TW201125896A - Liquid crystal aligning agents, liquid crystal aligning layers and liquid crystal display devices - Google Patents

Abstract

A liquid crystal alignment agent containing a polyamic acid is used to form a liquid crystal alignment layer having a small residual DC, wherein the polyamic acid is obtained by reacting an amine of formula (P), or a mixture of an amine of formula (P) and other amine, with a tetracarboxylic dianhydride. An LCD device without occurrence of burn-in can be obtained by suitably using the liquid crystal alignment layer. The ring P is pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine- 2,5-diyl or pyrazine-2,5-diyl, and k is 0 or 1; but when k=0, the ring P is pyridine-2,5-diyl or pyrimidine-2,5-diyl. The bonding position of amino is position-5 in these rings.

Description

201125896 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent containing a polyglycine or a derivative thereof, which is an aromatic ring having 1 or 2 nitrogen atoms The diamine is reacted with a tetracarboxylic dianhydride. The present invention relates to a liquid crystal alignment film obtained by the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. [Prior Art] The liquid crystal display element has been widely used as a display element for televisions, and has recently been used as a display element for televisions, starting from a display of a notebook or a desktop computer, and for various liquid crystal display devices such as a viewing window and a projection display of a video camera. In addition, it can also be used as an optoelectronic related component such as an optical head, an optical Fourier transform element, or a light valve. The mainstream of the prior liquid crystal display elements was a display element using nematic liquid crystal, and the twist was 9 Å. A twisted nematic (TN) type liquid crystal display element, usually twisted 18 turns. The above-described super twisted nematic (stn) type liquid crystal display element has been put into practical use as a thin film transistor (TFT) type liquid crystal display element using a thin film transistor. However, these liquid crystal display elements have disadvantages in that the viewing angle of the image can be appropriately recognized, and when viewed from the oblique direction, luminance or contrast is lowered, and luminance inversion of halftones is generated. In recent years, the problem of the viewing angle has been improved by the following techniques: a TN type liquid crystal display element using an optical compensation film, and a multi-domain vertical Alignment (MVA) type liquid crystal display using a vertical alignment and protrusion structure. Coplanar switching of components, or transverse electric field methods (Ιη·ρ_ 201125896

These improved technologies are being put into practical use (for example, refer to Patent Documents 1 to 3). The development of the liquid crystal display element technology is not only an improvement of its driving method and component structure, but also an improvement of the constituent components used for the display element. Among the constituent members used for the display element, in particular, the liquid crystal alignment film is one of the important factors related to the display quality of the element. With the improvement of the quality of the liquid crystal display element, the role of the liquid crystal alignment film has become important year by year. An important characteristic required for the liquid crystal alignment film to improve the display quality of the liquid crystal display element is, for example, a residual DC potential (Residual DC). If the residual DC is large, even if the voltage is turned off (〇FF) after the voltage is applied, the erased image remains, and a so-called "residuaHmage" is generated.曰 θ is a liquid crystal alignment agent which provides a liquid crystal element having a small storage charge (stC) red eh morphine by using a sulphur-containing melamine to solve the afterimage (see, for example, Patent Document 4). Further, a combination of ultraviolet light irradiation and a liquid crystal alignment agent containing a (tetra)amine acid containing a shot skeleton is proposed (for example, refer to Patent Document 5). These prior art have room for further research as a material for obtaining a liquid crystal alignment film for liquid crystal formation which is required to be further improved to obtain the obtained liquid crystal alignment film = milk characteristics or to obtain desired electrical characteristics. [Prior Art Document]: [Patent Document] Patent Document 1: Japanese Patent Publication No. Sho 63_21907, Patent Document 2: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. Hei. No. Hei. No. Hei. A polyphthalamide and a polyimine-based polymer of a liquid crystal alignment film 'an alignment film formed using the polymer, and a liquid crystal display element to which the alignment film is applied without causing a bura-in. [Means for Solving the Problem] The inventors found that a composition containing polylysine (a diamine having an aromatic heterocyclic ring having 1 or 2 nitrogens as a raw material) or a derivative thereof is used in a liquid crystal alignment agent. In the case of the liquid crystal display element having the liquid crystal alignment film formed by the liquid crystal alignment agent, low residual DC can be achieved, thereby completing the present invention. The liquid crystal alignment agent of the present invention is as described in the item [1] below. a liquid crystal alignment agent which contains at least one polymer selected from the group consisting of polylysines and derivatives thereof, wherein the poly-aracine is a diamine represented by the formula (P), or A mixture of a diamine and another diamine represented by the formula (P) and a tetracarboxylic dianhydride are obtained by reacting:

Wherein % P is a bismuth-2,5-diyl, tahe-3,6-:S (pyridazin-3,6-diyl), pyrimidine-2,5-diyl or pyrazine-2,5 -pyridin_ 2,5-diyl; k is 0 or 1; when k=0, ring P is π than bite 2,5-diyl or pyrimidine-2,5-diyl, and these rings The bonding position of the amino group is 5 bits. [Effect of the Invention] According to the present invention, it is possible to provide a liquid crystal display element which is low in residual j) C and is applicable to various driving methods. [Embodiment] First, terms used in the present specification will be described.

The diamine represented by the formula (P) is sometimes simply referred to as a diamine (p). The diamine represented by the other formula is also abbreviated as such. The tetracarboxylic dianhydride represented by the formula (1) may be abbreviated as p (anhydride). The tetracarboxylic dianhydride represented by the other formula is also abbreviated as such. (Meth) propylene oxime is a general term for acryloxy and decyl propylene oxime. "(Mercapto) acrylate" is a general term for acrylate and methacrylate, "(fluorenyl) acrylate" It is a general term for acrylic acid and mercaptoacrylic acid. The term "arbitrary" as used in the description of the structural formula means that the position is arbitrary and the number is arbitrary. Moreover, the expression "arbitrary A may be substituted by B, C or D" means that at least one a may be substituted by b, at least one A may be replaced by C, at least one A may be replaced by D, or a plurality of ^ It can be substituted by at least 2 of B~D. However, in the case where any _Ch2_ can be taken as a base and replaced by a base of the _Ch 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is not free from the fact that there is no chemical problem with the substituents that constitute the _ rhyme arbitrary __. In the case of P), bauxite <) uses the same notation in the evening formula: the ring, the binding group or the terminal group represented by the scorpion has the same ambiguity (four) 'but does not mean that it must be in all formulas At the same time, it is the same base within the scope of slavery 201125896. It may be the same base in a plurality of formulas or may be a different base in each formula. The present invention is constituted by the above item [1] and the following items [2] to [21]. [2] The liquid crystal alignment agent according to the item [1] wherein the diamine represented by the formula (p) is at least one of the diamines represented by the formulae (P-1) to (P-10):

[3] The liquid crystal alignment agent according to [2], wherein the diamine represented by the formula (P) is at least one of the diamines represented by the formulae (P-5) and (P-8). [4] The liquid crystal alignment agent according to any one of [1] to [3] wherein the other diamine is selected from the group consisting of the formula (VIII) and (X) to (XIII) having a side chain group. At least one diamine of the group of diamines: R1

In the formula (VIII), A3 is a single bond, _〇_, _c〇_, c〇〇_, _〇c〇_, _c〇nh-, 201125896-CH2O-, -CF^O- or carbon number 1~ a mercapto group of 6, wherein any -CH2_ in the alkylene group may be substituted by -0, -CH=CH- or -OC-; R1 is a group having a steroid skeleton, an alkyl group having 3 to 30 carbon atoms, a phenyl group having an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms as a substituent, or a group represented by the formula (IX), and any -CH2- of the alkyl group having 3 to 30 carbon atoms. Can be replaced by -Ο-, -CH = CH- or -OC-;

In the formula (IX), A4 and A5 are independently a single bond, -0-, -COO-, -0C0-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and an oxyalkylene group having 1 to 3 carbon atoms. Or an alkyleneoxy group having a carbon number of 1 to 3; the ring B and the ring c are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; R2 and R3 are independently a fluorine or a fluorenyl group, and f and g are independently 〇, 1 or 2; c, d and e are independent integers of 〇~2, and the total of c, d and e is 1 or more; when c is 2, 2 rings B may be the same or different, 2 A4 The same binding group may also be a different binding group; when d is 2, 2 A5 may be the same binding group or different bonding groups; when e is 2, 2 rings C may be the same R4 may be an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an alkoxyalkyl group having 2 to 30 carbon atoms, among these alkyl groups, the alkoxy group and the alkoxyalkyl group. Any hydrogen can be replaced by fluorine;

0-A6 (X) 201125896

In the formulae (X) and (XI), 'R5 is independently hydrogen or methyl; R6 is hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms; and R7 and R8 are independently a carbon number of 1 to 20 Alkyl' or phenyl; A6 is independently a single bond, -CO- or -CH2-;

In the formulae (XII) and (XIII), R9 is a fluorenyl group or an alkyl group having 2 to 30 carbon atoms, and any -CH2- of the alkyl group may be substituted by -〇-, _CH=CH- or -OC-; R1Q a carbon number of 6 to 22; R11 is a carbon number of 1 to 22; A7 is independently -0- or an alkylene group having 1 to 6 carbon atoms; and A8 is a single bond or a carbon number of 1 to 3 Alkyl; ring T is 1,4-subunit or 1,4-cyclohexylene; h is 0 or 1. [5] The liquid crystal alignment agent according to [4], wherein the other diamine is selected from the group consisting of formula (VIII-2), (νΐΙΙ-4)~(νΐΠ-6), (ΧΠ-2), ( At least one of the diamines represented by XII-4) and (XII-6): 201125896

(XII-6) In the formula, R23, R29 and R30 are independently an alkyl group having a carbon number of 1 to 30 or carbon.

