Nihon Chemical Co., Ltd.), and curry 1 EX-252 (manufactured by Nagase Chemtex). Examples of the deuterated double-epelled epoxy compound include hydrogenated 2,2-bis(4-phenylphenyl alkoxylated epoxide. As the brominated bisphenol-A epoxy compound, For example, 5050, 5051 (all manufactured by Japan Epoxy Resin Co., Ltd.), Ep〇t〇ht〇YDB-360, Epotohto YDB-400 (both manufactured by Toho Chemical Co., Ltd.), DER-530, DER - 538 (all manufactured by Dow Chemical Japan Co., Ltd.), and Epiclonl 52 and Epiclon 53 (both manufactured by DIC). Examples of the phenol novolak type epoxy compound include 152 and 154 (both 曰). This epoxy resin (manufactured by Epoxy Resin Co., Ltd.) 'YDpN_638 (made by Toho Chemical Co., Ltd.)' DEN431, DEN438 (all manufactured by Dow Chemical Japan) Epiclon N_77〇 (manufactured by DIC), EPPN-201 and EPPN-202 (all manufactured by Nippon Kayaku Co., Ltd.) As the nonylphenol novolak type epoxy compound, for example, 180S75 (made by Nippon Epoxy Resin), yDCN_70丨, YDCN_7〇2 (both Dongdu) Chemical (share) manufacturing) 'Epiclon N-665, Epiclon N-695 (all manufactured by DIC DIC), EOCN-102 S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (all manufactured by Sakamoto Chemical Co., Ltd.). As the double-check A varnish-type epoxy compound, for example, 157S70 (manufactured by Epoxy Epoxy Resin Co., Ltd.) and Epicl Nn 880 (manufactured by DIC Co., Ltd.) 108 201030060 i&gt;doc As the epoxy compound containing a naphthalene skeleton, for example,

Epiclon HP-4032, Epiclon HP-4700, Epiclon HP-4770 (both manufactured by DIC) and NC-7000 (manufactured by Sakamoto Chemical Co., Ltd.). As the aromatic polyglycidyl ether compound, for example, hydroquinone diglycidyl ether (the following structural formula E101), catechol diglycidyl ether ( The following structural formula E102), resorcinol diglycidyl ether (the following structural formula E103), tris(4-anthracene glycidyloxyphenyl)methane (the following structural formula E105) , 1031S, 1032H60 (all manufactured by Enamel Epoxy Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Japan), Denacol EX-20l (manufactured by Nagase Chemex), DPPN-503, DPPN- 502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (manufactured by Mitsui Chemicals Co., Ltd.), a compound represented by the following structural formula E106, and a compound represented by the following structural formula E107. ❹ 109 201030060, ___ A.. .aoc [化77]

As the dicyclopentadiene phenol type epoxy compound, for example, TACTIX-556 (manufactured by D〇w Chemical japan) and HP-7200 (manufactured by DIC) can be cited. Examples of the alicyclic diglycidyl mystery compound are, for example, A" cyclohexane dimethanol diglycidyl ether compound and Rikaresin DME-100 (manufactured by Shin Nippon Chemical and Chemical Co., Ltd.). 11〇 ii.doc 201030060

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (the following structural formula E108), diethylene glycol monoglycidyl ether (the following structural formula E109), and polyethylene glycol. Diglycidyl butane propylene glycol diglycidyl ether (structure E110 below), tripropylene glycol diglycidyl ether (structure E111 below) 'polypropylene glycol diglycidyl shunt, neopentyl glycol diglycidyl ether (described below Structural formula E112), 1,4-butanediol diglycidyl ether (Strong formula E113 below), 1,6-hexanediol diglycidyl, the following structural formula E114), dibromo neopentyl glycol diglycidyl Ether (Strong Formula E115 below) &gt; Denacol EX-810 ' Denacol EX-851 ^ Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931 ' Denacol EX-211 ' Denacol EX-212 ' Denacol EX-313 (both manufactured by Nagase Chemtex), DD-503 (made by ADEKA), Rikaresin W-100 (made by New Japan Physical and Chemical Co., Ltd.) 1,3,5,6-four shrinkage Glyceryl-2,4-hexanediol (Structure of Formula E116 below) 'GyryCerinp〇iygiyCidyi ether, sorbitol Sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether 'pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321 And Denacol EX-411 (both manufactured by Nagase Chemtex). 111 ”.doc 201030060 [化78]

(E110) (E111)

(E113) 10 (E112)

(E114) /Br

(E115)

(E116) As the polysulfide type diglycidyl ether compound, both FLDP-5〇 and FLDP are added as the bisphenol type epoxy compound, and γχ·4^ All of them are Japanese epoxy '(^ NC-3000P and NC_3000S (all manufactured by Nippon Kayaku Co., Ltd.). 崄)' As the diglycidyl ester compound, for example, dimethyl diglycidyl dicarboxylate can be cited. 117), o-p-dicarboxylic acid-pair stupid 112 201030060, glyceride (structure E118 below), bis(2- mercapto oxiranyl) phthalate (the following structure) The compound represented by the following structural formula E121, the compound represented by the following structural formula E122, and the compound represented by the following structural formula E123.

Ο 2 (E121)

(E123) Examples of the glycidyl ester epoxy compound include: 871 872 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epiei〇n 2〇〇, and Epicli〇n 働 (all manufactured by DIC) ), Denac〇1 Εχ_711 and Denac〇1 113 20103000.doc As the polyglycidylamine compound, for example, N,N-diglycidylaniline (the following structural formula E124), diglycidyl-ortho Toluidine (structure formula 下述125 below), hydrazine, hydrazine-diglycidyl-m-toluidine (structure Ε126 below), hydrazine, hydrazine-diglycidyl-2,4,6-tribromoaniline (below)结构127), 3_(Ν,Ν-diglycidyl)aminopropyltrimethoxydecane (the following structural formula: £128), ^[,:^,0-triglycidyl-p-aminophenol ( The following structural formula Ε129), hydrazine, hydrazine, 0-triglycidyl-m-aminophenol (the following structural formula Ε130), hydrazine, hydrazine, Ν', Ν'-tetraglycidyl-m-xylylenediamine oxime (TETRAD-X (Mitsubishi Gas Chemicals Co., Ltd.), the following structural formula Ε132), 1,3-bis(indene, Ν-diglycidylaminomethyl) cyclohexyl (TEtraD-C (Mitsubishi Gas Chemistry ( Share)), the following structural formula Ε1 33), 1,4-bis(indole, fluorene-diglycidylaminomethyl)cyclohexane (the following structural formula Ε134), 1,3-bis(indole, fluorene-diglycidylamino) cyclohexane Burning (the following structural formula Ε135), 1,4_double (1&lt;[,]^- diglycidylamino) cyclohexene (the following structural formula Ε136), 1,3-double (Ν,Ν-二Glycidylamino)benzene (the following structural formula Ε137), 1,4-bis(indole, fluorene-diglycidylamino)benzene (the following structural formula Ε138), 2,6-double (Ν,Ν_二Glycidylaminomethyl)bicycloindole.2.1]heptane (structure Ε139 below), hydrazine, hydrazine, Νη ❹ tetraglycidyl-4,4'-diaminodicyclohexyldecane (structure Ε140), 2,2-monomethyl-(&gt;^,1&lt;[',]^,-tetraglycidyl)_4,4'-diaminodiphenyl (the following structural formula Ε141), Ν ,Ν,Ν,,Ν·-tetraglycidyl_4,4,_ Diaminostilbene diphenyl ether (the following structural formula EM2), U,5_three (4_(1^^" glycidyl) Aminophenoxy)benzene (the following structural formula E143), 2,4,4,-bis(N,N-diglycidylamino)diphenyl- (the following structural formula ei44), three 114-i. Doc 201030060 (4-(N,N-diglycidyl) Aminophenyl)methane (structure E145 below), 3,4,3',4'-tetrakis(N,N-diglycidylamino)biphenyl (structured formula 146 below), 3,4 3', 4'-tetrakis (aerobic diglycidylamino) diphenyl ether (the following structural formula E147), a compound represented by the following structural formula E148, and a compound represented by the following structural formula E149.