Alkoxy groups having a number of from 1 to 30. [6] The liquid crystal alignment agent according to any one of [1] to [3] wherein the other diamine is a mixture of diamines having a side chain group selected from the group [4]. At least one of the group of diamines, and at least one selected from the group consisting of diamines having no side chain groups represented by formulas (I) to (VII) and (XV); H2N-X-NH2 /h h2n ^ Nh2 (Η) 11 201125896

H2N

ΝΗ·

H2N Ο (III) (IV) h2n nh2

(V) h2n nh2

(VI) nh2 h2n

R33 I Si-O I R34 (VII)

H2N - A3

R33 Si-A3-NH2 I R34 (XV)

In these formulas, X is a linear alkylene group having 2 to 12 carbon atoms; Y is independently a single bond, -0-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO- , -C(CH3)2-, -C(CF3)2-, -0_(CH2)t-0-, -S-, -SS-, -S02-, -S-(CH2)tS- or carbon number a linear alkylene group of 1 to 12, t is an integer of 1 to 12; Z1 and Z2 are hydrogen, but when Y is -NH-, -N(CH3)-, -CH2-, -C(CH3)2- Or -C(CF3)2- may also be bonded to each other to form a single bond; ring D is a strepto or 1,4-diazacyclohexylene; and R33 and R34 are independently an alkyl group having 1 to 3 carbon atoms. , or phenyl; A3 is independently an alkylene group having 1 to 6 carbon atoms, a phenylene group or a sub-phenyl group substituted by an alkyl group, and an in 1 to 10 integer, which is a ring or a sorrowful Any hydrogen may be substituted by fluorine, sulfhydryl, trifluoromethyl, -OH, -COOH, -S03H, -3,2, benzyl or hydroxy. [7] The liquid crystal alignment agent according to [6], wherein the other diamine is a mixture of diamines such as 12 201125896: selected from the group consisting of formula (VIII-2), (VIII-4) to (VIII-6) And at least one of a diamine having a side chain group represented by (XII-2), (XII-4) and (XII-6), and selected from the group consisting of formula (IV-1), (IV-2), (IV) -15)~(IV-17), (V-1)~(V-12), (V-33), (V-35)~(V-37), (VI-7), (VII-2 And at least one of the diamines having no side chain groups represented by (XV-1);

(VIII-2) (VIH-4)

(VIII-5) (VIII-6)

In the above formula, R23, R29 and R3G are independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. H2N-nh2 (IV-1)

(IV-16) 13 201125896

(V-4) (V-5) (V-β)

(V-10)

(V-11)

(V-12)

H2n

(V-36) (V-35)

(V-37) (VI-7) H2N-H〇/VN0^CH2^0/X〇_NH2 H2N-C3H6-Si-〇-Si-C3H6-NH2 ch3 ch3 [8]·Article [1] The liquid crystal alignment agent, wherein the polymer is a mixture of at least one selected from the group consisting of diamines represented by the formula (P-UKpqo) described in the item [2] and selected from the group [4] a polyamido acid or a derivative thereof obtained by reacting a mixture of at least one of the group of diamines having a side chain group and a tetracarboxylic dianhydride; and the selected from the item [6] At least one of the group of diamines having no side chain groups is a polylysine or a derivative thereof obtained by reacting with a reading acid anhydride. The liquid crystal alignment agent according to the item [1], wherein the polymer is a mixture of the following compounds: (P-1) to (P_10) represented by the item [2] a mixture of at least one of the group of diamines and a mixture of at least one selected from the group consisting of diamines having a side chain group described in the item [4] and a poly-proline which is reacted with two needles of tetracarboxylic acid or a derivative thereof; and at least one selected from the group consisting of diamines having no side chain group described in the item [6] and a group selected from the group consisting of diamines represented by the formulae (P_1) to (P-10) Polylysine or a derivative thereof obtained by reacting at least one mixture with tetra-baric acid dianhydride. [10] The liquid crystal alignment agent according to [1], wherein the polymer is a mixture of the following compounds: (Pl) to (p-10) selected from the item [2] At least one selected from the group consisting of diamines and at least one selected from the group consisting of diamines having a side chain group described in Item [4] and selected from the group [6] having no side chain groups Polylysine or a derivative thereof obtained by reacting at least one of a mixture of diamines with a tetracarboxylic dianhydride; and at least one of the above diamine having no side chain group and tetracarboxylic dianhydride The polylysine or its derivative obtained by the reaction. The liquid crystal alignment agent according to the item [1], wherein the polymer is a mixture of compounds obtained by the formula (p-1) to (P-) selected from the item [2]. 10) at least one selected from the group consisting of diamines and at least one selected from the group consisting of diamines having a side chain group described in the item [4] and not having a side selected from the group [6] a polyglycine or a derivative thereof obtained by reacting at least one of a group of diamines of a chain group with a two-needle acid; and a group selected from the group of diamines having no side chain group described above At least one and a polyglycine or a derivative thereof obtained by reacting a mixture of at least one selected from the group consisting of diamines represented by the formulae (P-1) to (P-10) with a tetrahydro acid- 15 201125896 needle. [12] The liquid crystal alignment agent according to [1], wherein the polymer is a mixture of the following compounds: (P-1) to (P-10) selected from the item [2] Polylysine obtained by reacting a mixture of at least one selected from the group consisting of diamines and at least one selected from the group consisting of diamines having no side chain groups described in item [6] with tetracarboxylic dianhydride Or a derivative thereof; and a polyamic acid or a derivative thereof obtained by reacting at least one selected from the group consisting of diamines having a side chain group described in the item [4] with a tetracarboxylic dianhydride. [13] The liquid crystal alignment agent according to [1], wherein the polymer is a mixture of the following compounds: a formula selected from the formula (ρ_ι) to (p_1〇) described in the item [2] Polylysine obtained by reacting at least one of a group of amines and at least one selected from the group consisting of diamines having no side chain group described in item [6] with a tetracarboxylic dianhydride or a derivative thereof And a mixture of at least one selected from the group consisting of diamines having a side chain group described in the item [4] and at least one selected from the group consisting of the diamines having no side chain groups; Polylysine or a derivative thereof obtained by reacting with a tetracarboxylic acid. The liquid crystal alignment agent according to any one of [1] to [13] wherein the tetracarboxylic dianhydride is at least one of aromatic tetracarboxylic dianhydride or aromatic tetracarboxylic dianhydride. A mixture of at least one of at least one of tetracarboxylic dianhydrides other than aromatic. [15] The liquid crystal alignment agent according to any one of [1] to [13] wherein the four acid dianhydrides are of the formula (H-1), (H-5), (H8)~ At least one of aromatic tetracarboxylic dianhydrides represented by (H1〇) and (H 22): 201125896

[16] The liquid crystal alignment agent according to any one of [1] to [[pi]], wherein the dihydro acid is an aromatic tetrahydro acid dianhydride represented by the formula (H-1): 0 0

Ο 0

The liquid crystal alignment agent of any one of [1] to [13], wherein the tetracarboxylic dianhydride is a mixture of the following compounds: formula (Η-1), (Η-5), (Η-8)~ at least one of aromatic tetracarboxylic dianhydrides represented by (H-10) and (H-22); and formula (S1), (S-6), (S-9) to (S) -10), (S-21) to (S-22), (S-30), (S-43) to (S-45), (S-48), and (S-52) At least one of tetracarboxylic dianhydrides.

Ο 〇 r\

(H-10) (H-22) 17 201125896 - · - r

[S-48] w [18]. The liquid crystal alignment agent according to [17], wherein the tetracarboxylic acid other than the aromatic group is the formula (S-1)' (s_6), (s_9), (S_45), (S-48; ^ (s, 5), at least one of the compounds of the formula [17]. The liquid crystal alignment agent according to [17], wherein the aromatic tetracarboxylic dianhydride is of the formula (H) The compound represented by the formula -1), the tetracarboxylic dianhydride other than the aromatic compound is at least one of the compounds represented by the formulae (S-1) and (S-48). [20] . A liquid crystal alignment film by which The coating film of the liquid crystal alignment agent according to any one of the above-mentioned items, wherein the liquid crystal display element has a pair of substrates, a liquid crystal layer formed between the pair of substrates, An electrode for applying a voltage to a liquid crystal layer, and a liquid crystal alignment film according to item [20]. The liquid crystal alignment agent of the present invention is a composition containing at least one polymer selected from the group consisting of polyacrylic acid and a derivative thereof. A derivative of polylysine, for example, 1) a polyanilin obtained by subjecting polylysine to a complete dehydration ring-closure reaction, 2) a part obtained by partially dehydrating a ring closure reaction of polylysine 201125896 The polyamidonic acid-polyamine copolymer and the 5-anhydride of the polyaniline obtained by replacing the four amines with the dicarboxylic acid A polyamido-imine which is obtained by partially or completely dehydrating one of the amine acid-polyamide copolymer. Preferred among these compounds are polydiamines and leucovorized polyamines, more preferably polyamidiamines. In the following description of the examples, 'polyamine' is used as a general term for poly-aracine and its derivatives unless otherwise specified.

Further, the polymer is a mixture of at least one diamine selected from the group consisting of diamines represented by formula (P) or a mixture of the diamine(s) and other diamines not represented by formula (P) with tetracarboxylic acid Poly-proline or its derivative obtained by the reaction of acid two needles.

(P) Ring P is pyridine-2,5-diyl, β-pyridazine_3,6-diyl, pyrimidine-2,5-diyl or pyridin-2,5-diyl' preferably η ratio Bite _2,5-diyl or tazin-3,6-diyl. And 'k is 0 or 1. That is, the diamine (ρ) is a 2-ring compound, but when it is a 2-ring, the ring P is a toluidine-2,5·diyl group at the 5-position with an amino bond, or an amino bond at the 5-position. The knot of pyrimidine _2 5-diyl. Preferred examples of the diamine (oxime) are shown below. More preferred of these diamines are diamines (Ρ-5) and (Ρ-8) 〇

Ηη2 (Ρ-2) (Ρ-4)

(P-6) ΝΗ 2 201125896

The monoamine (p) can be produced by a known method. For example, the method described in CN1733736A or CN101338462A can be used. The raw material diamine in the case of producing the polyamic acid used in the liquid crystal alignment agent of the present invention may be at least one diamine selected from the group consisting of diamines (P), and may further contain other diamines other than these diamines. At least one. That is, the ratio of use of the diamine selected from the group of fec(P), for example, in the proportion of the diamine raw material used in the production of polylysine, is preferably 1 〇 to 咖 m〇 1%, ^ good for 30~100 m〇l%. By setting the use ratio, the desired residual DC can be achieved in the liquid crystal display element. The other diamines can be classified into two types depending on their structures. That is, when the skeleton in which two amino groups are bonded is regarded as a main chain, it is a diamine having a radical (i.e., a chain group) and a diamine having no side chain group. By reacting a dimer having a side chain group with a tetracarboxylic dianhydride, a polylysine having a plurality of side chain groups relative to the polymer main chain can be obtained. By using such a side chain group (four) with respect to the polymer main chain, the liquid crystal alignment film formed of the liquid crystal alignment agent containing the polymer can increase the pretilt angle of the liquid crystal display element. That is, the side chain group has an effect of increasing the splaying. The side bond shoulder having a heterofilament is a group having 3 or more carbon atoms, and specifically, for example, an alkyl group having 3 or more carbon atoms, an alkoxy group having 3 or more carbon atoms, an alkoxyalkyl group having 3 or more carbon atoms, and a steroid having a steroid The base of the skeleton. The ring having one or more rings and having a terminal having a carbon number of 1 or more, an alkoxy group having a carbon number of 丨 or more, and an alkane having a carbon number of 2 or more 20 201125896 have an effect of having a side bond group. The diamines of these side chain groups are referred to as di-types. In the right, the diamine having a side chain group is sometimes referred to as a non-side chain type diamine. In some cases, it is necessary to combine the side chain type diamine with the non-side chain: = upper: = each element requires a vertical electric field as represented by the 乂 TN or VA mode.

= Therefore, a side chain type diamine is mainly used. At this time, the pretilt angle is controlled in advance, and the non-side chain type diamine can be used in combination. The ratio of the non-side chain type diamine to the side chain type diamine can be determined depending on the target pretilt angle. #然借配剂 Selecting the side chain base ' can also only make the chain type bribe. In the lateral & field mode, the pretilt angle is small and a high liquid crystal alignment property is required, so that at least one of non-side chain type diamines can be used. Thus, the liquid of the present invention can be applied to any type of liquid crystal display element. Specific examples of the side chain group are as follows. First, an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkenyl group, an alkenyloxy group, an alkenecarbonyl group, an alkenecarbonyl group, an alkene group can be exemplified. Oxycarbonyl, enaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylcarbonyl, and the like. Further, the alkyl group, the alkenyl group and the alkynyl group in these groups are each a group having a carbon number of 3 or more. However, in the alkyl group, the total carbon number is preferably 3 or more. Further, these groups may be linear or branched. Next, the terminal ring has an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms as a substituent, and 21 201125896 may, for example, be a stupid group or a benzene group. Base, phenylalkoxy, phenoxy, phenylcarbonyl, phenyloxyl, phenoxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexylalkyl, ring Hexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenoxy, bis(cyclohexyl)oxy, bis(cyclohexyl)alkyl, bis(cyclohexyl)phenyl, A cyclic structural group such as bis(cyclohexyl)phenylalkyl, bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenoxycarbonyl, or cyclohexylbis(phenyl)oxycarbonyl. Further, a collection ring group which is a group having two or more benzene rings, a group having two or more cyclohexane rings, or a group having two or more rings of a benzene ring and a cyclohexane ring is also exemplified. The binding group is independently a single bond, _〇---c〇0-, •OCO-, -CONH- or an alkylene group having a carbon number of 1 to 3, and the terminal ring has an alkyl group having 1 or more carbon atoms and a carbon number. 1 or more of a fluorine-substituted alkyl group, an alkoxy group having a carbon number of 丨 or more, or an alkoxyalkyl group having 2 or more carbon atoms is used as a substituent. The upper limit of the carbon number of these substituents is not particularly limited, and may be determined in consideration of manufacturing cost and physical properties. A group having a steroid skeleton can also be effectively used as a side chain group. A preferred example of the side chain type diamine is represented by the formula (νιΙΙα (χ)~(ΧΠΙ).

In the formula (VIII), Α3 is a single bond, -〇-, -CO-, -coo-, -OCO-, -CH20-, -CF2〇- or a mercapto group having a carbon number of 1 to 6, the sub-sinter Any -CHr· in the group may be substituted by -0, -CH=CH- or -OC-. Preferred examples of A3 are a single bond, -〇COO-, -0C0-, -CH20-, and an alkylene group having a carbon number of 1 to 3 22 201125896, and a particularly preferred example is a single bond, c〇〇_, _〇c〇 -, _CH2〇_, -CH2- and ·CH2CHr. ! ^ is a group represented by an alkyl group having an alkyl group having 3 to 30 carbon atoms, an alkyl group having a carbon number, or an alkoxy group having a carbon number as a substituent, or a formula (Ιχ), the carbon number 3~ Any -CHr in the 3-inch alkyl group can be replaced by _〇_. A preferred example of R1 is a styl group having an alkyl group having 3 to 30 carbon atoms, an alkyl group having a carbon number of SiO 2 or an alkoxy group having 1 to 3 〇 3 as a substituent, and a group represented by the formula (ι) . When the bonding position of the indole 3 is the i position, the bonding position of the two amino groups to the benzene ring is preferably 3 or 5 or 2 or 5.

In the formula (IX), A4 and A5 are independently a single bond, _〇...c〇〇-, -〇CO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and an oxyalkylene having a carbon number of 丨3. The group, or an alkyleneoxy group having 1 to 3 carbon atoms, is preferably a single bond or an alkylene group having a carbon number of 丨4. Ring B and Ring C are independently 1,4-phenylene or L4-cyclohexylene. R2 and r3 _ are independently fluorine or methyl. f and g are independently 0, 1, or 2, preferably 0. c, d and e are independently an integer 〇~2 and c, d and e are 1 or more in total. When c is 2, the two rings B may be the same or different, and the two A4 may be the same binding group or different bonding groups. When d is 2, two A5 groups may be the same binding group or different binding groups. Moreover, when e is 2, the two rings C may be the same or different. R4 is an alkyl group of a carbon number, an alkoxy group having 1 to 30 carbon atoms, or an alkoxyalkyl group having a carbon number of 2 to 30, and any hydrogen in the alkyl group, the alkoxy group and the alkoxyalkyl group. Can be replaced by fluorine. A preferred example of R4 is an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. 23 201125896

In the formulae (X) and (XI), 'R5 is independently hydrogen or a fluorenyl group. R6 is hydrogen, a carbon group having 1 to 20 carbon atoms or a rare carbon group having 2 to 20 carbon atoms. R7 and R8 are each independently an alkyl group having 1 to 20 carbon atoms or a phenyl group. A6 is independently a single key, -C0_ or _CHr. In the formula (X), preferably one of the two "NH2_Ph-A6-0-" is bonded to the 3-position of the steroid skeleton, and the other is bonded to the 6-position. Further, the bonding positions of the two amino groups and the stupid ring are preferably meta or para position with respect to the bonding position of A6. In the formula (XI), the bonding positions of the two "NH2_(R8-)Ph-A6-〇-, and the benzene ring are preferably meta or opposite to the carbon bonded to the steroid skeleton. Further, the bonding positions of the two amino groups to the benzene ring are preferably meta or para position relative to the bonding position of A6.

〇nh2 (10)) 24 201125896 R1〇 R11 H2N-r

In the formulae (XII) and (XIII), R is a decyl group having 1 to 3 carbon atoms, and any -CH2· in the alkyl group may be substituted by -Ο-, -CH=CH- or -esc-. R10 is a carbon group having a carbon number of 6 to 22, and R" is a carbon atom-based alkyl group. Eight 7 independent for _ 〇 or broken number Yao Ji. A8 is a single bond or a Wei group having a carbon number of 1 to 3. Ring T is a 1,4-subunit or a fluorene-cyclohexylene group. h is the bond between the amino group and the benzene ring, and it is a secret ride. The junction position of A7 is clearer. The knot position is the key of the phase lung and the bond of the benzene ring. The bond position of a is meta or para. - Mviii) has the following _. • 121^ (Vlll-2)

(VMM) H2N

(VIII-3) H2N0"c"OKX>r23 R23 h2n

25 201125896 h2n h2n \ > ^R23 y h2n (VIII-9) h2n (VIII-10) ) > -R23 h2n (VIII-11) In the formula (VIII-l)~(VIII-ll), R23 is carbon The alkyl group having 1 to 30 carbon atoms or the alkoxy group having 1 to 30 carbon atoms is preferably an alkyl group having 3 to 25 carbon atoms or a tertiary alkyl group having 3 to 25 carbon atoms. R25

R25 /

'c=〇

R25 0=C

5 XX JL X LI H2N' ^ΆνΗ2 HzN-^^NHz h2n^^nh2 η2ν^^νη2 (VIII-12) (VIII-13) (VIII-14) (VIII-15) r26 〇〆R26 u.NH2 uNH2 (VIII-16) (VIII-17) In the formulae (VIII-12) to (VIII-17), R25 is an alkyl group having 4 to 30 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms. R26 is an alkyl group having 6 to 30 carbon atoms, preferably an alkyl group having 8 to 25 carbon atoms. H2n h2n 0^\>27 0^K>27 H2N (VIII-19) h2n -r28 h2N (VI11-21) (VIII-18) H2N ,w"..., H2N A/III_1Q\ H2N h2n H2N (VIII- 20) H2N (VIM-21) 26 201125896

H2n

(VIII-23)

R27 (VIII-28) R·

27 (VIII-31) (VIII-32)

R‘ 27

CH3 ch3 II Si-O-Si-R27 II ch3 ch3 (VIII-37) In the formula (VIII-18) to (VIII-37), R27 is an alkyl group having 1 to 30 carbon atoms or an alkyl group having 1 to 30 carbon atoms. The oxy group is preferably an alkyl group having a carbon number of 3 to 25 or an alkoxy group having a carbon number of 3 to 25 27 201125896. R28 is hydrogen, fluorine, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -ON, -OCH2F, -OCHF2 or -OCF3, preferably an alkyl group having 3 to 25 carbon atoms, or Alkoxy group having a carbon number of 3 to 25.

Among the above diamines (VIII-1) to (VIII-43), preferred are diamines (VIII-1) to (VIII-11), more preferably diamines (VIII-2) and (νΐΠ_4) to (νΐΙΙ). -6). Specific examples of the diamine (X) are shown below. 28 201125896

29 201125896

30 201125896

Specific examples of the R23 R29 diamine (XII) are shown below.