115 201030060 [化80]

(E124)

(E126)

(E136)

116 201030060 it.doc [化81]

117 201030060 [化82]

(Ε148)

As the monomer having an oxiranyl group, polymethyl methacrylate glycidol vinegar. Glycidyl acrylate 妓 札 举 本 本 基 马 马 醯 醯 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 、 、 、 、 、 、 、 环 环 环 环 环 环 环 环 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚Benzyl ester-mercaptoacrylic acid glycosyl 118

201030060 H —..j-ii.aoc oil ester copolymer, butyl methacrylate-glycidyl methacrylate copolymer, methyl propyl acetoacetate 2-methyl acetoacetate Copolymer, (3-ethyl-3-epoxypropenyl)methyl methacrylate-methylpropanol &amp; glycidyl ester copolymer and styrene-glycidyl methacrylate copolymer. Examples of the monomer having an ethylene oxide group include glycidyl (meth)acrylate, 3,4-epoxycyclohexanacetate (meth)acrylate, and methyl glycidol (meth)acrylate. ester. Examples of the monomer other than the monomer having an oxiranyl group in the copolymer of the oxiranyl group-containing monomer include (meth)acrylic acid and (mercapto)acrylic acid. Ethyl ester, (mercapto) ethyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (methyl) Cyclohexyl acrylate, benzyl (meth) methacrylate, 2-hydroxyethyl (meth) acrylate, 2-methyl propyl acrylate, styrene, methyl styrene, chlorodecyl styrene , (mercapto) propionate (3-ethyl-3_glycidyl) methyl ester, fluorene-cyclohexylmaleimide φ and fluorenyl-phenylmaleimide.

As the glycidyl isocyanuric acid vinegar, for example, 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1Η,3Η,5Η)-three Ketone (l,3,5-triglycidyl-l,3,5-triazine-2,4,6-(lH,3H,5H)-trione) (T structural formula E150), 1,3-glycidyl -5-Dilyl-1,3,5-trisole_2,4,6_(1Ή,3ΡΙ,5ίί)-trione (structure E151 below) and glycidyl isocyanurate-type epoxy resin . 119 201030060 / ^/Ai.doc [Chem. 83]

(E150)

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and Epolead PB3600 (manufactured by Daicel Chemical Industry Co., Ltd.). As the cyclic aliphatic epoxy compound, for example, 2-mercapto-3,4-epoxycyclohexylfluorenyl 2,-fluorenyl-3,4'-epoxycyclohexylcarboxylic acid can be exemplified. Ester (Strong Formula E153 below), 2,3-epoxycyclopentane-2,3,-epoxycyclopentane ether (Structure of Formula E154 below), ε-Caprolactone Modification 3, 'Ring Oxycyclohexylmethyl-3Ί-epoxycyclohexanecarboxylate, diepoxide lemon dilute (Celloxide 3000 (DaiCd Chemical Industry Co., Ltd.)' 3,4_epoxycyclohexenylindolyl-3,' 4'·Epoxycyclohexenecarboxylate (Celloxide 2〇2lp (manufactured by Daicel Chemical Industry Co., Ltd.) 'The following structural formula E155) 'The compound represented by the following structural formula E156, CY-175, CY-177, CY-179 (both manufactured by CffiA-GEIGY), EHPD-3150 (manufactured by Daicel Chemical Industry Co., Ltd.), and cyclic aliphatic epoxy resin. 120 201030060 —^ &gt; / j^ii.doc [Chem. 84 ]

(E153) (E154)

(E155)

(E156)

Further, for example, the liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include a polymer compound other than polyglycine and a derivative thereof, and an age-related compound, and can be selected and used according to each purpose. For example, as the polymer compound, a surface molecule compound which is soluble in an organic solvent can be mentioned. From the viewpoint of controlling the electrical properties or the alignment properties of the crystal alignment film, it is preferred to add such a polymer compound to the liquid crystal alignment agent of the present invention. Examples of the polymer compound include polyamine, p〇lyurethane, polyurea, poly S, polyepoxide, and polyepoxide (p〇iyep〇xide). Polyester polyol (polyester P〇iyol), anthrone modified polyurethane and anthrone modified polyester. Further, as the low molecular compound, for example, 1) when it is desired to increase the coating thickness, a surfactant suitable for the purpose may be mentioned, and 2) when it is necessary to mention &amp; antistatic property, antistatic may be mentioned, 3) #敏When the adhesion to the substrate or the rubbing resistance is improved, a coupling agent for a chipping agent (along the agent) or a titanium system may be mentioned, and 4) when the hydrazine imidization is carried out at a low temperature, 醯Imidization catalyst. 121 201030060, —- r”. doc As the zebra calcining agent, for example, vinyl trimethoxys Uane, (10)-based triethoxy oxalate, N-(2-gas) may be mentioned. Ethyl ethyl)-3-aminopropyl fluorenyl dioxime oxime, N ♦ acetoyl ethyl) _ 3 _ amino propyl decyl trimethoxy oxime, p-aminophenyl trimethoxy sulphur, P-aminophenyldiethoxylate, m-amino-p-trimethoxy-zepa-sinter, m-aminophenyldiethoxylate, 3-aminopropyltrimethoxy oxime, 3-aminopropyltriethyl Oxygen-burning 'glycidoxypropyltrimethoxy decane, 3-glycidoxypropylmethyldimethoxydecane, 2_(3,4-epoxycyclohexyl)ethyltrimethoxywei, 3-Chloropropylf-yldimethoxy-#10 alkane, 3-apropylpropyltrimethoxydecane, 3-mercaptopropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane , (1,3-didecylbutylene)-3-(triethoxydecyl)-1-propylamine and n,n,-bis[3-(trimethoxydecyl)propyl] Ethylenediamine. Examples of the ruthenium amide catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; N,N-dimercaptoaniline, N,N-diethyl An aromatic amine such as a aniline, a phenylamine substituted with a methyl group, or an aniline substituted with a hydroxy group; a pyridine substituted with a thiol group, a 11-bit bite substituted by a thiol group, a quinoline, a methyl group Substituted wow® porphyrin, quinolin substituted by hydroxy group, isoquinoline, isoindolin substituted by methyl group, isoquinoline substituted by hydroxy group, imidazole, azole substituted by methyl group, substituted by hydroxy group a cyclic amine such as imidazole. The ruthenium amide catalyst is preferably selected from the group consisting of N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridyl. One or two or more of biting and isoquinoline. 122 201030060