R29

31 201125896 R30

In the formulae (XII-1) to (XII-3), R29 is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 3 to 30 carbon atoms or a carbon number of 3 ~30 alkoxy groups. In the formula (XII-4) to (XII-8), R3Q is an alkyl group having 1 to 30 carbon atoms or a carbon number of 32. 201125896 1 to 30 alkoxy group is preferably an alkyl group having 3 to 30 carbon atoms or carbon. Alkoxy groups of 3 to 3 Å. Specific examples of the monoamine (XIII) are shown below. H2n

Nh2 nh2 h2n

(XIII-3)

In the formula (XIII-I) to (xiii-3), r31 is an alkyl group having 6 to 22 carbon atoms, preferably a carbon group having 6 to 20 carbon atoms. R32 is a carbon group of carbon S1 to 22, preferably an alkyl group having 1 to 10 carbon atoms. In the specific examples of the above-mentioned side chain type diamine, preferred are diamines (VIII_2), (VIII-4) to (VIII-6), (XII-2), (χΠ-4), and (ΧΙΙ·6). . In order to exhibit a large pretilt angle in the liquid crystal display element, in the case of producing the polymer used in the liquid crystal alignment agent of the present invention, it is preferred to set the ratio of the above-mentioned side chain type diamine to the total amount of the diamine. It is m〇1%, more preferably 5~70 mol%. Preferred examples of the above diamine having no side chain group, i.e., a non-side chain type diamine, may be exemplified by the compounds represented by the formulae (I) to (VII) and (XV). h2n—X—nh2 (I) H2n n/ NH2 (")

H2n αΝ, (III) (IV) 33 201125896 z1 z2

In these formulas, X is a linear alkylene group having 2 to 12 carbon atoms. Y is independently a single bond, -0-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -C(CH3)2-, -C(CF3)2-,- 0-(CH2)t-0-, -S-, -SS-, -S02-, -S-(CH2)tS- or a linear alkylene group having 1 to 12 carbon atoms, and t is 1 to 12 Integer. Z1 and Z2 are hydrogen, but when Y is -NH-, -N(CH3)-, -CH2-, -C(CH3)2- or -C(CF3)2-, they may be bonded to each other to form a single bond. Ring d is a phenylene group or a 1,4-diazacyclohexylene group. R33 and R34 are each independently an alkyl group having a carbon number of 丨3 or a phenyl group. A3 is independently an alkylene group having a carbon number of 6, or a phenylene group substituted by an alkyl group. m is an integer of 1 to 1 。. Any hydrogen of the cyclohexane ring or the acyclic ring may be substituted by fluorine, methyl, trifluoromethyl, -OH, -C00H, _s〇3h, -P〇3H2, benzyl or benzyl. An example of the diamine (I) is shown below. H2N(CH2)2NH2 H2N(CH2)4NH2H2N(CH2)6NH2 (M) (IV) (1-3) Specific examples of the monoamine (II) are shown below. 34 201125896 H2N~{^NH2 H2N~Q-h (11-1) H2N-Γ ^|—NH2 (II-2) Diamine (III) Specific examples are shown below

Specific examples of the diamine (IV) are as follows: H2N-nh2 CH,

(IV-3) H2N-//-NH2 (IV-1) (IV-2) ch3 h2N-nh2 h3c (IV-4)

OH H〇 COOH h2nH^nh2 η2ν,v,nh: (IV-6) (IV-7) h2n ▽, νη9 (IV-8) HOOC h2n—^ -nh2 (IV-9)

Ho3s>

PO3H2

H2n-e v-nh2 2 H2hT V, NH2 (IV-11) (IV-12)

CF3 h2n nh2

Specific examples of (IV-17) diamine (v) are shown below. 35 201125896

H2N

(V-10)

(V-11)

(V-12) h2nh〇-°'sQ-nh2 h2n^Q-°'>0-nh2 (V-13)

(V-15) (V-14)

(V-17) (V-16)

(V-20) (V-21) H2n-〇~s_sh〇_nh2 ^~^ys^s^y~m2 (V-22) (V-23) 36 (V-24) 201125896 H2n-^s^ s^Knh2 (V-25)

Η2Ν-〇"8'ν^/"8^^_ΝΗ2 (V-26)

H3c ch3 h2n

NH, (V-29) O h2n- h2n H2N~^~^~S〇2~^ (V-31) (V-32) HV /0H OH OH II* ^^NH2 H2N^V^~C (V -33) (V-34) -nh2 (V-27) f3c h2ni

(V-

Specific examples of the diamine (νι) are shown below -nh2 h2n

(VI-2) l·1 nh2 PF3

30)

NHo (VI-1) 分 〇#nh2 h2N 〇 〇'

(VI-4)

NH〇 (VI-3) 37 201125896 H3C CH3H3C CH? (VI-5)

HzN /~NH, (VI-6) (VI-7) The specifics of the amine (VII) are as follows: Η^Λ// (VII-3) h3c ch; (VII-4)

M~QrQr\QrQr^ (VII-8) (VII-9) (VIMO) (VU-11)

H^°^ch^〇^NH2 HiLw〇^_N (VIM2) H3C ch3_~〇^〇^〇^〇~called „2(^^〇^〇分NH2 (VIM3) f3c cf3 (VII-14) ^^ The specific details of °'OxO^°'〇-nhj (VIM 5) diamine (XV) are shown below. (VII-16) nh2 38 201125896 ?h3 ch3 H2N-C3H6-Si-〇-Si-C3H6~N| -|, CH3 CH3 2 (XV-1) Among the above non-side chain type diamines, 'the preferred ones are diamines (ιν·ιΗιν·5), IV-WdV-n), 〇m)~(v_12), ' : :; 3), (V-35HV·37), ((4) (VH-5), and (predicate), the better is the second ν ι), (ιν_2), (ιν ι5) ~ (IV 17), (V-1)~(V-12), (V-33), (ν-3 5)~(ν-3 7), (VI-7), (VII-2)

And (XV-1) 〇 When the electrical characteristics such as the ion density of the liquid crystal display element are adjusted to a preferred range, such a non-side chain type diamine is used as a raw material of poly-branched acid in the liquid crystal alignment agent of the present invention. The total amount of the diamine is preferably from 1 to 98% by weight of the mole percent, more preferably from 10 to 95%, and still more preferably from 20 to 80%. As the diamine used in the present invention, diamines other than the diamines (I) to (VIH), (X) to (XIII) and (XV) can be used. Such a diamine is, for example, a diamine having an anthracene ring and a side chain diamine other than the diamines (VIII) to (XII).

Examples of the side chain type diamines other than the diamines (VIII) to (XII) are diamines (1,) to (g,). R35 h2n

(2*)

(1·)

39 201125896

The sputum and the heart are each independently a carbon number of 3 to 3 inches. The second derivative is used in the production of the polyamine 2 in the liquid crystal alignment agent of the present invention; it is used within the range of the degree of the effect of the present invention. ° = Polyurethane can also be added to the diamine in the monoamine. The molecular weight of the further-- or its derivative can be inhibited by adding the polymerization reaction of the step to the poly-proline, and the coating property of the liquid crystal alignment agent can be improved, for example, without losing the coating property. The addition ratio ^ __ molecular weight (four) should be adjusted. Two or more kinds of monoamines may be added without damaging the knot of the present invention. Examples of monoamines are aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octyl, n-decylamine, n-decylamine, n-decylamine, positive Dodecylamine, tridecylamine, tetrahedralamine, n-pentadecylamine, n-hexadecylamine, n-heptadesamine, n-dodecylamine, and tetradecylamine. In the present invention, when a diamine is reacted with a tetrabasic acid dianhydride to obtain a poly-branched acid, a mixture of a diamine selected from the group of diamines (P) and another diamine can be used as described above. In this case, one of the preferable examples of the other diamine is at least one selected from the group consisting of diamines (VIII) and (X) to (xm). Another preferred embodiment of the other diamine is at least one of the side chain type 201125896 diamine selected from the group consisting of diamines (vm) and (Χ)~(ΧΙΙΙ) and selected from the group consisting of diamines (Ι)~(νπ And (χ v) a group of non-side chain t-amines to: >, a mixture of species. The above items [4] to [7] are preferred examples of the combination of a diamine, a side chain type diamine and a non-side chain type diamine selected from the group consisting of monoamines (P). In the present invention, a polyglycine which is obtained by reacting a mixed diamine with a tetracarboxylic dianhydride as described above may be used as a polymer component, or a mixture of polyamic acids having different raw materials may be used as a polymer component. One of the preferred examples of the mixture of polyaminic acids is a mixture of polyaminic acids: at least one selected from the group consisting of diamines (p) and selected from the group consisting of diamines (Vm) and (χ) a mixture of at least one of the side chain type diamines of the group of ~(χπι), or a non-side of the group of diamines (1) to (VII) and (χ V) further added to the diamine mixture a polyamic acid obtained by reacting a mixture of at least one of a chain diamine with a tetracarboxylic dianhydride; and at least one of the non-side chain type diamine or at least one of the non-side chain type diamines and selected from the group consisting of Polylysine obtained by reacting a mixture of at least one of diamines of a group of diamines with tetracarboxylic dianhydride. The polymers shown in the above items [8] to [11] correspond to these polyaminic acid mixtures. Another preferred example of the mixture of polylysine is a mixture of polylysines: at least one of the diamines selected from the group consisting of diamines (oxime) and one selected from the group consisting of monoamines (I)~( a polylysine obtained by reacting a mixture of at least one of a non-side chain type diamine of VII) and (XV) with a tetracarboxylic dianhydride; and a selected from the group consisting of diamines (VIII) and (X) At least one of a side chain type diamine of the group (XIII) or a mixture of at least one of the side chain type diamines and at least one of the above non-side chain type diamines and a tetracarboxylic dianhydride Proline. The polymers shown in the above items [12] and [13] correspond to these polyamido acid mixtures. 41 201125896 The tetracarboxylic dianhydride used in the present invention may be a compound ' or a mixture of two or more compounds. The tetracarboxylic dianhydride may, for example, be an aromatic dianhydride or a tetracarboxylic dianhydride other than an aromatic compound. Examples of the aromatic ortho-tetracarboxylic dianhydride are an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic acid tetracarboxylic acid. Further, the aromatic tetracarboxylic dianhydride represents a divalent bond bonded to an aromatic group. a compound of water. The alicyclic four-reactive acid two-pin represents a compound obtained by dehydration of four carboxyl groups which are debonded from the rim group. Aliphatic sulphate sulphate sulphate The sulphate sulphate is not shown in the following.

(H-12) (H-13) Lu 42 201125896

ο (Η-22) Ο

Among the above aromatic tetracarboxylic dianhydrides, preferred are anhydrides (Η-1) (Η-5), (Η-8)~(Η-10) and (Η-22), particularly preferably anhydrides (Η). -1). Examples of the alicyclic tetracarboxylic dianhydride are shown below.

(S-3) Ο 0 Ο Ρ 0 0

〇 (S-1) (S, 43 201125896 ch3 CHa 0 ch3 ch3

y 0 1 / V Q: X 0 Ϊ ll 0 Λ) (S-8) (S-9) 0 〆0 0 , 0

0· r o (S-12) 0 X)C° °U S (S-15) 0 r 0 (S-16)

o o 0 (S-14) 0 c° π 0 (S-17) 0 Λ

(S-19)

0 (S-18) O

O O

(S-25)

0

<0

(S-20) O O

(S-29)

(S-35)

Ό

• 0 0

0 44 201125896 〇

〇 〇

〇 V 〇 π〇Χίπ Λ Ο 〇

(S-41)

(S-42)

Among the above alicyclic tetracarboxylic dianhydrides, preferred are anhydrides (S-1) to (S-5), (S-8) to (S-30) and (S-35) to (S-46). More preferably, it is an acid anhydride (S-1). Examples of the aliphatic tetracarboxylic dianhydride are shown below.

45 201125896

(S-53) and (S-52) = aliphatic four-two, preferably (four), (s_48)

The coating properties of the liquid crystal alignment agent are improved by the effect of the invention. When the polyamic acid is produced, it is also possible to add the two retinoids to the four test needles. Thereby, the polymerization reaction in the formation of the poly-aracine can be terminated, and the progress of the further progress of the polymerization can be suppressed. That is, the molecular weight of the obtained polymer (polyaracine) can be easily controlled, and for example, the ratio of the addition of the carboxylic acid anhydride can be appropriately adjusted without considering the molecular weight of the target polyglycolic acid. Further, # does not impair the effect of the present invention, and the type of the bis-alkaliic acid to be added may be more than one type. Examples of the dicarboxylic anhydride are maleic anhydride, o-arsenic acid, 2 anhydride, n-decyl succinic anhydride, n-dodecyl succinate, n-tetradecyl succinic anhydride, n-hexadecyl amber Anhydride and 1,2-cyclohexanoic acid ^ 46 201125896 Inventive towel 'in the manufacture of poly-acid, can also be added step by step. By adding a compound of monoisocyanate, the resulting polypyrene is modified to a modified 'molecular weight. # By using the terminal = proline, for example, the coating properties of the liquid crystal can be improved without impairing the effects of the present invention. From the above viewpoint, the addition amount of the monoisoxamic acid compound is preferably 1% relative to the total amount of the diamine and the tetrafine H. The mono-isocyanate compound is, for example, isocyanuric acid and naphthalene isocyanate.

The polyglycolic acid used in the present invention can be produced in the same manner as the known polyaminic acid used in the formation of the polyimide film. The total loading amount of tetralin is preferably about the same as that of one (four) total molars (mole ratio (10) ~ 丨). The molecular weight of the polyaraminic acid is preferably A 10, _~·, _, more preferably 2 Å to 2 Å, in terms of polystyrene-equivalent weight average molecular weight (Mw). The molecular weight of the poly-aracine can be determined from the measured values of the gel permeation chromatography (10) C). Polylysine can be confirmed by the presence of a large amount of a poor solvent to form a solid, which is then analyzed by IR or NMR. The polylysine is decomposed by an aqueous solution of a strong alkali such as KOH or NaOH, and the extract obtained by the organic solvent is analyzed by GC, HPLC or GC-MS to confirm the raw materials used. The liquid crystal alignment agent of the present invention may further contain other components than the above polyamic acid. The other components 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 Nadiimide compound from the viewpoint of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The content of the alkenyl-substituted nadir oxime 201125896 is preferably 0.01 to 0.50 based on the weight ratio of the poly-aracine in the liquid crystal alignment agent. The above-mentioned dilute-substituted nadirimine compound is preferably a compound which is soluble in a solvent for dissolving polyglycine or a derivative thereof of the present invention. A particularly preferred example of such an alkenyl-substituted nadirimine compound is a double {4-(allylbicyclo[2.2.1]hept-5-rare-2,3-dual rebellion represented by the formula (lna-1). N,N'-m-phenylenedifluoryl-bis(allylbicyclo[2.2.1]hept-5-ene-2, represented by the formula (Ina-2). 3-, direindolimine) and formula (Ina-3), n, N,-hexaindolyl-bis(dipropylbicyclo[2.2.1]hept-5-rare-2,3- Dicarboxy quinone imine).

Such a baked-substituted nadir-enamine compound can be used, for example, as described in Japanese Patent No. 2729565, wherein the diazide-substituted nadicarboxylic anhydride derivative and the diamine are in the range of 80 to 220. A compound obtained by reacting at a temperature of hydrazine for 0.5 to 20 hours or a commercially available compound. Further, for example, from the viewpoint of stabilizing the electrical properties of the liquid crystal display device for a long period of time, the liquid crystal alignment agent of the present invention may further contain a radically polymerizable unsaturated double bond other than the alkenyl-substituted nadirimine compound 48 201125896 compound of. The content of the compound having a radically polymerizable unsaturated double bond is preferably from 〇〇1 to 〇5〇, based on the weight ratio of the polyglycolic acid. The compound having a radically polymerizable unsaturated double bond may, for example, be a (meth) acrylate, a (meth) acrylamide derivative or the like, and a bismaleimide, and more preferably have a Further, the (meth) propyl acid derivative of the two or more radically polymerizable unsaturated double bonds, and the liquid crystal alignment agent of the present invention may further contain, for example, from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display device. Oxazine compound. The content of the oxazine compound to be added is preferably from 0.01 to 20% by weight based on the weight ratio of polyamic acid. The compound represented by the following formula (a) to (f) is exemplified by the oxime compound.

In the above formula, 'R1 and R2' represent an organic group having 1 to 30 carbon atoms. R3 to R6 represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. χ denotes a single bond, _〇_, _s_, _s s_, -S02-, -CO-, -CONH-, -NHCO-, -C(CH3)2-, -C(CF3)2-, _(CH2) m·, _〇-(cH2)m-〇-, or -S-(CH2)mS-. Here, m is an integer from 1 to 6. Y independently represents a single bond, _〇_, _s_, _c〇-, -c(ch3)2-, 49 201125896 ----r-C(CF3)2- or an alkylene group having 1 to 3 carbon atoms. Any hydrogen of the benzene ring and the naphthalene ring may be substituted by fluorine, methyl, -OH, -COOH, -S03H, or -P〇3h2. The oxazine compound can be produced by the same method as the method described in the publication of the Japanese Patent Publication No. 2004-009708, the Japanese Patent Publication No. Hei.

Further, the term "consideration from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element" may further contain a sulphur compound having the following oxazoline structure. Further, a compound having an oxirane group may be added, and a polymer other than polyamine may be added. In addition, various additives may also be added, for example: 1) a surfactant for achieving a related purpose may be added when it is desired to improve the coating property, 2) an antistatic agent may be added when antistatic is necessary to be improved '3) when it is desired to improve When the adhesion or the abrasion resistance of the substrate is increased, a decane coupling agent or a titanium coupling agent may be added, and 4) when imidization is carried out at a low temperature, a ruthenium-based catalyst or the like may be added. Further, for example, from the viewpoint of self-adjusting the coatability of the liquid crystal alignment agent or the concentration of the polyamic acid, the liquid crystal alignment agent of the present invention may further contain a solvent. The solvent is not particularly limited as long as it has a solvent capable of dissolving a polymer component. In other words, a plurality of solvents, such as a solvent which is usually used in the production step or use of a polymer component such as polyamic acid or a soluble polyimine, can be appropriately selected depending on the purpose of use. The solvent may be used singly or in combination of a plurality of solvents. Examples of the aprotic polar organic solvent which is a mother liquor for polyamic acid include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N_f-based 50 201125896 decylamine, N1-propionamide, N, N • dimethyl ethyl N, N-dimethyl ketoamine, N two “stone γ-butane vinegar and other internal fermentation. 6 base armenamine, diethyl acetamide, US r = Examples of other solvents for the purpose of coating, such as lactic acid, oxybutanol, tetralin, isophora, ethylene glycol monobutyl ether, ethylene glycol, and glycols such as diethylene glycol mono(10) Monofilament shouted acetic acid, three items, fine