Between 0 wt% and 1 minus the total weight of the amine or its derivative is usually '~30 wt%, preferably 0.1 wt% to ίο μ%. In the case of the present invention, for example, the present invention is in the form of an acrylic polymer. Acrylic acid-based polymer, other polymer components such as polyamidoximine, which is a reaction product of tonic acid dianhydride, two ships, or a reaction product thereof with diamine. Further, for example, the liquid crystal alignment agent I of the present invention further contains a solvent from the viewpoint of adjusting the coatability of the liquid crystal alignment agent or the concentration of the polyamic acid/the bamboo organism. The solvent is not particularly limited as long as it has a solvent having the ability to dissolve the polymer component. The solvent broadly includes a solvent which is usually used in the production step or use of a polymer component such as polyglycolic acid or soluble polyimine, and can be appropriately selected depending on the purpose of use. The solvent may be a solvent or a mixed solvent of two or more solvents. The solvent may be a good solvent of the polyaminic acid or a derivative thereof or another solvent for the purpose of improving coatability. Non-quality 123 201030060, ___..^^ι.αοο sub-polar organic solvent for the poly-proline or its derivative is Ν-methyl-2-pyrrolidone (N-methyl -2-pyrrolidone), dimethyl imidazolidinone, N-methyl caprolactam, N-methyl propionamide, anthraquinone, Ν-Dimethyl ethoxylated amine, dimethyl sulfoxide, N,N-dimethylformamide, hydrazine, hydrazine-diethyl decylamine, diethyl Internal vinegar such as acetylamine and γ-butyrolactone. Examples of the other solvent for the purpose of improving coatability and the like include alkyl lactate, 3-methyl-3-methoxybutanol, and tetralin ( Tetraethylene glycol monoalkyl ether such as tetralin), isophorone, ethylene glycol monobutylether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol Propylene glycol monoalkyl ether such as monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoterpene ether, propylene glycol monobutyl ether, malonic acid such as diethyl malonate A dipropylene glycol monoalkyl group such as an alkyl ester or a dipropylene glycol monoterpene ether, or a compound thereof such as an acetic acid g.

Among these compounds, the solvent is particularly preferably N-mercapto-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylenediethanol monoethyl ether, propylene glycol monobutyl ether. , propylene glycol monoterpene and dipropylene glycol single mystery. In the present invention, the concentration of the molecular component containing the polyamic acid or the derivative thereof in the liquid crystal alignment agent is not particularly limited, and is preferably wt} wt% to 40% by weight. When the liquid crystal alignment agent is applied onto a substrate, it is necessary to adjust the film thickness, and it is necessary to use a solvent in advance to separate the high scores contained in the lion. The concentration of the surface molecular component is preferably 彳, which is equal to 4 〇 wt%, from the viewpoint of adjusting the degree of drilling of the solvent in the liquid crystal alignment agent. Further, the concentration of the polymer component in the liquid crystal alignment agent may be adjusted depending on the method of applying the liquid crystal alignment agent. When the coating method of the liquid crystal alignment agent is a spinning method or a printing method, in order to maintain the film thickness favorably, the concentration of the neutron component is usually 1 G wt% or less. For other coating methods, such as dipping (dipping or inkjet_(10) method, there is a possibility to reduce the concentration. On the other hand, if the polymer component has a degree of greater than or equal to 0.1 wt%, Then, the film thickness of the obtained liquid crystal alignment film tends to be an optimum thickness. Therefore, in a usual spin coating method, a printing method, or the like, the concentration of the ruthenium molecular component is greater than or equal to wt%, preferably 0.5 wt%. 1% by weight. However, depending on the method of applying the liquid crystal alignment agent, it may be used at a lower concentration. Further, when the liquid crystal alignment agent of the present invention is used for producing a liquid crystal alignment film, the liquid crystal alignment agent of the present invention The viscosity can be determined according to the mechanism or method of forming the film of the liquid crystal alignment agent. For example, when a film of a liquid crystal alignment agent is formed using a printing machine, the liquid aa alignment of the present invention is obtained from the viewpoint of obtaining a sufficient film thickness. The degree of dryness of the agent is preferably 5 mPa·s or more, and the viscosity of the liquid crystal alignment agent of the present invention is preferably 100 mPa·s or less, more preferably l〇mpa.s. 8〇mpa.s. When the liquid crystal alignment agent is applied by spin coating to form a film of a liquid crystal alignment agent, the degree of penetration of the liquid crystal alignment agent of the present invention is preferably 5 mPa·s to 200 mPa·s. More preferably, it is 1 〇 mpa.s 〜1 〇〇 125 201030060, mP a. s. The viscosity of the liquid crystal alignment agent can be reduced by dilution of the solvent or aging with stirring. The liquid crystal alignment agent of the present invention may contain a kind of The form of the polyaminic acid or a derivative thereof may be in the form of a polymer blend of two or more kinds of polyacrylic acid or a derivative thereof. The liquid crystal of the form of the polymer blend The alignment agent may, for example, be a liquid crystal alignment agent containing polylysine or a derivative thereof A &amp; B, polyamine or its derivative A comprising a diamine in the formula (1) and One or more of the diamines having a side chain structure represented by the formula (11), and one or both of the polycarboxylic acid or the tetracarboxylic dianhydrides of the derivatives A and B thereof contain the above formula (TC-1) - one or more kinds of tetracarboxylic dianhydride represented by the formula (TC-14) and others One or more kinds of carboxylic acid dianhydride. Poly-proline or a derivative A thereof is preferably a polyamine or a derivative thereof containing the diamine having a side chain structure. Polylysine or a derivative thereof Preferably, it is a polyaminic acid or a derivative thereof containing a diamine other than a diamine having a side chain structure. The tetradecanoic acid dianhydride represented by the above formula (TC-1) to (TC_14) The other tetracarboxylic dianhydride may be contained in at least one polyamic acid or a derivative thereof mixed in the polymer blend, and may be contained in both the polyaminic acid or its derivatives A and B. It may also be included in all polyamines or their derivatives mixed in the polymer blend. The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method of producing a liquid crystal alignment film from a liquid crystal alignment agent, for example, a step of forming a coating film of the liquid crystal alignment film of the present invention by forming the liquid crystal alignment agent 126 201030060 of the present invention, and The coating film is obtained by a step of heating and calcining. For the liquid crystal alignment film of the present invention, the film obtained in the calcining step may be subjected to a rubbing treatment as needed. The coating film can be formed by applying the liquid crystal alignment agent of the present invention onto a substrate of a liquid crystal display element, as in the production of a usual liquid crystal alignment film. The substrate may be a glass substrate such as an electrode such as an Indigo Tin Oxide ITO electrode or a color filter (c〇i〇r mter). ® As a method of applying a liquid crystal alignment agent onto a substrate, a spin coating method, a printing method, a dipping method, a falling method (droping method), an ink jet method, and the like are generally known. These methods are equally applicable in the present invention. The calcination of the coating film can be carried out under the conditions required for the dehydration and ring closure reaction of the polyaminic acid or its derivative. The calcination of the coating film is generally known as a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like. These methods are equally applicable in the present invention. It is usually preferably 15 Torr. 〇 ~ As one ❷ Between the left and right temperatures for 1 minute ~ 3 hours. The rubbing treatment can be performed in the same manner as the rubbing treatment generally used for the alignment treatment of the liquid crystal, only

In the range in which the effects of the present invention can be obtained, the liquid crystal alignment film can be carried out as long as it is sufficiently delayed. Especially excellent U mm ~ (U mm' platform moving speed is 5GGrPm~2, 〇G〇rpm. 'In addition to the rubbing method, it is usually 201030060, the other wonderful plant (four) method. Zen, other steps r two =:== : holding == the step of drying the coating film, or == rubbing treatment reading (10) the step of cleaning, etc. burning step smoke 'the drying step is usually 〇 ==: the method of heat treatment, Adding on the hot plate: a method of treatment, etc. These methods are also applicable to the money step. The drying step is preferably carried out at a temperature within a range in which the dissolved ship is sufficiently evaporated, preferably with the crucible. The burning step _ temperature phase _ is applied to the lower temperature h. As a cleaning method for cleaning the liquid crystal alignment film before and after the treatment using the cleaning (4) g&, _: ^(bmshing), jet atomization (10) ❹ = ray), Steam cleaning or ultrasonic cleaning. These methods can be used individually or in combination. As the cleaning liquid, pure water, various alcohols such as mehtyl alcohol, ethanol, and isopropanol, aromatic hydrocarbons such as benzene, toluene, and xylene, and dichlorobenzene can be used. A ketone such as a halogen solvent such as methylene chloride, such as acetoxime or methyl ethyl ketone, is not limited to these. Of course, these cleaning solutions can use a sufficiently cleaned impurity with less impurities. This cleaning method can also be applied to the cleaning step of forming the liquid crystal alignment film of the present invention. The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably from 1 nm to 300 nm, and more preferably from 30 nm to 150 nm. The liquid crystal distribution of the present invention can be measured by using a well-known film thickness measuring device such as a surface turret or an ellipsometer. The liquid crystal display device of the present invention has: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode applying a voltage to the liquid crystal layer; and a liquid crystal alignment film 'aligning the liquid crystal molecules In the intended direction. The liquid crystal alignment film is a liquid crystal alignment film of the present invention. The substrate may use the glass substrate described above for the liquid crystal alignment film of the present invention, and the electrode may be formed on the glass substrate as described above for the liquid crystal alignment film of the present invention. The liquid crystal layer is formed of a liquid crystal composition sealed in a gap between a pair of opposing substrates, wherein the pair of opposing substrates is formed by forming a liquid crystal alignment film on one of the pair of substrates. The faces are facing toward the other substrate. The liquid crystal composition is not particularly limited, and each crystal group having a positive dielectric constant of positive or negative dielectric constant can be used. Preferred liquid crystal compositions having a positive dielectric anisotropy are exemplified by liquid crystal compositions disclosed in Japanese Patent No. 3,228, Japanese Patent No. 263 M35, and Japanese Patent Laid-Open No. 5-5 Japanese Patent Publication No. 1735, Japanese Patent Publication No. 8-157826, Japanese Patent Laid-Open No. Hei 9-241644, Japanese Patent Laid-Open No. Hei 9-241644 (Japanese Patent Publication No. L, Lit Kaiping No. 9-302346 (ΕΡ806466Α1 says 曰利特开平8) ]&quot;168 bulletin (ΕΡ722998Α1 says 129 doc 201030060 (EP885271A1 t), g ^ ^ ^ (EP844229A1 蚩, α ^ 特千千-10-20416, Japanese patent special ω2= Li Tekaiping 1〇· _6 No. 2000-087040, Japanese-Japanese Gazette, 曰本专利Special Dielectric Constants are different from each other. = 〇〇1养2, etc. As disclosed in the following patents: Nissei, liquid crystal composition Japanese Laid-Open Patent Publication No. 57-114532, Japanese Patent Unexamined Patent Publication No. 2-4725, 'Sakamoto Gazette, Japanese Taichi Co., Ltd., Japanese Patent Special Open Side 3 No. 10-168076, Kaiping 8 _ _9 bulletin, This patent is open to the public. ^^^^23tr^t, 〇-168453 a^- 〇10-236990, the A newspaper, the Japanese patent special patent (4) Ping 1G 23=1 Kaiping 1G·236&quot; Japanese Patent No. 10-236994, Japanese Patent, Japanese Patent Laid-Open Patent No. Hei-Ping No. 1-23, No. 10-237000, No. 10-237024, too ~ Bulletin, Japanese Patent Unexamined Patent (four) Ping 1 (&gt;m卩号公告, Japanese No. 10-237076; Japanese Patent Special Kaiping (Em7261A1) ϋ ϋ ί ίο-(10) Peach Bulletin, Japanese Taichi, Japanese Patent Special Open No. 10-287874, Eighth 2nd Japanese = 875, Japanese paste special = Patent No. u__ 丨1. 581, 曰 on A, Special Open 2000-256307, 130 201030060,

Japanese Laid-Open Patent Publication No. 2001-019965, Japanese Laid-Open Patent Publication No. Hei. No. Hei. Even if one or more optically active compounds are added to the liquid crystal composition having positive or negative dielectric anisotropy for use, there is no influence at all. The liquid crystal display device of the present invention is obtained by forming a liquid crystal alignment film of the present invention on at least one of a pair of substrates, and bringing the liquid crystal alignment film inward so that the obtained pair of substrates pass through the spacer ( Spacer) ® is a liquid crystal layer formed by sealing a liquid crystal composition in a gap formed between the substrates. In the production of the liquid crystal display device of the present invention, a step of attaching a polarizing film or the like to the substrate may be further included as needed. The liquid crystal display element of the present invention can form various liquid crystal display elements for electric field mode. The liquid crystal display element for the electric field method includes a liquid crystal display element for applying a voltage to the liquid crystal layer in a direction in which the electrode is in a level with respect to a surface of the substrate, or the electrode is opposite to The surface of the substrate is a vertical electric field type liquid crystal display element that applies electricity to the liquid crystal φ layer in a vertical direction. The liquid crystal display element for a lateral electric field method does not have a large pretilt angle. Therefore, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is suitable for a liquid crystal display element for a transverse electric field method, wherein the liquid crystal alignment agent of the present invention Polylactoic acid or a derivative thereof having no side chain structure, such as polylysine or a derivative thereof obtained from a diamine having no diamine having a side chain structure. The vertical electric field mode liquid crystal display element needs to exhibit a large pretilt 131 ... doc 201030060: a liquid crystal alignment film formed by a liquid crystal alignment agent formed by a liquid crystal alignment agent, wherein the liquid crystal display element of the present invention =: (4) a bacterium having a side chain structure such as polyfluorene 2 or its emitter obtained from a diamine having a diamine having a side chain structure. As described above, the liquid helium alignment film produced by using the liquid crystal alignment agent of the present invention as a raw material is suitably used in a liquid crystal display device of various display driving methods by appropriately selecting a polymer which is a raw material. The liquid crystal display element of the present invention can be rotated to have elements other than the constituent elements. In the liquid crystal display device of the present invention, a constituent element which is generally used for a liquid crystal display element such as a polarizing plate (polarizing film), a wavelength plate, a light-scattering film, and a driving circuit can be mounted. [Examples]

Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples. The compounds used in the examples are as follows. &lt;tetracarboxylic dianhydride&gt;

Compound: Ethylenediaminetetraacetic acid dianhydride: EDDA Compound: 1,4-phenylenediamine tetraacetic acid dianhydride: PhDDA