Propylene glycol, propylene glycol monoalkyl ether, malonic acid-ethyl vinegar, etc., dipropylene glycol monoalkyl ether, dipropylene glycol mono (tetra), etc., acetates of these compounds Equivalent ester compounds. Particularly preferred solvents among these solvents are N methyl·2 kisses, N,N-dimercaptoacetamide, dimercaptopurine, γ_τ_, ethylene glycol monobutyl, and diethylene glycol monoethyl hydrazine. , two diol monobutyl hydrazine, propylene glycol monomethyl bond, and dipropylene glycol monoterpene. In the present invention, the concentration of the polymer component containing the polylysine in the liquid crystal alignment agent is not particularly limited, and is preferably 〇. When the liquid crystal alignment agent is applied onto a substrate, it may be necessary to previously dilute the polymer component contained in the solvent in order to adjust the film thickness. In this case, the viscosity of the polymer component is preferably 40 wt% or less from the viewpoint of adjusting the viscosity of the liquid crystal alignment agent to a viscosity suitable for mixing the solvent in the liquid crystal alignment agent. Further, the concentration of the above polymer component in the liquid crystal alignment agent can be adjusted according to the method of applying the liquid crystal alignment agent. When the method of applying the liquid crystal alignment agent is a spin coating method or a printing method, the film thickness is favorably maintained, and in many cases, the concentration of the polysiloxane composition is 10 wt% or less. It is also possible to further reduce the concentration by other coating methods such as dipping or ink jet. On the other hand, when the concentration of the polymer component is 〇·1 wt% or more, the film thickness of the obtained liquid crystal alignment film is easily optimized. Therefore, the concentration of the polymer component is 0.1% by weight or more, preferably 〇5 to 1% by weight, in a usual spin coating method or printing method. However, it can also be used at a lower concentration depending on the coating method of the liquid crystal alignment agent. Further, in the case of use in the production of a liquid crystal alignment film, the viscosity of the liquid crystal alignment agent of the present invention can be determined depending on the means 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 by using a printing machine, it is preferably 5 mPa or more from the viewpoint of obtaining a sufficient film thickness, and is preferably 1 μmpa from the viewpoint of suppressing printing unevenness. Below s, more preferably 10 to 80 mPa.s. When the liquid crystal alignment agent is applied by a spin coating method to form a film of a liquid crystal alignment agent, from the same viewpoint, it is preferably 5 to 2 Å mPa.s' or more preferably 10 to 1 Å mpa.s. The viscosity of the liquid crystal alignment agent can be reduced by dilution with a solvent or aging with stirring. 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 for producing a liquid crystal alignment film from a liquid crystal alignment agent. For example, the liquid crystal alignment film of the present invention can be obtained by the steps of forming a coating film of the liquid crystal alignment agent of the present invention. The step of heating and simmering. Regarding the liquid crystal alignment film of the present invention, the film obtained by the calcination 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 to a substrate of a liquid crystal display element in the same manner as in the production of a normal liquid crystal alignment film. 52 201125896 The substrate may be a glass-breaking substrate such as an indium tin oxide (IT〇) electrode or a color filter. A method of applying a liquid crystal alignment agent onto a substrate is generally known by a spin coating method, a printing method, a dipping method, a dropping method, an ink jet method, or the like. These methods are equally applicable to the present invention. The calcination of the coating film can be carried out under the conditions required for the polyphosphonic acid to exhibit dehydration and ring closure reaction. The simmered simmering is generally known as a method of heating (IV) for heating or infrared sniffer, a method of adding treatment on a hot plate, and the like. These methods are also applicable to the present invention, preferably at a temperature of about 150 to 300 ° C for 1 minute to 3 hours. The rubbing treatment can be carried out in the same manner as the 麾 2 treatment which is generally used for the alignment treatment of the liquid crystal alignment film, as long as the conditions for retarding the crystal of the present invention are delayed. The special condition is that the hair pressure is Q 2 to 〇 8 2, the moving speed is 5 to 250 mm/sec, the rotation speed of the roller is 5 〇〇 2, and the alignment treatment method of the liquid crystal alignment film is in addition to the rubbing method. = Knowing that there is a photo-alignment method or a transfer method. In the range in which the effect of the present invention (4) is obtained, these other alignment treatment methods can be used in combination in the rubbing treatment. The liquid crystal alignment film invented by Niu Mi can be obtained by a method (IV) which further includes other than the above steps. Such other steps are, for example, a method in which the drying frequency of the coating film is cleaned and the like, and the method of heat treatment is performed in the aging process. Suitable for the drying step. The dry step-free operation is preferably carried out at a temperature at which the solvent is evaporated, more preferably 53 201125896 is carried out at a lower temperature relative to the temperature of the simmering step towel. The cleaning method using the cleaning liquid for the liquid crystal alignment film before and after the alignment treatment may, for example, be brushing, spraying, jet cleaning or ultrasonic cleaning. (4) The method can be carried out separately or in combination. The cleaning solution may be pure water, or various alcohols such as decyl alcohol, ethanol, isopropanol, benzene, sulfonate, dimethyl strepene, etc., hydrocarbons, dioxins, bismuth solvents, propylene, etc. 'But it is not limited to these cleaning solutions. Of course, these cleaning fluids need to be thoroughly cleaned up. This cleaning method can also be applied to the cleaning step in 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 Å to 30 Å, more preferably from 30 to 15 Å. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as pulverized (pn) filGmetei·) or tree (elHpsGmeter). The liquid crystal display device of the present invention comprises a pair of substrates, a liquid crystal layer containing liquid crystal molecules formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film of the present invention for aligning the liquid crystal molecules with the mosquito (4). As the substrate, the glass substrate described in the liquid crystal alignment film of the present invention can be used, and the electrode can be an ITO electrode formed on a glass substrate as described in the liquid crystal alignment film of the present invention. The liquid crystal layer is formed of a liquid crystal composition sealed between substrates which are inside the liquid crystal alignment film surface. The liquid crystal composition to be used is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. A preferred liquid crystal composition having positive dielectric anisotropy is exemplified by Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei No. 5_5〇1735, No. 54 201125896, Japanese Patent Ping Ping 8·157826 private newspaper, (4) Foot Bulletin, Sakamoto Patent Special Kaiping & 44 44 Kaiping (ΕΡ885272Α1 manual), Japanese Patent Special Kaiping 9 ^ Newspaper (ΕΡ806466Α1 book), Japanese Patent Special Kaiping 819, Bulletin

L 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 _6 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 4报8^^^ I ITnn^'9 ^-104869 Winter patent special Kaiping 10_1ό 0 Shi baobao, Japanese 1 (Μ_3 bulletin, Japan Zhenzhan ^ newspaper, Japanese patent special open patent patent special Kaiping 1Q_2 ^^1 ( ) · 236989 bulletin, Japanese 1〇-23_ bulletin, Japanese patent ^ 报 newspaper, Japanese patent special open flat patent special open flat financial Lai = Ping 1G · 236993 bulletin, Japanese 1 〇 cut _ bulletin, 曰本 patent曰 专利 专利 专利 专利 专利 专利 专利 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Bulletin No. 5, 曰唬 曰唬 曰, 曰 专利 特 55 55 55 201125896 = No. 3 bulletin (EP967261A1 manual), day Japanese Laid-Open Patent Publication No. Hei. No. 2000-256307, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. The liquid crystal composition disclosed in Japanese Laid-Open Patent Publication No. 2001-019965, Japanese Patent Application Laid-Open No. Hei. Or a negative liquid crystal composition may be used by adding one or more optically active compounds. The liquid crystal display element of the present invention can form various liquid crystal display elements for electric field mode. a liquid crystal display element for applying a voltage to the liquid crystal layer in a horizontal direction with respect to a surface of the substrate, or the electrode is perpendicular to a surface of the substrate The liquid crystal layer

A vertical electric field mode in which a voltage is applied is used for a liquid crystal display element.

The liquid crystal display element for the transverse electric field mode may not exhibit a large pretilt angle. Therefore, in the liquid crystal display device for a transverse electric field method, a liquid crystal alignment film formed of a liquid crystal alignment agent containing a non-side chain type polyacrylic acid is used, which is a non-side chain type. Derived from diamines. The liquid crystal display element for the longitudinal electric field mode needs to exhibit a large pretilt angle. Therefore, in the liquid crystal display device for a vertical electric field method, a liquid crystal alignment film formed of a liquid crystal alignment agent containing a side chain type polyamic acid, which is a side chain type diamine or A mixture of diamines containing the side chain type diamine. 56 201125896 As described above, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can be suitably used in liquid crystal display elements of various displayless driving modes by suitably selecting a polymer as a raw material thereof. The liquid crystal display element of the present invention may further have elements other than the above-described constituent elements. As such other constituent elements, a polarizing film (polarizing film), a wave plate, and light scattering can be mounted in the crystal display element of the present invention.

The film, the driver circuit, and the like generally have (4) constituent elements in the liquid crystal display element. [Examples] The present invention will be illustrated by way of examples in which the compounds used are as follows. &lt;tetracarboxylic dianhydride&gt; Anhydride (H-1): both stearic acid dianhydride phthalic anhydride (Sl). 1,2,3,4-cyclobutane tetracarboxylic acid two-needle: acid anhydride (S_48 ··Ethylenediaminetetraacetic acid dianhydride: &lt;Diamine&gt; Diamine (1&gt;_5) : 2,5_bis(4-aminophenyl) 吼diamine core 8) : 2,5_double (4) Aminophenyl) diced diamine (^4): 4,4,-diaminodiphenylmethaneamine (V-7): 4,4,-diaminodiphenylethene-7) ·bis(4)amino group Phenyl)_1,4·diazacyclohexane 4 St) ( R29==n-heptyl)· U·bis(4 phenylaminophenyl)benzyl)-4-n-heptylcyclohexanebenzene • 卿 amino phenyloxy) amine (ΧΠ·6-1) (R30 di-n-heptyl): U · bis (4_(4-aminophenoxy) 57 201125896 phenyl)-4-(2-(正Heptylcyclohexyl)ethyl)cyclohexane DAPY: 2,6-diamino. Bipyridine DAPM : 2,4-diaminopyrimidine PPD 2 gas group _5_(4_Aminophenyl) mocking &lt;solvent&gt; NMP: N-methyl_2_pyrrolidone BC : butyl cellosolve (Ethylene glycol monobutyl ether) &lt;Synthesis of poly-proline acid&gt; [Synthesis Example 1] A diamine (P-5) was placed in a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet. 1.673 g and dehydrated NMP 3〇.〇g 'dissolved under a dry nitrogen stream. Next, 0.6984 g of an acid anhydride (H-1), 0.6280 g of an acid anhydride (s-1), and 70.0 g of a dehydrated NMP were added, and the mixture was reacted at room temperature for 15 hours. In the case where the reaction temperature rises during the reaction, the reaction temperature is suppressed to about 70. 〇 The following reaction. BC 1 〇 〇 g was added to the obtained solution to obtain a polyglycine solution having a concentration of 6 wt%. Polylysine was used as PA1 and its weight average molecular weight was 27,300. The weight average molecular weight of polylysine was determined by diluting the obtained polylysine with a dish of a disc acid-DMF (phosphoric acid/DMF = 0.6/100, weight ratio) to a concentration of about 2 wt%. Using a 2695 Sepamticm Module · 2414 differential refractometer (manufactured by Waters Co., Ltd.), the mixed solution was measured as a developing solvent by a GPC method, and converted to polystyrene. Further, the column was measured using HSPgel RT MB-M (manufactured by Waters Co., Ltd.) under the conditions of a column temperature of 50 ° C and a flow rate of 0.40 mL / min. 201125896 [Synthesis Examples 2 to 12] The polyamic acid solutions (PA2) to (PA12) were prepared based on Synthesis Example 1 except that the tetracarboxylic dianhydride and the diamine were changed in the manner shown in Table 1. The results including Synthesis Example 1 are summarized in Table 1. &lt;Table 1&gt; Synthesis Example Polyamine Acid Solution No. Anhydride Diamine Weight Average Molecular Weight Compound mol% Compound mol% 1 PA1 H-1 S-1 50 50 P-5 100 27,300 2 PA2 H-1 S-1 50 50 P-5 XII-4-1 90 10 27,600 3 PA3 H-1 S-1 50 50 P-5 Vl XII-4-1 50 40 10 31,000 4 PA4 H-1 S-1 60 40 P-5 Vl XII -4-1 50 40 10 30,400 5 PA5 H-1 S-48 50 50 P-5 Vl XII-4-1 50 40 10 39,200 6 PA6 H-1 S-1 50 50 P-5 V-7 XII-4 -1 50 40 10 27,000 7 PA7 H-1 S-1 50 50 P-5 VI-7 XII-4-1 50 40 10 28,200 8 PA8 H-1 S-1 50 50 P-5 Vl XII-6-1 50 40 10 29,400 9 PA9 H-1 S-1 50 50 P-5 Vl 30 70 35,500 10 ΡΑΙΟ H-1 S-1 50 50 P-5 Vl XII-2-1 30 60 10 32,400 11 ΡΑ11 H-1 S -1 50 50 P-8 100 29,000 12 PA12 H-1 S-1 50 50 P-8 XII-4-1 90 10 25,100 [Comparative Synthesis Examples 1 to 9] 59 201125896 Change four in the manner shown in Table 1. The polyaminic acid solutions (PA13) to (PA21) were prepared based on Synthesis Example 1 except for the carboxylic acid dianhydride and the diamine. The results are summarized in Table 2. <Table 2> Comparative Synthesis Polylysine Solution No. Sodium diamine Weight average molecular weight Compound mol% Compound mol% 1 PA13 S-1 ~~ 50 50 V-1 100 38,300 2 PA14 S-1 50 50 V- 7 100 45,000 3 PA15 H-1 S-1 35 65 V-1 100 40,200 4 PA16 H-1 S-1 50 50 DAPY 100 5,500 5 PA17 H-1 S-1 50 50 DAPM 100 2,000 6 PA18 H-1 S -1 50 50 PPD 100 2,400 7 PA19 H-1 S-1 50 50 V-1 DAPY 70 30 44,200 8 PA20 H-1 S-1 50 50 V-1 DAPM 70 30 35,700 9 PA21 H-1 S-1 50 50 V-1 PPD 80 20 33,900

A polyglycine solution (PA7) having a concentration of 6 wt% prepared in Synthesis Example 7 and a polyglycine solution (PA13 to PA15) having a concentration of 6 wt% prepared in Comparative Synthesis Examples 1 to 3 were 20/. The weight ratio of 80 (the former/the latter, solution 1 / solution 2) was mixed to prepare a liquid crystal alignment agent (PA22 to PA24). The composition ratios of PA22 to PA24 are summarized in Table 3. <Table 3> Polyproline solution No. Solution 1 Solution 2 Mix ratio (solution 1 / dissolve one' PA22 PA7 PA13 20/80 - PA23 PA7 PA14 20/80 PA24 PA7 PA15 20/80 ~~-~ --* -- 60 201125896 In a polyglycine solution (PA7) having a concentration of 6 wt% prepared in Synthesis Example 7, 'double {4_(ene is added in an amount of 1% by weight relative to the weight of the polymer, respectively) Propylbicyclo[2.2.1]hept-5-rare-2,3-dioxabenzimimine)phenyl}anthraquinone, 2-(3,4-epoxycyclohexyl)ethyltrioxene Liquid crystal alignment agent (PA25) based on sulphate, 4,4-methylene bis(indene, hydrazine diglycidyl aniline) or N,N_(1,2-di-diethylidene) bis acrylamide ~PA28). The composition ratio of PA25 to PA28 is summarized in Table 4. <Table 4> Poly-proline solution No. lysine solution No. Additive amount Wt% rA25 PA3, {4-(Lactyl propyl Ring [2.2.1]hept-5-rare-2,3-dicarboxyindenine)"phenyl}oxime 10 PA26 PA3 2-(3,4-epoxycyclohexyl)ethyl=decyloxy Decane 10 rA27 PA3 methyl bis(N,N-diglycidyl aniline) 10 PA28 PA3 \&gt; 1-(1,2-dihydroxy-ethylidene)-propionate 10 [ Example 1] &lt;Production of Liquid Crystal Display Element&gt; A polyglycine solution (PA1) having a concentration of 6 Wt% synthesized in Synthesis Example 1 was added by adding NMP/BC = 1/1 (weight ratio). The solvent was mixed and the whole was diluted to 4 wt% to prepare a liquid crystal alignment agent. A liquid crystal display element was produced as follows using the obtained liquid crystal alignment agent. <Method for Producing Liquid Crystal Display Element> Liquid crystal alignment by spin coating method The agent was applied to a glass substrate with a ruthenium electrode attached to Ermu' to form a film having a film thickness of 100 nm. After coating, it was dried by heating at 8 ° C for about 1 minute, and then at 210. (: 15 minutes under: Heat treatment to form a liquid crystal alignment film. Using a friction treatment device manufactured by Iinuma Gauge Manufacturig Co., 201125896, the amount of hair in the alignment cloth (hair length 18 nim: rayon) is 〇仙咖, The moving speed of the platform is mm/see, the viewing rotation speed is 丨, and the obtained liquid crystal alignment is processed under the condition of _ ah. New Zealand, after the liquid crystal alignment film is ultrasonically cleaned in ultrapure water for 5 minutes, at 12 Dry at 〇 ° C for 30 minutes. 于4 μιη of the gap material is spread on one glass substrate, and the surface on which the liquid crystal alignment film is formed is turned off, and the anti-parallel unit is sealed in the opposite direction so that the rubbing direction is antiparallel. . The composition of the crucible is placed under the field of the material, and the injection port is sealed with a light hardener. Next, heat treatment was performed for 30 minutes under ii 〇〇 C to produce a liquid crystal display element.

C5h” 17wt. %

F 16wt.«

F 10wt. % 5wt.%

6wt.% 62 201125896 ---C---

[Examples 2 to 19] Polyhexyl acid solutions (PA2 to PA12 and j&gt;a22 to PA28) having a concentration of 6 wt% as described in Table 1, Table 3 and Table 4 were added by adding NMP/BC = l/ The mixed solvent of i (weight ratio) was diluted to 4 wt% as a whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in the example. [Comparative Examples 1 to 9] The polyglycine solution (PA13 to PA21) having a concentration of 6 wt% as described in Table 2 was added by adding a mixed solvent of nmP/BC = 1/1 (weight ratio). The overall dilution was 4 wt%, and a liquid crystal alignment agent was prepared. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. &lt;Evaluation of electrical characteristics&gt; The liquid crystal display elements produced in Examples 1 to 19 and Comparative Examples 丨 to 9 were subjected to measurement of residual DC as follows. 1) Measurement of residual DC After the DC voltage of 3 v was superimposed on a rectangular wave of 30 Hz and 3 V for 30 minutes, the flash-eliminating voltage after 10 minutes was measured, and the absolute value of this value was taken as residual DC. Further, in the test method of the example of the present invention, it can be said that the residual DC is a value of 1 〇 mv or less. 63 201125896 <Table 5> Test No. Polyamine acid solution No. Residual DC (mV) after 10 minutes Example 1 PA1 6 Example 2 PA2 1 Example 3 PA3 0 Example 4 PA4 2 Example 5 PA5 3 Example 6 PA6 3 Example 7 PA7 1 Example 8 PA8 4 Example 9 PA9 2 Example 10 ΡΑΙΟ 1 Example 11 ΡΑ 11 5 Example 12 ΡΑ 12 1 Comparative Example 1 ΡΑ 13 38 ___ Comparative Example 2 PAH 55 Comparative Example 3 PA15 35 ____ Comparative Example 4 PA16 * Unable to measure -._ _Comparative Example 5 PA17 * Unable to measure - Comparative Example 6 PA18 * Unable to measure __Comparative Example 7 PA19 34 -.___Comparative Example 8 PA20 19 __Comparative Example 9 PA21 38 -__Example 13 PA22 9 -- Example 14 ~ PA23 4 ~~X Example 15 PA24 5 - Example 16 PA25 6 Example Π PA26 9 -^ Example 18 PA27 3 Example 19 ] PA28 0 * Unable to measure: Polyurethane solution has low viscosity, so it can cause friction scars. The residual DC was measured. As shown in Table 5, it can be seen that when a polyamine is produced by using a diamine (P) as a raw material, and a liquid crystal alignment agent containing the polyamic acid is prepared, a liquid crystal display having a liquid crystal alignment film obtained from the liquid crystal alignment agent is obtained. In the element, the result of lowering the residual DC is remarkable. [Simple description of the map] 64 201125896 None. [Main component symbol description] No 0

Claims (1)