Compound. Glycol-bis-(2-aminoethyljun)tetraacetic acid dianhydride: EGDA

Compound: 1,2-bis-(aminoindenyl)-cyclohexene tetraacetic acid dianhydride: CDA compound: pyromellitic acid dianhydride: PMDA compound: cyclobutane tetraphthalic acid dianhydride: CBDA compound: butane Tetraphthalic acid dianhydride: BUTDA 132 ii.doc 201030060 Compound: 3,3'-4,4'-benzophenone tetradecanoic acid dianhydride: 311) Eight compounds. 3,3'-4,4'- Phenyltetradecanoic acid dianhydride: 〇8 compound·Qin-2,3,6,7-tetracarboxylic dianhydride: NTCA compound: naphthalene-1,4,5,8-tetradecanoic acid two needles: &lt;Diamine&gt;

Compound: 4,4'-diaminodiphenylmethane: DDM

Compound: 4,4'-diaminodiphenylethane: DDET

Compound: 4,4'-diaminodiphenyl_ : DDE

Compound: 2,2-bis{4-[4-aminophenoxy]phenyl}propane: baPP Compound: 4-bis(4-aminophenyldiazolidine:dAc

Compound: N,N'-bis(4-aminophenyl(9)-di-didecylethylenediamine: DMEDA

Compound: 1,3,5-diamino-7, ‘triazole: DATA

Compound: 1,1-bis((aminophenoxy)phenyl)_4_(pentylcyclohexyl)cyclohexane: 5HHBA

Compound: U-bis{4-[(4-cylylphenyl)indenyl]phenyl}_4-n-heptylcyclohexane: 7HBZ

Compound: 1,1-bis(4-(4-aminophenoxy)phenyl)_4_n-heptylcyclohexane: 7HBA

Compound: 1,1-bis((aminophenoxy)phenyl)_4-(heptylcyclohexyl)ethyl)cyclohexane: 7H2HBA &lt;solvent&gt; NMP · N-methyl-2-*» Ketone BC. Butyl cellosolve (ethylene glycol monobutyl) 133 201030060,

-----jI.QOC &lt;1. Synthesis of Polyproline&gt; [Synthesis Example 1] 2.7320 g was placed in a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen inlet. DDM and 75.0 g of dehydrated NMP were stirred and dissolved under a stream of dry nitrogen. Next, 1.7652 g of EDDA and 1.5028 g of PMDA were added, and after reacting for 30 hours, 19.0 g of BC was added to synthesize a 6 wt% polylysine solution (hereinafter also referred to as Varnish) (Al). When the temperature rises due to the reaction temperature in the reaction of the raw material, the reaction temperature is suppressed to about 70. (: or 70 ® ° (: The reaction is carried out below. Further, the weight average molecular weight of the polylysine obtained in A1 is 70,700. The weight average molecular weight of polyglycine is determined as follows: using phosphoric acid - DMF mixed solution (phosphoric acid / DMF = 〇.6 / l 〇〇: weight ratio) to dilute the obtained poly-proline to make the polyglycine concentration about 1 wt%, and then use the 2695 separation module (separati 〇n module), 2414 differential refractometer (manufactured by Waters), and the mixed solution was used as a developing solvent and measured by the Gpc method, and then converted into polystyrene. In addition, the column was made of HSPgel ❹ RTMB-M (manufactured by Waters). The measurement was carried out under the conditions of a column temperature of 4 〇〇c and a flow rate of mL35 mL/min. [Synthesis Example 2 to Synthesis Example 47] The tetracarboxylic dianhydride was changed as shown in Tables 1 to 4. In addition to the diamine, a poly-bristamine solution (A2) to a poly-proline solution (A44) and a poly-proline solution (B1) to a poly-branched acid solution (B3) were prepared according to Synthesis Example 1. 1 'The results are summarized in Table 1 to Table 4. 134 s 1X20 e — die [Ϊ] H &lt; i Ί Γ Γ »t Η 70700 66100 46200 1 08000 74700 191200 99400 130100 154400 I 69100 91000 83600 79100 116100 ! 58300 68200 98700 , 73200 65000 80500 59100 Diamine (mol%) I DATA I DMEDA ο ο ο ο ο ο ο BAMPP 〇〇〇〇g § 冢I BAPPj 〇DDE 〇DDET 〇〇〇DDM 〇o ο Four oxo-dianhydrides (mol%) NPDA (N NTCA *Ti BPDA ν-&gt; cn BTDA ! m BUTDA »Λ&gt;&lt;Ν CBDA : ο (S ο ο ο Ο PMDA沄o Ο EDDA 〇〇〇〇〇〇(N m CO *Ti &lt;Ν CN V% m aligning agent &lt;inch&lt;&lt;\〇&lt; 00 &lt; A10 1 All I |Α12 I 1 Α13 I La14 ...I 1 A15 I A16 I Α17 1 Α18 Α19 1 1 A20 | A21 Synthesis Example 1 Synthesis Example 2 Ashing Example 3 Synthesis Example 4 | 1 Synthesis Example 5 1 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 1 I synthesis example ίο | 1 synthesis example 11 | 1 combination Example 12 1 1 Synthesis Example 13 1 Synthesis Example 14 1 I Synthesis Example 15 | | Synthesis Example 16 1 1 Synthesis Example 17 1 Synthesis Example 18 1 1 Synthesis Example 19 1 Synthesis Example 20 1 Synthesis Example 21 1 ο s 1Χ20 oOP .Ja—ε [&lt;Nd υ bml *«pi ... φ ίΓ »w •JauI 77600 94900 86400 78200 102100 91000 72500 42800 81900 Side chain diamine (mol%) | 7H2HBA | 〇| 7HBA | 〇 | 7HBZ | 5HHBA | 〇T—&lt; 〇〇〇〇〇 diamine (mol%) | DMEDA | | DAC | 〇BAMPP § | DDET | § | DDM | § Four rebel two needles (mol%) | CBDA | PMDA | ED | EDDA | 〇4 K , I A22 I A23 I LA24 JI A25 II A26 II A27 I | A28 I A29 I A30 Synthesis Example 22 Synthesis Example 23 Synthesis Example 24 Synthesis Example 25 | Synthesis Example 26 I | Synthesis Example 27 I Synthesis Example 28 | Synthesis Example 29 I Synthesis Example 30 201030060 o gFJ-az, inch 6&lt;Νε [s 00-ε 00 b 6 inch 0003⁄4 00 s 00 inch S 242 003 4 009 009- 0S- 00 inch S inch 00638 00A66 0096 inch oos^ οι ΟΙ °l

(0/οϊ 鍩M (o/olouofed 镏赛0 ddwvffl 1ωαα 001 001 001 0°l 06 ΟΟΪ 001 06 00- 06 2αα 02 001 001 001 vas να20· V8 va〇3 vai νααω os Ο inch 0*° 0 inch ° inch inch ο inch 0 inch 0 inch 0 inch inch inch ο inch 0 inch 0 inch inch inch inch inch οε οε οε οε 02 οε °e οε οε 02 οε ιεν β § οι εεν 03 inch εν inch £5^φ οι 03 οι 00- οι 9εν L2 8εν 6εν ο vs ν

-V

Inch ν ε inch ν 9V 6£ 5哒&lt;0 A pair of 5^φ 201030060, [Table 4] Alignment agent tetradecanoic acid (m〇i%) diamine (mol%) Weight average molecular weight PMDA CBDA DDM DDET Synthesis Example 45 B1 50 50 100 51500 Synthesis Example 46 B2 50 50 100 48000 Synthesis Example 47 B3 65 &gt; 35 100 62600 Polyamine prepared at a concentration of 6 wt% synthesized in Synthesis Example 23, Synthesis Example 36, and Synthesis Example 30 The acid solutions (A23, A36, and A30) and the polyglycine solution (B1 to B3) having a concentration of 6 wt/min synthesized in Synthesis Examples 45 to Synthesis 47 were 20/80 by weight (the former/the latter). The mixture was mixed to form a liquid crystal alignment agent (A45 to A51). The composition of A45~A51 is summarized in Table 5 ° [Table 5]

Additive varnish varnish weight ratio A45 A23 B1 A23/B 1=2/8 — A46 A23 B2 A23/B2^2/8 A47 A23 B3 Α23/Β3^2?8~~~ A48 A36 B1 Α36/Β1=2/ 8 A49 A36 B2 Α36/Β2=2^ A50 A36 B3 Α36/Β3=2/8 A51 A30 B1 Α30/Β 1=2/8 The concentration synthesized in Synthesis Example 4, Synthesis Example 14 and Synthesis Example 32 is 6 A double {4-(allylbicyclo[2,2,1:|heptane-2) with an average polymer weight of 10 wt°/〇 was added to the wt% polyaminic acid solution (A4, A14, and A32). , 3_dicarboxy quinoid imine) phenyl}methane, N'N-(1,2-di-ethylidene) bis acrylamide, 2-(3,4-epoxycyclohexyl)ethyltrimethyl Oxydecane, ammonia 138 201030060^ propyl triethoxy decane, 4,4'-fluorenylene bis (N,N-diglycidyl amide) and 1,3-double (4,5-di Hydrogen-2-oxazolyl)benzene to form a liquid crystal alignment agent (A52 to A60). The composition of A52 to A60 is summarized in Table 6.

❹ 139 .doc 201030060 [Table 6] Additives for varnish additives (wt%, Α52 Α4 double {4-(allylbicycloindole 2,2,11 broad _5-female 2,3_dicarboxy fluorene) Amine) phenyl hydrazine methane 10 Α 53 Α 4 ...... dihydroxyethylidene bis acrylamide 10 Α 54 Α 14 double {4 · (dilyl propyl bicyclo [2, 2, 11 g-5- Alkene-2,3-dicarboxy styrene]imine}methane 10-10 Α55 Α14 2:(3,4-cyclohexylcyclohexyl)ethyl=methoxyoxane Α56 Α14 arylpropyl=wide Oxygen 暮· Hyun 1 10 1〇Α57 Α14 4,4-methylene-substituted w N--glycidyl aniline) Α58 Α32 double {4-(Anobinylbicyclo[2,2,ηhept-5-lean -2,3-carboxy quinone imine) 笨 丨 丨 methane 1 〇Α 59 Α 32 彡-(3,4-epoxycyclohexyl)ethyl = methoxy montane 10 Α 60 Α 14 1,3- double (4, 5-Hydroxy-2-oxazolyl)benzene 10 (Production of Liquid Crystal Display Element) [Example 1] To a polyglycine solution (A1) having a concentration of 6% by mass synthesized in Synthesis Example 1 A mixed solvent of NMP/BC=l/l (;t ratio) was added and the whole was diluted to 4 wt%' to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the following manner. (Manufacturing method of liquid crystal display element) A liquid crystal alignment agent was applied to two glass plates with IT 〇 electrodes attached by a rotator to form a film having a thickness of 7 〇 nm. After the film is applied, it is added under the crucible, dried for about 5 minutes' and then heat treated at 21 () t for 2 () minutes, ί = crystal alignment film. Then, the alignment treatment is performed by rubbing the surface on which the liquid crystal is provided with the two-phase ❹* by a rubbing device. Then, f is at 120. After the solution was ultrasonically cleaned for 5 minutes, it was dried in a container at 120 C for 30 minutes. Spreading 7 on the square glass substrate is called _, so that the liquid crystal alignment _ surface is formed and the rubbing direction Ρ 140 20103006 (^ —..^n.doc is arranged in parallel, and then hardened with epoxy. The agent was subjected to a dense direction to form an antiparallel cell having a gap of 7 μm. The liquid crystal composition shown below was injected into the diterpene unit, and a photocuring agent was used to seal the injection port.

I7wt. %

CaH7 CeHn CzHs

17WL% iewt.% 10Wt% C3H7

F 5wL% C5H11 C2H5 C3H7 C5H11

F 10WL % 6wt % 0Mft % 13wt% 141 201030060, [Example 2 to Example 51] To A2 to A5, A10 to A29, A31 to A37, A39, A40, A42, A43, A45 to A50 and A52 to A60 A mixed solvent of NMP/BC = 1/1 (weight ratio) was added and diluted so that the concentration of polyproline was 4.0 wt% to 5.0 wt% as a whole, thereby preparing a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. [Comparative Example 1 to Comparative Example 9] A mixed solvent of NMP/BOIA (weight ratio) was added to A6 to A9, A30, A38, A41, A44 and A51, and diluted so that the concentration of polyglycine was 10 as a whole. 4.0 wt ° / 〇 ~ 5.0 wt%, thereby preparing a liquid crystal alignment agent. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. (Confirmation of Flow Orientation) The liquid crystal display element produced by the above method was sandwiched between polarizing plates placed on a crossed Nicoles, and it was visually confirmed whether or not the flow alignment could be seen. (Preparation of Substrate for Delay Measurement) A transparent glass substrate is used as the substrate of the measurement substrate. ® The varnish A1 obtained in Synthesis Example 1 was coated on the transparent glass substrate by a spinner. The coating conditions were 2,000 and 15 seconds. After coating, the film was pre-baked at 80 ° C for about 3 minutes, and then heat-treated at 21 ° C for 2 minutes to form a liquid crystal alignment film having a film thickness of about 7 Å. The friction processing device made by Iirmma-gauge Co., Ltd. 'in the rubbing cloth (hair length L8mm: rayon (4) (10))) has a hair injection amount of 142 ii.doc 201030060 of 0.40 mm, and the flat life is t, * From rpm, fi^^K6〇mm/SQCi^^ ^000 to obtain the measurement of the county plate (four) secret Yalai for miscellaneous treatment, from (delay (R) determination)

The retardation (R) of the alignment film was determined using an ellipsometer (spect_〇pic elliPS〇meter) M_2000UaA.woollam c〇Jnc. The larger the value of R, the liquid crystal alignment _ extends in the rubbing direction, thereby having high uniaxial alignment. As a result, it can be said that the black display is good. In the test method of the embodiment of the present invention, the delay is preferably greater than equal ^

143 doc 201030060 [Table 7] Directional agent flow alignment delay (nm) Example 1 A1 〇 0.399 Example 2 A2 〇 0.301 Example 3 A3 〇 0.337 Example 4 A4 〇 0.655 Example 5 A5 〇 0.516 Comparative Example 1 A6 X 0.102 Comparative Example 2 A7 X 0.054 Comparative Example 3 A8 X 0.081 Comparative Example 4 A9 X 0.169 Example 6 A10 〇 0.771 Example 7 All 〇 0.615 Example 8 A12 〇 0.690 Example 9 A13 〇 0.574 Example 10 A14 〇 0.689 Implementation Example 11 A15 〇0.551 Example 12 A16 〇0.647 Example 13 A17 〇0.622 Example 14 A18 〇0.833 Example 15 A19 〇0.457 Example 16 A20 〇0.936 Example 17 A21 〇0.452 Example 18 A22 〇0.334 Example 19 A23 〇 0.612 Example 20 A24 〇 0.599 Example 21 A25 〇 0.590 Example 22 A26 〇 0.602 Example 23 A27 〇 0.618 Example 24 A28 〇 0.511 Example 25 A29 〇 0.485 〇: no flow alignment, χ: flow alignment _i.doc 201030060 [Table 8]

Alignment agent flow alignment retardation (nm) Comparative Example 5 A30 X 0.109 Example 26 A31 〇0.325 Example 27 A32 〇0.566 Example 28 A33 〇0.489 Example 29 A34 〇0.410 Example 30 A35 〇0.463 Example 31 A36 〇0.422 Example 32 A37 〇0.736 Comparative Example 6 A3 8 X 0.060 Example 33 A39 〇0.578 Example 34 A40 〇0.550 Comparative Example 7 A41 X 0.088 Example 35 A42 〇0.495 Example 36 A43 〇0.471 Comparative Example 8 A44 X 0.069 Implementation Example 37 A45 〇0.349 Example 38 A46 〇0.496 Example 39 A47 〇0.376 Example 40 A48 〇0.322 Example 41 A49 〇0.349 Example 42 A50 〇0.331 Comparative Example 9 A51 X 0.080 Example 43 A52 〇0.310 Example 44 A53 〇0.312 Example 45 A54 〇0.677 Example 46 A55 〇0.471 Example 47 A56 〇0.406 Example 48 A57 〇0.422 Example 49 A58 〇0.482 Example 50 A59 〇0.450 Example 51 A60 〇0.577 〇: No flow alignment , χ : Flow alignment shown in Table 7 and Table 8, liquid crystal display using a liquid crystal alignment film obtained by the following liquid crystal alignment agent In the case, the obtained liquid alignment is eliminated, 145 201030060, -..., fi.doc has an extremely high retardation effect, and the liquid crystal alignment agent is a liquid crystal containing a polyamic acid containing EDDA and other tetracarboxylic dianhydride in the monomer. An aligning agent. The present invention has been disclosed in the above embodiments, and it is not intended to limit the invention to those skilled in the art, and may be modified and practiced without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims. [Simple description of the diagram] None. [Main component symbol description]

146

Claims (1)

201030060, VII. Patent application scope: 1. A liquid crystal alignment agent containing polylactoic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine, the liquid crystal alignment agent being characterized by: The tetracarboxylic dianhydride contains one or more kinds of tetracarboxylic dianhydrides represented by the following general formulae (TC-1) to (TC-14), and one or more other tetradecanoic acids. ^ 147 201030060, [Chem. 2] In the formula (TC-1), X represents -(CH2)m-, and at most two -CH2- may be independently -Ο-, but here -Ο-discontinuous, -S-, -COO-, - OCO-, -CO-, -CONH-^-CnH2nN(CmH2mCOOH)CnH2n-^-CH(CmH2mOH)- &gt;, CH(CnH2n+1)_, -CHCH- or -C tri C-substitution, the above Formula (TC-1) 201030060, m in X independently represents an integer of 0 to 30, n independently represents an integer of 1 to 30; in the formula (TC-4) to (TC-7), Υ is independent Ground represents a single bond, -0-, -S-, -S_S-, _S〇2_, -CO-, -CONH_, -NHCO·, -ΝΗ·, -N(CH3HCH2)mN(CH3)-, -C( CH3)2-, -C(CF3)2_, -(〇!'_, -0-(CH2)m-0-, -S-(CH2)m-S_, the above formula (TC-4)~ m in the formula (TC-7) represents an integer of 1 to 6; in the formula (TC-5), Z represents a single bond or does not exist; in the formula (TC-2) to the formula (TC-7) The hydrazine bonded to the cyclohexane ring or the benzene ring may be independently substituted by -F, -CH3, -CF3, -OH, -COOH, ❹_S〇3H, -P〇3H2 'TC- The hydrogen bonded to the benzene ring in 3) may be substituted by a benzyl group; in the formula (TC-2) to the formula (TC-8), R1 independently represents -(CH2)m-, at most two -CH2- can be independently -〇-, Here, -O-discontinuous, -S-, -COO-, -OCO-, -CO-, -CONH-, -CH(CmH2mOH)·, -CH=CH-〇C- are substituted, the above formula (TC-2)~ m in the formula (TC-8) independently represents an integer of 〇30; in the formula (TC-8), Α1 is independently an alkyl group having a carbon number of 1 to 10, and a carbon number of 1 ～10 alkoxy group, acetamide, fluorine, chlorine or bromine, A2 independently represents an alkyl group having 1 to 3 carbon atoms, m represents an integer of 〇~3, and n represents an integer of 〇~4; In TC-9), R33 and R34 each independently represent an alkyl group or a phenyl group having a carbon number of i to 3, and A3 independently represents an anthracenylene group, a phenylene group or a substituted alkylidene group '1' represents 1~ An integer of 6 , m represents an integer of 丨~1〇; in the general formula (TC-10), 'A3 denotes a single bond, _0_, _c〇〇_, _〇c〇, _c〇_, -CONH- or -(CH2) M-'in the above formula (Gua 1〇), m of A3 represents an integer of 6 and R1 represents a group having a steroid skeleton or a group represented by the following formula (B), when bonded to a benzene ring The positional relationship between the two amino groups is 149 201030060H, and R1 further contains an alkyl group having a carbon number of 1 to 30, when its positional relationship is meta-R' Further comprising an alkyl group or a phenyl group having 1 to 30 carbon atoms, wherein 'any -CH2- may be independently -CF2-, -CHF-, -〇-, but here -0-discontinuous, -CH=CH- or -OC-substituted, -CH3 may be substituted by -CH2F, -CHF2 or -CF3, the hydrogen of the phenyl group is independent, and is represented by F, -CH3, _〇CH3, _0CH2F, - Replaced by OCHF24-OCF3; [Chemical 3] (B) In the general formula (B), A4 and A5 each independently represent a single bond, but here -0-discontinuous, -COO-, -0C0-, -CONH-, -CH=CH- or a carbon number of 1 to 12 Alkenyl' R2 and R3 each independently represent _F or _€113, and ring S independently represents 1,4-phenylene, 1,4-cyclohexene, 1,3-dioxane-2,5 _Diyl, pyrimidine-2,5-diyl, bite-diyl, naphthalene+5.diyl, ca._2,7-diyl or oxime-9,10-diyl' R4 represents -H, -F, an alkyl group having 1 to 3 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having a carbon number of 丨3 to 3, _C=N, -0CH2F, -OCHF2 or -〇 CF3 'a and b respectively represent integers of 〇~4, c, d, and e respectively represent integers of 〜3, and f&amp;g independently represents integers 〇~2 and c + d+e$l; In the formula (Τ(Μ1) and (TC_12), 'R5 independently represents -Η or even, and V represents _H, or an alkyl group having a broken number or an alkenyl group having a carbon number of 2 to 20, and a6 independently represents a single Key, _c〇_ or -CH2·; In the general formula (TC-12), RW independently represents ugly, carbon 150 _i.doc 201030060 number 1 to 20 alkyl or phenyl; general formula (TC-13) And in the general formula (TC-14), A7 independently represents -0- or In the general formula (TC-13), R9 represents -H or a carbon number of 1 to 30, and in the alkyl group, any of the groups having a carbon number of 2 to 30 is - CH-- can be replaced by 'but here-Ο-discontinuous, -CH=CH- or -CSC-, A8 represents not a single bond or a carbon number of 1 to 3, and the ring T represents 1,4-times. Phenyl or 1,4-cyclohexene 'h represents 0 or 1; in the formula (TC-14), R10 represents an alkyl group having 6 to 22 carbon atoms, and R11 represents -H or an alkyl group having 1 to 22 carbon atoms. 2. The liquid crystal alignment agent according to claim 1, wherein the other four resorcinic acid two needles comprise two needles of aromatic tetraacid. 3. Liquid crystal alignment as described in claim 2 The aromatic tetra-acid dianhydride is represented by the following structural formula (1), structural formula (2), structural formula (5) to structural formula (7), structural formula (10), and structural formula (13). And at least one of the compounds represented by the structural formula (14) The liquid crystal alignment agent according to claim 1, wherein the tetracarboxylic dianhydride comprises one of an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic acid two needle. Or both parties. 5. The liquid crystal alignment agent according to claim 1, wherein the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride are the following structural formula (15), structural formula (16), At least one of the compounds represented by the structural formula (21) to the structural formula (25) and the structural formula (29) to the structural formula (31), [Chemical 5] (15) The liquid crystal alignment agent according to any one of the items 1 to 5, wherein the diamine further comprises a side chain represented by the following general formula (I) and formula (II) One or more of the structural diamines, 152 (i) 201030060, . &gt; ^rlX.ClOC [Chemical 6] R12 (II) In the general formula (I) and the general formula (H), 'A9 independently represents -〇- or a carbon number of 1 to 6 in the formula (1), 'Rl2 represents or a carbon number of 1 to 30. Any -CH2- of the alkyl group having a carbon number of 2 to 30 in the alkyl group may be replaced by -0- 'but here -〇·discontinuous, -CH=CH- or -C=C·' A1Q Represents a single bond or an alkenyl group having 1 to 3 carbon atoms, ring T represents 1,4-phenylene or 1,4-cyclohexene, h represents 0 or 1, and 'R15 represents carbon in the formula (II) The alkyl group '16' of 6 to 22 represents an alkyl group having 1 to 22 carbon atoms. 7. The liquid crystal alignment agent according to claim 6, wherein the diamine having a side chain structure is selected from the group consisting of the following general formula (1-1), general formula (1-2), and general formula ( 1-4) and at least one of the compounds represented by the formula (1-7), 153 J.doc 201030060 [Chem. 7] In the above formula, R13 and R14 each represent an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the diamine further comprises the following general formula (III) to general formula (X), and general formula (N) And a diamine having no side chain structure represented by the general formula (8), ❹ 154 201030060 ii.doc η2ν-χ-νη2 (III) η η2ν^^νη2 (IV) Η2Ν〇-η θΝΗ2 (V) ο (VI) (VII) H2N—(~A11士士 (X) 155 201030060 rioc In the formula (III), 'X represents -(CH2)m-, and in the above formula (III), m of X represents an integer of 1 to 6, and the formula (V) and the formula (VII) to the formula In (IX), γ independently represents a single bond, -Ο-, _S-, -S_S-, -S02-, -CO-, -CONH-, -NHCO·, -NH-, _N(CH3HCH2)mN (CH3 )·, -C(CH3)2-, -C(CF3)2-, -(CH2)m-, -0-(CH2)m-0_, -S-(CH2)mS-, the above formula (V) And m of γ in the general formulae (VII) to (IX) represents an integer of 1 to 6, and in the general formula (VII), Z represents a single bond or does not exist, and in the general formula (8), r19 and R2G are independently An alkyl group or a phenyl group having 1 to 3 carbon atoms, A11 independently represents a methylene group, a phenylene group or a subphenyl group substituted by an alkyl group; i represents an integer of 1 to 1-6, and j represents an integer of 1 to 10; In the formula (IV) to the formula (IX), the hydrogen bonded to the cyclohexane ring or the benzene ring may be independently, -CH3, -CF3, -OH, -COOH, -S03H, -Ρ03Η2 Alternatively, the hydrogen bonded to the benzene ring in the formula (VI) may be substituted by a benzyl group; in the formula (N), A1 independently represents an alkyl group having a carbon number of 1 to 4 and a carbon number of 1 to 4 alkoxy, acetamide, fluorine, chlorine or bromine, A2 independent Represents an alkyl group of 1~3 carbon atoms, m represents an integer of ~ 3 billion, [eta] represents an integer of 0~4; formula ⑷ in. It represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a benzyl group. The liquid crystal alignment agent according to claim 8, wherein the diamine having no side chain structure is selected from the following structural formula, structural formula (VI-2), and structural formula (VI-15) )~Structure formula (νΐ-Π), Structural formula (VII-1)~Structure formula (VII-13), Structural formula (VII-32), Structural formula (VII-34)~Structure formula (VII-36), Structural formula (ΧΙ-2), structural formula (χ-3), structural formula (N)-l, structural formula (Ν)·2, structural formula (Ν)-14, and structural formula (a-Ι) At least one of the compounds, 156 201030060 H w / ., γΐ丈.doc [化9] 2 ~ ί ί ί ί ί ί ί ί ί 3) ❹ (VII-5) Nh2 © (VII-32) (VIM 3) 157 201030060 /pif.dOC [化10] h2n N—^j)-NH2 h2N—N^^N—ζ^)-ΝΗ3 (VII-35) (VII-34) CH3 ch3 H2N—C3H5—Si-0~Si—C3H6—NH2 ch3 ch3 (X-3) (Xl-2) 10. The liquid crystal alignment agent according to claim 6, wherein the polyaminic acid or a derivative thereof comprises two polylysines or derivatives thereof A and B, the polylysine or The derivative A contains one or more kinds of diamines having a side chain structure represented by the formula (I) and the formula (II) in the above-mentioned diamine, and One or both of the polyamic acid or derivatives of the tetracarboxylic dianhydrides of the derivatives A and B include tetracarboxylic dianhydride represented by the above formula (TC-1) to formula (TC-14). One or more and other tetracarboxylic dianhydrides. The liquid crystal alignment agent as described in any one of the above-mentioned items of the present invention, further comprising a nadic ylidene compound selected from an alkenyl group, having a radical polymerizable unsaturated double bond. One or more of a compound, an oxazine compound, an oxazoline compound, and an epoxy compound. A liquid crystal alignment film which is formed by heating a coating film of the liquid crystal alignment agent according to any one of claims 1 to 11. A liquid crystal display device comprising: a pair of substrates; a liquid crystal layer containing liquid crystal molecules and formed between the pair of substrates; an electrode for applying a voltage to the liquid crystal layer; and aligning the liquid crystal molecules at a predetermined A liquid crystal alignment film in a direction; the liquid crystal display element is characterized in that: the liquid crystal alignment film is a liquid crystal alignment film according to item 12 of the patent application scope. 159 201030060 d ___ .fii.doc IV. Designated representative map: (1) The designated representative of the case: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 3