201125896—f 7. Patent application scope: ^ L type liquid crystal alignment agent containing at least one polymer selected from the group consisting of polylysine and any other organism thereof, the polyglycolic acid is of the formula ( The diamine represented by P) or the mixture of the diamine represented by the formula (P) and another diamine is reacted with tetrahydro acid dianhydride: Wherein % P is pyridine-2,5-diyl, 嗒嗓_3,6-diyl, pyrimidine_2,5.diyl or pyrazine-2,5-diyl; k is hydrazine or 1; When 〇, ring p is pyridine-2,5-diyl or pyrimidine-2,5-diyl, and the bonding position of the amino group in these rings is 5 positions. 2. The liquid crystal alignment agent according to claim 1, wherein the diamine represented by the formula (P) is at least one of those represented by the formula (Ρ-1) to (Ρ-1〇): 3. The liquid crystal alignment agent according to claim 2, wherein the diamine represented by the formula (P) is at least one of the formulae (P_5) and (P_8). 4. The liquid crystal alignment 66 201125896 agent according to any one of claims 1 to 3, wherein the other diamine is selected from the group consisting of formula (VIII) and (X) to (XIII) having a side bond group. At least one diamine of the group of monoamines: R1 In the formula (VIII), 'A3 is a single bond, _〇_, _c〇~c〇〇_, 〇c〇·, c〇NH_, _αί2α, _α?2〇_ or an alkylene group having a carbon number of 1 to 6, Any avuo·, _ch==CH4_CeC_ substituted in the alkylene group; R1 is a group having a steroid skeleton, an alkyl group having 3 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms or a carbon number of 1 to 30. a phenyl group having an alkyl group as a substituent, or a group represented by the formula (Ιχ), and any one of the alkyl groups having 3 to 30 carbon atoms may be substituted by, for example, —CH=CH— or —OC—; In the formula (IX), 'A4 and A5 are independently a single bond, _〇_, _c〇〇_, _〇c〇_, -CONH-, an alkylene group having a carbon number of 1 to 4, and an oxygen group having a carbon number of 3 An alkyl group, or an alkyleneoxy group having 1 to 3 carbon atoms; a ring B and a ring c are independently a fluorene, a 4 phenylene group or a 1 4 4 _ cyclohexylene group; R 2 and R 3 are independently a fluorine or a fluorenyl group, and f and g are independently 〇, i or 2, and e are independent integers of 0 to 2, and c, d, and e total 1 or more 'when c is 2' 2 ring B may be the same or different, and 2 A4 may be the same combination The base may also be a different binding group; when d is 2, '2 A5 may be the same binding group or different bonding groups; when e is 2, 2 rings c may be the same or different; R4 is Carbon number 如~ such as alkyl group, 67 201125896 Alkoxy group having 1 to 30 carbon atoms or alkoxyalkyl group having 2 to 30 carbon atoms, in any of these alkyl groups, alkoxy groups and alkoxyalkyl groups Hydrogen can be replaced by fluorine; In the formulae (X) and (XI), R5 is independently hydrogen or a fluorenyl group, R6 is hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and R7 and R8 are independently a carbon number of 1 to 20 of Alkyl, or phenyl, A6 is independently a single bond, _c〇- or -CH2-; R9 In the formulae (XII) and (XIII), R9 is a fluorenyl group or an alkyl group having 2 to 30 carbon atoms, and any -CH2- of the alkyl group may be -〇-, -CH=CH- or -C三C- Substituted; R10 is an alkyl group having 6 to 22 carbon atoms; R11 is an alkyl group having 1 to 22 carbon atoms; A7 is independently an alkylene group having a number of -0 or 1 to 6 carbon atoms; and A8 is a single bond or a carbon number of 1 to An alkylene group of 3; a ring T 68 201125896 is a 1,4-phenylene group or a 1,4-cyclohexylene group; h is 0 or 1. 5. The liquid crystal alignment agent according to claim 4, wherein the other diamine is selected from the group consisting of formula (VIII-2), (VIII-4) to (VIII-6), (ΧΙΙ-2), ( At least one of diamines represented by ΧΙΙ-4) and (ΧΙΙ-6): (VIII-5) (VIII-6) R30 In the above formula, R23, R29 and R3G are independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. 6. The liquid crystal alignment according to any one of claims 1 to 3, wherein the other diamine is a mixture of diamines selected from the group consisting of the side chain described in claim 4 At least one selected from the group consisting of diamines, and at least one selected from the group consisting of diamines having no side chain groups represented by formulas (I) to (VII) and (XV); H2N-X-nh2 ( I) .R33 H2N—A3—[-Si—0 (XV) R33 Si——A3—NH2 R34 In the formula, X is a linear alkylene group having 2 to 12 carbon atoms; each Y is independently a single bond, -0-, -CO-, -NH-, -N (CH3) )-, -CONH·, -NHCO-, -C(CH3)2-, -C(CF3)2-, -0-(CH2)t-0-, -S-, -SS-, -S02-, -S-(CH2)rS- or a linear alkylene group having 1 to 12 carbon atoms, t is an integer of 1 to 12; Z1 and Z2 are hydrogen, but Y is -NH-, -N(CH3)-, ·&lt;:Η2-, -C(CH3)2- or -C(CF3)2· may also be bonded to each other to form a single bond; ring D is phenylene or 1,4-diazacyclohexylene R33 and R34 are independently a C 1~3 alkyl group, 201125896 - · - r - or a phenyl group; A3 is independently a C9-C6 alkylene group, a phenylene group, or a phenylene group substituted by an alkyl group. m; m is an integer from 1 to 10; any hydrogen of the cyclohexane or benzene ring may be fluorine, methyl, trifluoromethyl, -OH, -COOH, -S03H, -P〇3H2, benzyl or hydroxy Benzyl substitution. 7. The liquid crystal alignment agent according to claim 6, wherein the other diamine is a mixture of diamines selected from the group consisting of formula (VIII_2), (VIII-4) to (VIII-6), (Xli_2) And (XII_4) and (XII-6) at least one of a diamine having a side chain group, and a selected from the group consisting of a formula (ΙλΜ), (ιν_2), (ιν·15)~(IV-17), (V- 1) ~(V-12), (V-3 3), (V-3 5)~(V-3 7), (VI-7), (VII-2) and (XV-1) At least one of diamines having no side chain groups; (νΙ&quot;·2) (VIM) 71 201125896 In the above formula, R23, R29 and R3Q are independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms; 2N The liquid crystal alignment agent of claim 1, wherein the polyposition is a mixture of the following compounds: ^ selected from the formula (pl) of the scope of the patent application. ～(ρ_1〇) represents: a mixture of at least one of the group of amines and at least one selected from the group consisting of 2 groups of diamines having a side chain group described in claim 4, and reacting with tetracarboxylic acid a polylysine or a derivative thereof; and a polyamine obtained by reacting at least one selected from the group consisting of diamines having no side chain groups as described in claim 6 and tetracarboxylic dianhydride Acid ρ derivative. 9. The liquid crystal alignment agent according to claim 1, wherein the polymer is a mixture of the following compounds: (p·) to (ρ_1〇) selected from the second item of the patent application scope. a polydecylamine obtained by reacting at least one of a group of diamines and at least one selected from the group consisting of diamines having a side chain group in the fourth aspect of the patent range with tetracarboxylic dianhydride An acid or a derivative thereof; and a group of at least one selected from the group consisting of diamines having no fiber group described in claim 6 of the patent application and a group selected from the group consisting of diamines represented by the formula CMHIM0) Polyammonic acid or a derivative thereof obtained by reacting a mixture with tetrazoic acid. The liquid crystal alignment agent of claim 1, wherein the t compound is a mixture of the following compounds: a formula selected from the second item of the patent application scope (P-D~(1&gt;). _1 〇) indicates a group of diamines _ at least one species and at least one selected from the group consisting of diamines having a side chain group described in claim 4 of the patent application, and is selected from the application for the purpose of the 2011. a polyamido acid or a derivative thereof obtained by reacting a mixture of at least one of the group of diamines having no side chain groups described in the item with a tetracarboxylic dianhydride; and the non-side chain group A poly-proline or a derivative thereof, which is obtained by reacting at least one of a diamine with a tetra-acidic acid. The liquid crystal alignment agent according to claim 1, wherein the polymer is a mixture of the following compounds: At least one selected from the group consisting of diamines represented by the formulae (P-1) to (p-10) described in the second paragraph of the patent application, and selected from the group consisting of those selected in claim 4 At least one of the group of side chain diamines and selected from the sixth item of claim 5 a derivative of a polyamido acid obtained by reacting a mixture of at least one of a group of diamines having no side chain groups with a tetracarboxylic dianhydride; and a group selected from the group consisting of the diamine having no side chain group 12. At least one selected from the group consisting of a mixture of at least one of a group of diamines represented by the formula (ρ-υ~(ρ·ιο) and a polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride. The liquid crystal alignment agent of claim i, wherein the polymer is a mixture of the following compounds: (4) to (P, representing: at least a group of amine groups) and = a mixture of a group of diamines having no side chain groups as described in the sixth aspect of the patent, and an amino acid or a living organism thereof; and 74 201125896 derivatives. The liquid crystal alignment agent according to the above item 1, wherein the polymer is a mixture of the following compounds: a group selected from the group consisting of the diamines represented by the formula (p-ι) to (p_10) described in the second paragraph of the patent application. At least one of the group and two selected from the group consisting of the sixth aspect of the patent application a polyamido acid or a derivative thereof obtained by reacting a mixture of at least one of the group with a tetracarboxylic dianhydride; and A is obtained by a group having a side chain group selected from the fourth aspect of the patent application. At least one group of the group and an acid selected from the group of the diamines having no side chain group;; = a mixture of the mixture and the fermented amine agent obtained from the reaction of the four Wei and the two fields, and the range of the H in the JL range is 1~ The liquid crystal alignment as described in any of the three items, or the == at least two species of the four or two needles of the fragrant family, and at least two of the two livers of the second liver: at least one of the four acid acids other than the aromatic ones. The item "in the four practice two porch is the formula" - the liquid crystal alignment said the material family four and \\ Ρ η 夕 夕 - species: (ΗΜΟ) (Η-22) 75 201125896 '-~Γ—The liquid crystal alignment f in the No. 1 to 3 of the agent Li Fanyuan, the tetra-acid-- is the aroma of the formula (Η·1) Family reading acid two needles: (Η-1) 1 The liquid crystal alignment according to any one of Items 1 to 3 of the patent range, wherein the tetracarboxylic acid dianhydride is a mixture of the following compounds: At least one of the aromatic tetraacids represented by the formulas (Η-1), (Η-5), (Η·8)~(Η-10), and (Η·22); and the formula (S1), S-6), (S-9)~(S-10), (S-21)~(S-22), (S.3〇), (S-43)~(S-45), (S -48) and (S-52) at least one of tetradecanoic acid other than aromatic; (H-5) (H-8) (S-1&gt; (S-6) (S-9) (S-10) (S-21) (S-22) (S-30) (S-43) 76 201125896 18. The liquid crystal alignment agent according to claim 17, wherein the tetracarboxylic dianhydride other than the aromatic is a formula (S1), (S-6), (S-9), (S-45) At least one of the compounds represented by (S-48) and (S-52). 19. The liquid crystal alignment agent according to the invention of claim π, wherein the aromatic tetracarboxylic dianhydride is a compound represented by the formula (Η-1), and the tetracarboxylic dianhydride other than the aromatic is a formula (S) At least one of the compounds represented by -1) and (S-48). 20. A liquid crystal alignment film which is formed by heating a coating film of a liquid crystal alignment agent according to any one of claims 1 to 19. A liquid crystal display device comprising: a pair of substrates; a liquid crystal layer formed between the pair of substrates; an electrode for applying a voltage to the liquid crystal layer; and the liquid crystal alignment film of claim 20. 77 201125896 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the 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: