TW201237065A - Liquid crystal alignment agents for photo-alignment, liquid crystal photo-alignment layers, and liquid crystal displays using the same - Google Patents

Abstract

A liquid crystal alignment agent contains polyamic acid or derivative thereof obtained by reacting cyclobutanetetracarboxylic dianhydride or a mixture of tetracarboxylic dianhydride containg cyclobutanetetracarboxylic dianhydride with a specific diamine. The specific diamine contains at least two nitrogen atoms besides the nitrogen atom of the amino group in the molecular. The liquid crystal alignment agent is used to form a photo-alignment layer having good sensitivity of chemical variation caused by light irradiation, excellent alignmentability of the liquid crystal molecular, and high transparency. Furthermore, the photo-alignment layer is used in a liquid crystal display device capable of sustaining electric properties commonly needed in the liquid crystal alignment layer such as high voltage holding ratio, low ion contents, and low residual charge etc.

Description

[Technical Field] The present invention relates to a liquid alignment type liquid alignment agent using a photo-alignment method, and a photo alignment film and a liquid crystal display element using the same. [Prior Art]

Various display devices such as a display of a personal computer (monit〇r), a liquid crystal television, a viewfinder of a video camera, a projection display, and an optical printer head (optical printer head) In the optoelectronic related components such as optical epipolar transform (Opticai Fourier transform) elements and light valves, the mainstream of liquid crystal display elements that are currently commercialized and generally circulated is the use of nematic liquid crystals. Display component. TN (Twisted Nematic') mode, STN (Super Twisted) is widely known as a display mode of nematic liquid crystal display elements.

Nematic 'super twisted nematic) mode. In recent years, in order to improve one of the problems of these modes, that is, the narrow viewing angle, a TN-type liquid crystal display element using an optical compensation film and a MVA (Multi-domain Vertical Alignment) using vertical alignment and protrusion structure technology have been proposed. The vertical alignment mode or the IPS (in-piane switching) mode of the loose electric field mode is practical. In order for these liquid crystal display elements to have uniform display characteristics, it is necessary to uniformly control the molecular arrangement of the liquid crystals. Specifically, the liquid crystal molecules on the substrate are uniformly aligned in one direction; the liquid crystal molecules have a certain inclination angle (pretilt angle) from the substrate surface. This kind of action is the liquid crystal 201237065 40462pif alignment film. The liquid crystal alignment film is an important factor related to the display quality of the liquid crystal display element. With the improvement of the quality of the display element, the role of the liquid crystal alignment film has become important year by year. The liquid crystal alignment film is formed using a liquid crystal alignment agent. The liquid crystal alignment agent which is mainly used at present is a solution (varnish) obtained by dissolving polylysine or soluble polyimine in an organic solvent. After the solution is applied onto a substrate, a film is formed by heating or the like to form a polyimide film. As a method of imparting the property (alignment treatment) of the liquid crystal molecules to the film, a rubbing method is now industrially used. In the rubbing method, a cloth in which fibers such as nylon, rayon, or polyester are transferred is used to rub the surface of the liquid crystal alignment film in one direction, whereby uniform alignment of liquid crystal molecules can be obtained. However, in the rubbing method, there are problems in that a display defect caused by adhesion of shavings or fiber impurities or the like of the alignment film generated in the step or a thin film transistor (Thin-Film-Transistor 'TFT due to generation of static electricity) A display failure caused by destruction of components. In order to solve this problem, an optical alignment method in which light is applied to the formed film to perform alignment treatment has been proposed, and various alignments such as photodecomposition method, photo isomerization method, photodimerization method, and photocrosslinking method have been introduced so far. The mechanism (for example, refer to Non-Patent Document 1 and Patent Document 1 to Patent Document 5). The photo-alignment method has the following advantages: the uniformity of the alignment is higher than that of the rubbing method, and since it is a non-contact alignment method, the film is not scratched, and the display of the liquid crystal display element is reduced by dust or static electricity. The reason and so on. Although a large number of materials using a liquid alignment method using a light alignment method in 201237065 film (hereinafter sometimes referred to simply as "photoalignment film,") have been studied, it is reported that polyimine is used (the polyfluorene) The photoalignment film of the imine in which a tetracarboxylic dianhydride, especially a cyclobutane tetracarboxylic dianhydride is used as a raw material can align the liquid crystal molecules uniformly and stably (for example, refer patent document 1). The formed film is irradiated with ultraviolet rays or the like to impart a function of the polyimine which has a function of causing a chemical change to align the liquid crystal in a fixed direction. However, the photo-alignment film of this type has a problem of poor electrical characteristics. In other words, the amount of impurity ions is increased as compared with the alignment film by the rubbing method, and the voltage holding ratio is lowered. In order to solve this problem, various studies have been conducted on the molecular structure of the polyimine (see, for example, Patent Document 2 and Patent). Document 3) On the other hand, the photo-alignment method is referred to as burnt energy because of its small anchoring energy and poor alignment of liquid crystal molecules. In order to overcome this lack of P Mody.

The vanillo of the crystal display element is reduced. [Prior Art] [Patent Document 1] [Patent Document 1] The present invention has the following problems: the response speed of the liquid crystal display element is lowered or caused by 9-297313 publication 201237065 40462pif [Patent Document 2] Japanese Patent Laid-Open 2_· _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ [Non-Patent Document] • [Non-Patent Document U Liquid Crystal, Vol. 3, No. 4, p. 262, 1999] SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal alignment agent for forming a photoalignment film, The light alignment film has the following properties: it can maintain electrical characteristics required for a liquid crystal alignment film such as a high voltage holding ratio, a small amount of ions, and a small residual charge, and has good sensitivity to chemical changes of light irradiation and excellent alignment of liquid crystal molecules. High light transmittance. Another object of the present invention is to provide a photo-alignment film using the liquid crystal alignment agent and to provide a liquid crystal display element using the photo-alignment film. The present inventors have found that the use of poly-amic acid or a derivative thereof (the poly-tyranamic acid or a derivative thereof is a tetrabutyric acid or a cyclobutanic acid dianhydride) a chemical change of light-aligning film formed by a liquid crystal alignment agent formed by a liquid crystal alignment agent obtained by reacting a mixture of a diene acid and a needle with a specific diamine having at least two nitrogen atoms other than a nitrogen atom of a molecule in the molecule The present invention has been completed in terms of good sensitivity, excellent alignment of liquid crystal molecules, and high light transmittance. The present invention includes the following constitutions. [1] A liquid crystal alignment agent containing a tetracarboxylic dianhydride and a diamine to be reacted with 201237065 40462pif of a polyamic acid or a derivative thereof and used to form a liquid alignment film for photoalignment, wherein the tetrasodium oxyacid The needle comprises a tetrapoxic acid two-needle represented by the following formula (I); the diamine contains at least 1 selected from the group consisting of diamines represented by the following formula (N-1) and formula (N-2); Species

In the formula (I), RA to RD are independently hydrogen or an alkyl group having a carbon number of i to 4;

(N-1) In the formula (N-1), RE is independently an i-valent organic group; RF is independently hydrogen, a monovalent organic group or a halogen; and Z is a divalent group containing an alkylene group having 1 to 5 carbon atoms. base;

In the formula (N-2), RG is independently an i-valent organic group or a halogen; RH is independently a monovalent organic group; 201237065 40462pif m is independently an integer of 〇~3; and η is an integer of 〇~4. [2] The liquid crystal alignment agent according to the above [1], which contains an alkyl group having a size of 1 to 3 carbon atoms independently, and RF is independently hydrogen, carbon number 1 to 3 alkyl 2, chlorine Or a lysine or a derivative thereof obtained by reacting a diamine represented by the formula (N-1) or a mixture of an amine containing the diamine with a tetracarboxylic dianhydride. The liquid crystal alignment agent according to the above [1] or [2], which contains the formula (N-1) in which the respective para positions in the phenyl groups at both ends of the molecule have an amine group. A polyamine or a derivative thereof obtained by reacting a diamine or a diamine mixture containing the diamine with a tetracarboxylic dianhydride. [4] The liquid crystal alignment agent according to any one of the above [1] to [3], which contains an amine selected from the group consisting of the following formula: (n-1-20) Polylysine or a derivative thereof obtained by reacting at least one of the group or a diamine mixture containing the diamine with a tetracarboxylic dianhydride; h2n-^(Nl-1) H2N-^^^^ch2) h5j--Q)-nh2 (Nl-2) H2N—^ ^-/j-(ch2)3-/j-Qhnh2 (Nl-3) H2N—^ (Nl-4) H2N—(Nl-5) 9 20123706540462pif

^_λ24η2)-^2-^-ι η2ν-^^-^-(〇η2)4-Λ-<^-ι-o-^ c _ 〒3H7 C3H7_H〇KN - c3H7 c3h7 C3H7 C3H7~〇~N ^CH2)rN-〇^N

H2N h2n 2 h2n 2 2 h2n h2n h2n h2n c2h5 c2h 'j-(CH2)5-N C3H7 C3H7 j-ch2-n / C3H7 J-(CH2)irN- C3H7 J-(CH2)-N-

2

H2 h2

H2n 俨h7 C3H7 H2N—“—N—(CH2)HM

H2 h2 (Nl-6) (Nl-7) CN-1-8) (Nl-9) (Nl-10) (Nl-11) (Nl-12) (Nl-13) (Nl-14) (Nl -15) h2n

(N-l-16)

H2N

(N-l-17) h2n

(N-l-18) h2n

H2 (N-l-19)

H2N

The liquid crystal alignment agent according to any one of the above-mentioned items, wherein the RG is independently an alkyl group having a carbon number of 1 to 1 Å, a diamine represented by the formula (N-2) having a carbon number of 1 to 10, an alkoxy group, an aminomethyl sulfonyl group, a fluorine, a gas or a bromine, and rh is independently an alkyl group having 1 to 3 carbon atoms or containing the same Polylysine or a derivative thereof obtained by reacting a diamine mixture with a tetracarboxylic dianhydride. [6] The liquid crystal alignment agent according to any one of the above [1], wherein the formula (N-) which has an amine group in each of the phenyl groups at both ends of the molecule is contained. 2) Polyamine or a derivative thereof obtained by reacting a diamine or a diamine mixture containing the diamine with a tetracarboxylic dianhydride. [7] The liquid crystal alignment agent according to any one of the above [1], wherein the composition is selected from the following formula (N-2-1) to (N-2-15). a polyglycine or a derivative thereof obtained by reacting at least one of the groups of diamines or a diamine mixture containing the diamine with a tetracarboxylic dianhydride; 11 201237065 4U4bZpit

(N-2-1) (N-2-2) (N-2-3) (N-2-4) (N-2-5) (N-2-6) (N-2-7) ( N-2-8) s 12 201237065 40462pif

(N-2-9) (N-2-10) (N-2-11) (N-2-12) (N-2-13) (N-2-14) (N-2-15) [ (8) The hydrating alignment agent according to any one of the above items [1] to [6] which contains the formula and formula (N-2-2) described in the above item [7] And a derivative of at least one of the diamines or a mixture of the amines containing the diamine and the tetracarboxylic dianhydride. The liquid crystal alignment agent according to any one of the above-mentioned items, wherein the composition further comprises a formula selected from the group consisting of the following formulas (ΠΙ) to (Ιχ) and (XV) At least a mixture of diamines of the group of diamines represented by the group 13 201237065 40462pif Polyamic acid or a derivative thereof obtained by reacting tetracarboxylic dianhydride; H2N-A, -NH2id h2n''~^nh2 H2n nh2 h2n^-^ , nh2

H2n

(III) (IV) (V) (VI) (VII) (VIII) (IX) (XV) In the formula (III), A1 is -(CH2)m-, and m is an integer of 1 to 6; In (V), formula (VII) and formula (IX), X is a single bond, -0·, -S-, -ss-, -S02-, -CO-, -NH-, -N(CH3)- , -C(CH3)2-, -C(CF3)2-, -(CH2)m-, -0-(CH2)m-0-, or -S-(CH2)mS-, m is 1~6 In the formula (VII), L1 and L2 are -Η, but when X is -NH-, -N(CH3)-, -CH2-, -C(CH3)2-, or -C(CF3) 2-time can also be mutually

S 14 201237065 forms a single bond; in formula (VIII) and formula (IX), Y is a single bond, -0-, -S-, -C0-, -C(CH3)2-, -C(CF3 2, or an alkylene group having a carbon number of 1 to 3; in the formula (XV), R33 and R34 are independently an alkyl group having 1 to 3 carbon atoms or a phenyl group; and G is independently an alkylene group having 1 to 6 carbon atoms. a phenyl group or a phenyl group substituted by an alkyl group; m is an integer of 1 to 1 Å; and in the above formulas, the -H of the cyclohexane ring or the benzene ring may also be -F, -CH3, -OH, -COOH, _S03H, -Ρ03Η2, benzyl, or hydroxybenzyl. The liquid crystal west-directing agent as described in any one of the above-mentioned items [1] to [9] which contains a diamine mixture and a tetracarboxylic acid which further comprise a diamine having a side chain structure. A poly-proline or a derivative thereof obtained by reacting an anhydride. The diamine having a side bond structure is at least one selected from the group consisting of diamines represented by the following formulas (X) to (XIV); [11] The liquid crystal alignment agent according to the above [10] , among them,

In the formula (X), Z1 is a single bond, -CH2〇-n-〇ch2-> . an integer of ～6, uranium check-, -CO-, -COO-, -OCO-, -CONH- -CF20-, _〇Cf2_, or _(CH2)m_,m is i Any -CH2- in the alkylene group may also be substituted by -Ο-, -CH= 15 201237065 40462pif CH- or -CeC-; R3 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 an alkoxy group having 1 to 30 carbon atoms as a substituent, or the following formula (Xa) Any of the -CHr of the alkyl group having 1 to 30 carbon atoms may be substituted by -Ο-, -CH=CH- or -CeC-;

In the formula (Xa), 9 A2 and A3 are independently a single bond, -0-, -COO-, -OCO-, -CONH-, -CH=CH-, or a carbon number of 1 to 12, a and b is independently an integer of 〇~4; and ring B and ring C are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine- 2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl, or fluoren-9,10-diyl; R4 and R5 are independently - F or CH3, f and g are independently an integer of 〇~2; R6 is -F, -OH, -CN, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or a carbon number of 2~ Alkoxyalkyl group of 30, in these alkyl groups, alkoxy groups, alkoxyalkyl groups, any -H may be substituted by -F, and any -CHr may also be -CF2 or the following formula (s) Substituted by a divalent group; 201237065 40462pif

In the formula (S), R35 and R36 are independently a cyclyl group of carbon number 3, m is an integer of 1 to 6; c, d and e are independently an integer of 〇~3, and c + d+egl;

In the formula (XI) and the formula (XII), R7 is independently -H or -CH3; R8 is -Η, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms; Α4 is independently a single bond, _c〇- or -CH2·; In the formula (XII), R9 and R1G are independently an alkyl group having 1 to 20 carbon atoms or a phenyl group;

201237065 4U40ZplI

(XIII) (XIV) In the formulae (XIII) and (XIV), A5 is independently -O- or a carbon number of 1 to 6; in the formula (XIII), R11 is -Η or a carbon number of 1 Any alkyl group of -30, the -CH2- of the alkyl group may also be substituted by -0-, -CH=CH- or -C-C-; A6 is a single bond or an alkylene group having a carbon number of 1 to 3; T is 1,4-phenylene or 1,4-cyclohexylene; h is 0 or 1; in the formula (XIV), R12 is an alkyl group having 6 to 22 carbon atoms; and R13 is a carbon number of 1~ 22 alkyl. [12] The liquid crystal alignment agent according to any one of the above [1], wherein the liquid crystal alignment agent is further selected from the group consisting of the following formula (An-Ι) to (An-6). At least one of the groups of compounds is a tetracarboxylic dianhydride that reacts with a diamine;

18 S 201237065 40462pif

Ο Ο 〇Λυ1—G1—Υ^Ο ϊ Υ ο ο (Αη-2)

In the formula (An-Ι), formula (Αη-4) and formula (Αη-5), X1 is independently a single bond or -CH2-; in the formula (An-2), 'G1 is a single bond, carbon number 1 -20 of the appearance base, -CO-, -〇-, -S-, -SOr, -C(CH3)r, or -C(CF3)r; in the formula (An-2)~ (An-4 Wherein 'Y1 is independently one selected from the group consisting of the following three valent groups; > N-

X in the formula (An-3) ~ formula (An_5) towel 'ring £ represents the carbon number of 3 ~ 1 〇 of the early cyclic hydrocarbon base or carbon number 6 ~ 2 〇 Yi Yi ring, the base of any hydrogen It can also be substituted by thiol, ethyl or phenyl; 201237065 40462pif The bond attached to the ring can be attached to any carbon constituting the ring or to the same carbon; Λ 2 bonds in the formula (An-6) , X11 is a stretching base having a carbon number of 2 to 6;

Me represents a thiol group, and ph represents a phenyl group. [13] The crystal alignment agent according to any one of the above-mentioned items (1) to (11), wherein, further, a formula (2), a formula (2), a formula (5), and a formula (7) are further used. And at least one of the aromatic tetrazoic acid-inducing group represented by the formula (17) as a tetracarboxylic dianhydride which reacts with a diamine;

[14] The crystal alignment agent according to any one of the above items [n] to [n], wherein, further, the following formula (23) is used,

The formula of the formula (44), the formula (49) and the formula A and the tetramine dianhydride of the lipid group are used as the four-rebel dianhydride reacted with the diamine; eve 201237065 4U462pif

The liquid, the alignment agent according to any one of the above items [1] to [11], wherein the aromatic tetracarboxylic acid selected from the above item [13] is further used. At least one of the group of the dianhydrides and at least one selected from the group consisting of the alicyclic tetracarboxylic dianhydrides and the aliphatic tetracarboxylic dianhydrides described in the above [14] Reaction of tetracarboxylic dianhydride. [16] A liquid crystal alignment agent, which is a mixture of at least two of the liquid crystal alignment agents according to any one of the items [5] to [15]. The liquid crystal alignment agent of any one of the above-mentioned [1] to [16] further comprising an alkenyl substituted imide compound, an epoxy compound, and a decane selected from the group consisting of an alkenyl group. At least one of the coupling agents. [18] The liquid crystal alignment agent according to the above [17], wherein the alkenyl substituted ruthenium imine compound is selected from the group consisting of bis[4-(allylbicyclo[2.2.1]heptene_ 2,3-dicarboxy quinone imine)phenyl]methane, N,N,-m-phenylenedifluoryl-bis(10)propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine), and 21 201237065

At least one species of the group consisting of 4U40^piI N,N'-hexa-indenyl-bis(allylbicyclo[2 21]hept-5,2,3 dibasic]. [19] The liquid crystal alignment agent according to the above [17], wherein the dilute-substituted ruthenium imine compound is bis[4_(dipropylbicyclo[m]g-:-5-ene_2 , 3_dicarboxy quinone imine) phenyl] methane. [Claim] The liquid crystal agent according to any one of the above [19], wherein the inclusion amount is 0.01 with respect to the total amount of the polyaminic acid or a derivative thereof. Wt% to 50 wt% of an alkenyl-substituted ruthenium imine compound. [21] The liquid crystal alignment agent according to the above [[pi]], wherein the epoxy compound is selected from the group consisting of N, N, N', N, _ tetraglycidyl_m-xylylenediamine, 1,3- Bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N,,N,_tetraglycidyl-4,4'-diaminodiphenylnonane, 2_[ 4-(2,3epoxypropoxy)phenyl]-2-[4-[l,l-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl] Phenyl]propane, 3,4-epoxycyclohexenylmethyl-3,4'-epoxycyclohexenecarboxylate, N-phenylmaleimide-methyl propylene glycol glycidol At least one of the group consisting of a vinegar copolymer and 2-(3,4-epoxycyclohexyl)ethyltrimethoxylate. [22] The liquid crystal alignment agent according to the above [Π], wherein the epoxy compound is N,N,N',N,-tetraglycidyl-4,4'-diaminodiphenylanthracene Burning or 2-(3,4-ί ethoxy hexyl) ethyl tributoxylate. [23] The liquid crystal alignment agent 'wherein' according to the above [π], [21] or [22] is contained in relation to the total amount of the polyamic acid or a derivative thereof 1 wt% to 40 wt% of an epoxy compound.

The liquid crystal alignment agent according to the above item [17], wherein the ceramsite coupling agent is selected from the group consisting of ethylene tris oxide gas, and ethylene triethoxy oxime , Ν-(2.Aminoethyl)_3_aminopropylmercaptodimethoxydecane, N_(2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-amino Phenyl trimethoxy decane, p-aminophenyl triethoxy decane, m-aminophenyl trimethoxy decane, m-aminophenyl triethoxy decane, 3-aminopropyl trioxane Baseline, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxyoxydecane, 3-glycidoxypropylmercaptodimethoxydecane, 3-chloropropyl Methyldimethoxydecane, 3-propyltrimethoxydecane, 3-mercaptopropenyloxypropyltrimethoxydecane, 3·mercaptopropyltrimethoxydecane, N-(l,3_ At least one of the group consisting of dimercaptobutylidene)_3_(triethoxydecylalkyl)propylamine, and hydrazine, Ν'-bis[3-(trimethoxydecyl)propyl]ethylenediamine 1 species. [25] The liquid crystal alignment agent according to the above [[pi]], wherein the oxime coupling agent is 3-aminopropyltriethoxydecane. [26] The liquid crystal alignment agent according to the above [[pi]], wherein the inclusion of the polyamine or a derivative thereof is 0.1 wt% ~ 1 〇 wt% of Shi Xi Shao coupling agent. [27] A liquid crystal alignment film for photoalignment, which is formed by applying the liquid crystal alignment agent according to any one of the above [1] to [26] on a substrate, The step of heating and drying the substrate coated with the alignment agent, and irradiating the film with polarized ultraviolet rays. [28] A liquid crystal alignment film for photo-alignment, which is formed by the liquid crystal alignment agent 23 201237065 4〇462pif according to any one of the above items [1] to [26]. Step of Substrate_L The step of heating and drying the substrate coated with the alignment agent, irradiating the dried film with a step of irradiating the ultraviolet ray, and then heating and baking the film. [29] A liquid crystal alignment film for photo-alignment, which is formed by the following steps, wherein the liquid crystal alignment agent according to any one of the above [1] to [5] is disposed on a substrate, The step of heating and drying the substrate coated with the alignment agent, the step of heating and calcining the dried film, and the step of irradiating the film with polarized ultraviolet rays. [30] A liquid crystal display element according to any one of the above [27], wherein the liquid alignment film for photoalignment according to any one of the above [27]. [Effect of the Invention] According to the present invention, it is possible to obtain electrical characteristics such as high voltage holding ratio, small ion amount, and small residual charge, and the sensitivity of chemical change due to light irradiation is good, the alignment of liquid crystal molecules is excellent, and the light transmittance is high. Light alignment film. Further, it is possible to obtain a liquid crystal display element having excellent display characteristics of the photoalignment film. [Embodiment] The liquid crystal alignment agent of the present invention contains a reaction product of tetracarboxylic dianhydride and a diamine, that is, polylysine or a derivative thereof. The derivative of the poly-proline is a component which is dissolved in a solvent when a liquid crystal alignment agent to be described later is used as a solvent, and when the liquid crystal alignment agent is formed into a liquid crystal alignment film to be described later, it can be formed into a polyfluorene. A component of a liquid crystal alignment film containing an imine as a main component. Examples of such a derivative of polylysine include soluble polyimine, polyphthalate, and polyamine amide, and more specifically, 1) all amine groups of polyglycine Polyimine which is formed by dehydration ring closure reaction with a carboxyl group, 2)

S 24 201237065 40462pif Partially carried out a dehydration ring-closing reaction of a partial polyimine, 3) a polyglycolic acid is converted into an ester polyarylamine, 4) a tetras-acid dianhydride compound Dehydrating a part or all of the poly-proline-polyamine copolymer obtained by replacing a part of the acid dianhydride with an organic dicarboxylic acid, and 5) the poly-proline-polyamide copolymer A polyamidoquinone imine formed by a ring closure reaction. The polyamic acid or a derivative thereof may be one type of compound or two or more types. The tetracarboxylic dianhydride contains a tetracarboxylic dianhydride represented by the following formula (I).

The liquid crystal alignment agent of the present invention is applied onto a substrate, dried by preheating, and linearly polarized light that is irradiated with ultraviolet rays through a polarizing plate, and the polymer main chain substantially parallel to the polarizing direction is derived from the above formula ( The cyclobutane ring of the structural unit of the tetracarboxylic dianhydride shown in I) produces a photodecomposition reaction. Since the main chain of the polymer substantially parallel to the polarizing direction is selectively decomposed, the component oriented in a substantially right-angle direction with respect to the polarization direction of the ultraviolet ray to be irradiated becomes a dominant component in the main chain of the polymer forming the film. . Therefore, after the substrate is heated to dehydrate and close the polyamic acid to form a polyimide film, the liquid crystal molecules of the liquid crystal composition injected into the unit assembled using the substrate are irradiated with ultraviolet rays. The direction of the polarized light is in the direction of a right angle, and the long axis is aligned and aligned. The step of polarizing the film to ultraviolet light may be carried out before the heating step for polyimidization, or may be carried out after heating and polyimidization. RA to RD in the formula (I) are independently hydrogen or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms is specifically a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a t-butyl group. Preferably, ra to rd is hydrogen or a mercapto group, and more preferably hydrogen. The tetracarboxylic dianhydride represented by the formula (I) may be used alone or in combination of two or more. The tetracarboxylic dianhydride represented by the formula (Ί) may also be used in combination with other tetracarboxylic dianhydrides. The tetracarboxylic dianhydride represented by the formula (I) in the mixture of the tetracarboxylic dianhydride at this time may be used in a proportion of 10% by weight or more, preferably 50% by weight or more, and more preferably 80% by weight or more. The diamine contains at least one selected from the group consisting of diamines represented by the following formula (N-1) and formula (N-2). H2n

(f) m (f) m (N-1) (N-2) NH2 In the formula (N-1), RE is independently a monovalent organic group. Among the monovalent organic groups, an alkyl group is preferred, and an alkyl group having 1 to 3 carbon atoms is preferred. The alkyl group having 1 to 3 carbon atoms is specifically a mercapto group, an ethyl group, a n-propyl group, and an isopropyl group, and more preferably 26 201237065 40462pif is selected as a mercapto group. RF is independently hydrogen, a monovalent organic group or a halogen. Among the monovalent organic groups, an alkyl group is preferred, and an alkyl group having 1 to 3 carbon atoms is preferred. The alkyl group having 1 to 3 carbon atoms is specifically a mercapto group, an ethyl group, a n-propyl group, and an isopropyl group, and more preferably an anthracenyl group. The halogen is preferably fluorine, gas and bromine. Further, among these, hydrogen is more preferable. Z is a divalent group including an alkylene group having 1 to 5 carbon atoms, and preferably an alkylene group having 1 to 5 carbon atoms. The bonding position of the amine group in the phenyl group at both ends of the molecule may be arbitrary, preferably a para position and a meta position, and more preferably a para position. In the formula (N-2), RG is independently a monovalent organic group or a halogen. Among the monovalent organic groups, an alkyl group, an alkoxy group and an amine fluorenyl group are preferred. Among the alkyl groups having 1 to 10 carbon atoms, an alkyl group having 1 to 4 carbon atoms is more preferable. The alkyl group having 1 to 4 carbon atoms is specifically a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group, and more preferably a mercapto group. Among the alkoxy groups having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms is more preferable. The alkoxy group having 1 to 4 carbon atoms is specifically a decyloxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a third butoxy group, and more preferably It is a methoxy group. The halogens are preferably fluorine, gas and bromine. RH is independently a monovalent organic group. Among the monovalent organic groups, an alkyl group is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred. The alkyl group having 1 to 3 carbon atoms is specifically a mercapto group, an ethyl group, a n-propyl group, and an isopropyl group, and more preferably an anthracenyl group. m is independently an integer of 0 to 3. When m is an integer selected from 1 to 3, it is preferably 1 to 2, and more preferably 1. Preferably m is 0 or 1. When m is 2 or 3, RG may be the same or different. η is an integer from 0 to 4. When η is an integer selected from 1 to 4, it is preferably 1 to 2, and more preferably 1. η is preferably 0 or 1, more preferably 0. The bonding position of the amine group in the phenyl group at both ends of the molecule may be arbitrary, preferably in the para position and the meta position, and more preferably 27 201237065 40462pif is selected as the para position. Specific examples of the diamine represented by the formula (N-1) are compounds represented by the following formula (N-1-1) to the formula (N-1-20). H2n ( ch3 ch

N-CH

H2 (N-l-1) h2n

CH3 CH^/=\ N-(CH2)-N-NH2 (N-1-2) h2n

CH3 CH I n-(ch2 h2 (N-l-3) h2n

H2n

Ch3 9H -(ch2 ch3 ch I n—(ch2)

H2 (N-l-4)

H2 (N-1-5) h2n

C2h5 -ch2 h2n

C2H5 ____ -(CH2)2-fsJ-NH2

C2H5 H2N-^^~N-(CH2)5~N--N 2 2 (Nl-6) (Nl-1) (Nl-8) (Nl-9) (Nl-10) 201237065 40462pif C3H7 C3H7 (Ν -1-11) H2N—^ N—CH2~N~^ NH2 __ 〒3H7 C3H7_ H2N~^^-^_(CH2)2'^IH0-NH2 (Ν-1-12) χ=>. ^3Η ??3Η^=\ Η2Ν—Ν-(CH2)3~Ν-^~~^—ΝΗ2 (Ν-1-13) c3h7 c3h7 η2ν~^~^~Ν-(CHq-Ν-^~^~ΝΗ2 (Ν-1-14) 〒3Η7 C3H7_ η2Ν—(CH2)^—νη2 (Ν-1-15) Η2Ν~^~^一(Ν-1-16) Η2Ν—(CH2)2—^~^~~ ΝΗ2 (Ν-1-17) JH2 (Nl-18) η2ν 乂)η^η〇Η〇η2)3-^~^η^~ν

Η2 (Ν-1-20) A specific example of the diamine represented by the formula (Ν-2) is a compound represented by the following formula (Ν-2-1) to (Formula-2-15). 29 20123706540462pif

(N-2-1) (N-2-2) (N-2-3) (N-2-4) (N-2-5) (N-2-6) (N-2-7) ( N-2-8) 30 201237065 40462pif

(N-2-9) (N-2-10) (N-2-11) (N-2-12) (N-2-13) (N-2-14) (N-2-15) In a specific example, a diamine represented by the formula (Nl-2), the formula (njj), and the formula (N-2-2) is preferred. The diamine represented by the formula (N-1) and the diamine represented by the formula (N_2) may be used singly or in combination of two or more. The diamine represented by the formula (N-1) and the diamine represented by the formula (N2) may also be used in combination with the f-diamine. In the diamine mixture, the -amine represented by the formula (N) and the diamine represented by the formula (N-2) are used in a ratio of 10 wt% or more to 31 201237065, and may be used for 7 歳, more preferably 80. More than wt%. Examples of the amine, the diamine represented by the diamine, and the other diamine represented by the formula (Ν·2) include a diamine having no side chain structure and a diamine having a side chain structure. Such other diamine may be an anthracene compound or two or more compounds. The liquid crystal alignment agent of the present invention can be preferably used, for example, in a liquid crystal display device in which a liquid crystal molecule is aligned in parallel with a substrate and operated by an electric field, such as an IPS mode. In this case, it is not necessary to have the liquid crystal molecules have a pretilt angle with respect to the substrate surface, and therefore it is preferred to use a diamine having no side chain structure as the other diamine. The diamine having no side chain structure is at least one selected from the group consisting of diamines represented by the following formulas (III) to (IX) and (XV).

S 32 201237065

I v I H2N—A’—NH2i〇~x_0-

H2N"n~^NH H2N nh2 h2n^-^nh2

0^γνγΌΝΗ2 h2n

(III) (IV) (V) (VI) (VII) (VIII) (IX) (XV) In the formula (III), A1 is -(CH2)m-, and m is an integer of 1 to 6. In formula (V), formula (VII) and formula (IX), X is a single bond, -Ο-, -S-, -SS-, -S〇2-, -CO-, -NH-, -N (CH3)-, -C(CH3)2-, -C(CF3)2-, -(CH2)m-, -0-(CH2)m-0-, or -S-(CH2)mS-,m An integer from 1 to 6. In the formula (VII), L1 and L2 are -H, but when X is -NH-, -N(CH3)-, -CH2-, -C(CH3)2-, or -C(CF3)2- It is also possible to bond to each other to form a single bond. In the formulae (VIII) and (IX), Y is a single bond, -o-, -s-, -co-, -C(CH3)2-, -C(CF3)2-, or a carbon number of 1~ 3 alkyl groups. In the formula (XV), R33 and R34 are independently an alkyl group or a phenyl group having 1 to 3 carbon atoms, and G is independently 33. 201237065 40462pif an alkylene group having a carbon number of 1 to 6, a phenyl group or an alkyl group. Phenyl 'guar is an integer from 1 to 10. Further, in the above formulae, the -H of the cyclohexane ring or the benzene ring may be substituted by -F, -CH3, -OH, -COOH, -SO3H, -P〇3H2, benzyl or hydroxybenzyl. Examples of the diamine represented by the formula (III) include diamines represented by the following formulas (III-1) to (III-3). H2N-<CH2)2-NH2 H2N-<CH2)4-NH2 h2N-(CH2)6-nh2 (III-l) (III-2) (m.3) Diamine represented by formula (iv) For example, a diamine represented by the following formula (iv_i) and formula (IV-2) can be mentioned.

The diamine represented by the formula (v) is, for example, a diamine represented by the following formula (v_(V-3).

CH, which is represented by the following formula (VI-1): The diamine represented by the formula (VI) is, for example, a diamine represented by the formula (VI-17). 34 20123706540462pif h2n_

η2νΛΝΗ2 (VI-1) (VI-2) OH

H2

H2

PH

H2N~Ss // ~NH2

Hz iS h2n^^^nh2 (VI-6)

(VI-7)

H2Ah2 (VI-8)

(VM6) CF3 ΗζΝ-~NHz (Vl-17) The diamine represented by the following formula (VII-1) to the formula (VII-36) is exemplified as the diamine represented by the formula (VII). 35 201237065 40462pif H2NjOTxNH2 (VII-1)

(VII-4)

36 201237065 40462pif

(VII-30) (VII-28)

(VII-29)

HO OH

(VII-31) (VII-32) OH H /=\ /^X r hzn-\_m>-nh2 j uxa HO^ H〆\^'nh2 (VII-34) (VII-35) (VII-33 )

Examples of the diamine represented by the formula (VIII) include diamines represented by the following formulas (VIII-1) to (VIII-6). 37 201237065 40462pif

The diamine represented by the formula (IX) is, for example, a diamine represented by the following formula (IX-1) to (IX-16).

38 S 201237065 40462pif h2n

(IX-l) nh2

(ΙΧ·2)

Nh2

(IX-10) (CH2)6 Η2Ν^〇Ό^σΝΗ2

Nh2 h2n (IX-11)

(IX-12)

The diamine represented by the formula (XV) is, for example, a compound represented by the following formula (XV-1). 9h3 ?h3 H2N-C3H6-Si-〇-S Bu C3H6-NH2 ch3 ch3 (XV-1) 39 201237065 40462pif The liquid crystal of the present invention (4) may also be called liquid crystal molecules must be relative to two sides: for example, a pretilt angle In the liquid crystal display device of the formula, the Ϊ Γ H H shape can also be represented by a diamine represented by the formula (Ν-1) and a diamine having a side chain structure represented by the formula (Ν-2): use. Further, when the pretilt angle is to be appropriately adjusted, the diamine having no side chain structure and the diamine having a side flank may be mixed in the diamine represented by the formula ((6)) and the diamine represented by the formula (10)). Use both. The diamine having a side chain structure is at least one selected from the group consisting of diamines represented by the following formulas (X) to (XIV). R3 (X) Λ Η2Ν-ΐ^ΓΝΗ2 In the formula (X), Ζ1 is a single bond, -〇-, _c〇-, -COO-, -OCO-, -CONH-, -CH20-, -〇CH2- , -CF20_, _〇CF2·, or -(CH2)m-, m is an integer from 1 to 6 ' Any _CH2_ in the alkyl group can also be _〇_, _CH = CH- or -CsC- R3 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 an alkoxy group having 1 to 3 carbon atoms as a substituent, or the following formula The group represented by (Xa), any -CH2- of the alkyl group having 1 to 30 carbon atoms may be substituted by _〇_, _ch=CH- or -CeC-; 201237065

In the formula (Xa), A2 and A3 are independently a single bond, -Ο-, -COO-, -OCO-, -CONH-, -CH=CH-, or an alkylene group having a carbon number of 1 to 12, a and b is independently an integer of 0 to 4; ring B and ring C are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxoxa-2,5-diyl, ^ Bite ^^-diyl~^ than bite ^:-diyl'na-!^-diyl, naphthalene-2,7-diyl, or onion-9,10-diyl, R4 and R5 are independently - F or CH3, f and g are independently an integer of 0 to 2; R6 is -F, -OH, -CN, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or a carbon number of 2~ 30 alkoxyalkyl group, in these alkyl, alkoxy, alkoxyalkyl groups, any -H may also be substituted by -F, any -CH2- may also be -CF2- or the following formula (s Substituted by a divalent group; f \ R35 1 • T °7 1 —Si — I (s) R36 L R36 In the formula (s), R35 and R36 are independently an alkyl group having 1 to 3 carbon atoms. m is an integer of 1 to 6; c, d and e are independently integers of 0 to 3, and c + d + egl. 41 201237065 -τν/τν^μΑί·

In the formulae (XI) and (XII), R7 is independently -Η or -CH3; R8 is -Η, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms; Α4 is independently a single bond, - CO- or -CH2-; In the formula (XII), R9 and R1G are independently an alkyl group having 1 to 20 carbon atoms or a phenyl group.

S 42 201237065 X/ , ^ ▲ ^ on R11 A6

In the formula (XIII) and the formula (XIV), A5 is independently -Ο- or an alkylene group having 1 to 6 carbon atoms; in the formula (XIII), R11 is -anthracene or an alkyl group having 1 to 30 carbon atoms. Any -CH2- of the alkyl group may also be substituted by -Ο-, -CH=CH- or -CeC-; A6 is a single bond or an alkylene group having a carbon number of 1 to 3; Or a 1,4-cyclohexylene group; h is 0 or 1; in the formula (XR〇, R12 is an alkyl group having 6 to 22 carbon atoms; and, R13 is an alkyl group having 1 to 22 carbon atoms. Examples of the diamine represented by X) include a diamine represented by the following formula (X-1) to formula (X-37) and a formula (X-38) to (X-43): 43 201237065 40462pif

twenty four

twenty four

In the formula (X1) to the formula (X-ll), R23 is preferably 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 5 to 25 carbon atoms or a carbon number. 5 to 25 alkoxy groups. Further, R24 is preferably 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 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. 44 201237065 40462pif

(X16) (X-17) In the formula (X-12) to the formula (X-17), R25 is preferably an alkyl group having 4 to 30 carbon atoms, and more preferably an alkyl group having 6 to 25 carbon atoms. In the formula (X-16) and the formula (X-17), R26 is preferably an alkyl group having 6 to 30 carbon atoms, more preferably an alkyl group having 8 to 25 carbon atoms. 45 201237065

(X-21)

(X-24) (X-22)

(X-27)

46 201237065 40462pif

(X-29) (X-30)

In the formula (X-18) to the formula (X-37), R27 is preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably an alkyl group having 3 to 25 carbon atoms. Or alkoxy groups having a carbon number of 3 to 25. Further, R28 is preferably -F, a carbon number of 1 to 30, an alkoxy group having 1 to 30 carbon atoms, -CN, -〇CH2F, -OCHF2 or _OCF3, more preferably 3 to 25 An alkyl group having a burning group or a carbon number of 3 to 25. 201237065 HUHUZ-piJ.

The diamine represented by the formula (X) is preferably a diamine represented by the formula (X1) to the formula (χ_η), more preferably a diamine represented by the formula (χ·2) and the formula (Χ4) to the formula (Χ6). . In the formula (XI) ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- 6 I stand up. Moreover, the two amine groups are respectively linked to the position of the bond position of A or

S 48 201237065 40462pif. The diamine represented by the formula (XI) is, for example, a diamine represented by the following formula (XI-1) to formula (XI-4).

In the diamine represented by the formula (XII), in the formula (XII), two "NH2-(R1C)-)Ph-A4-0-" are bonded to the phenyl group, respectively, but preferably with respect to the bond. The carbon with a steroid skeleton is bonded to the meta or para carbon. Further, the two amine groups are bonded to the phenyl group, respectively, but it is preferably bonded to the meta or para position with respect to A4. Examples of the diamine represented by the formula (XII) include a diamine represented by the following formula (XII-1) to the formula (XII-8). 49 201237065 40462pif

50 s

201237065 HUHOZpiI

51 201237065

Nh2 In the diamine represented by the formula (XIII), in the formula (XIII), two amine groups are bonded to the phenyl group, respectively, but it is preferably bonded to the meta or para position with respect to A5. Examples of the diamine represented by the formula (XIII) include a diamine represented by the following formula (XIII-1) to (XIII-8).

S 52 201237065 R29

(ΧΠΙ-1) (ΧΠΙ-2) (ΧΠΙ-3) (ΧΠΙ-4) (ΧΙΠ-5) 53 201237065 40462pif

(ΧΠΙ-8) In the formula (XIII-1) to the formula (XIII-3), R29 is preferably -H, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably carbon. A number of 3 to 30 alkyl groups or a carbon number of 3 to 30 alkoxy groups. Further, in the formula (XIII-4) to the formula (XIII-8), R3G is preferably -H, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably 3 to 30 carbon atoms. 30 alkyl or an alkoxy group having a carbon number of 3 to 30. In the diamine represented by the formula (XIV), in the formula (XIV), 2

54 S 201237065 40462pit amine groups are bonded to the phenyl group, respectively, but are preferably bonded to the meta or para position relative to A5. The diamine represented by the formula (XIV) is, for example, a diamine represented by the formula (XIV-1) to the formula (XIV-3).

Η2ν (Xiv-i)

(XIV-2)

In the formula (XIV-1) to the formula (χΙν_3), r31 is preferably an alkyl group having 6 to 22 carbon atoms, and more preferably an alkyl group having 6 to 20 carbon atoms. R32 is preferably an alkyl group having _H or a carbon number of 1 to 22, and more preferably an alkyl group having a carbon number of 丨~(7). The diamine having a side chain structure is preferably a compound represented by the formula (χ_2), the formula (χ·4) ～ ((-6), the formula (ΧΙΙΙ-2), the formula (χιπ_4), and the formula (xnu). At least one of them. The other diamine in the present invention may be a diamine other than the diamine represented by the above formula (111) to formula (IX), formula (XV) and formula (X) to formula (XIV). Examples of such other diamines include a naphthalene type diamine having a naphthalene structure, a first type diamine having a first structure, and a side chain structure other than the formula (νίπ)~(() 55 201237065-·-r — Diamine. Examples of the other diamines include compounds represented by the following formulas (丨') to (8').

- R3S R3vf /R3S η^-〇^〇^νη2 (1.) (2·) O')

The number of carbon atoms is 3^3 (^ in the form of a liquid crystal alignment agent of the present invention, which is represented by the above-mentioned diamine in the diamine which is the polyamine of the other diamine. The ratio of the effect of the present invention to the degree of the other diamine may be 40 mol / or less, and the monoamine in the amine may be relative to the diamine. The formation of a polymerization reaction in which the termination step of the polymerization reaction is carried out by replacing a part of the diamine with a single termination.

S 56 201237065 40462pif Thus, the molecular weight of the obtained polymer (polylactoic acid or its coke bio) can be easily controlled by such substitution, and for example, the liquid crystal alignment can be improved without impairing the effects of the present invention. The scale damage and the effect of the present invention may be, for example, an aniline, a 4-anisidine, a cyclohexylamine, a n-butylamine, a n-pentylamine, a n-hexylamine or an n-heptylamine. N-octylamine, n-decylamine, n-decylamine, n-alkylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine n-pentadecylamine, n-hexadecyl Amine, n-heptadecylamine, n-octadecylamine, and n-icosylamine. In the present invention, mixed with tetrahydro acid dianhydride represented by formula (J), 四, = four rebellion The acid dianthracene is at least one selected from the group consisting of the following formula (a).

Vx1xH〇 (An-1)°γγ1<!>(An-3) A ° Υ ϊ 〇 ο (Αη-2) Ο

Ο

(Αη-4) Ph

(An-5)

Ph ph \ Ph 9〇:

Mev 〇- χΐν -Si

A

Si: , X11-

Me

Ph Ph (An-6) O (0 57 201237065 in formula (An-1), formula (An_4) and formula (A is a single bond or -CH2-; independent m in ^ (Μ 2) towel G疋 single bond, An exothermic group having a carbon number of 1 to 2 G, --, -〇-, -S〇2-, -C(CH3)2·, or -C(CF3)2_; in the formula (An-2) to the formula Un_4 Wherein γ1 is independently one selected from the group of valence groups; valley-b- > N-

Any gas of X may also be a sulfhydryl group or a di(4) group, which may also be bonded to a fine carbon of a structure, and two bonds are in the formula (An-6);

The Me table is dry and the alkyl group is 2~6; j.. " and Ph represents phenyl. Other tetracarboxylic dianhydrides can be used as compounds. The above-mentioned four kinds of compounds may be classified into two types of an anhydride, an alicyclic tetracarboxylic dianhydride, and the like, and may be roughly classified into an aromatic tetradecanoic acid tetradecane dianhydride. At least one of the two compounds which are bonded to the aromatic 9 as follows: The carboxyl group formed by 58 201237065 40462pif anhydride. The aromatic tetracarboxylic dianhydride may, for example, be a compound represented by the following formulas (1) to (18). Ο Ο 0 0 0

59 201237065 40462pif

The aromatic tetracarboxylic dianhydride is preferably a compound represented by the formula (1), the formula (2), the formula (5) to the formula (7), and a formula (1), and more preferably represented by the formula (1). Compound. The alicyclic tetracarboxylic dianhydride refers to a compound in which at least one of the two acid anhydrides is an acid anhydride formed by two slow groups bonded to the alicyclic compound. Examples of the alicyclic tetra-baric acid dianhydride include the following formulas (24) to (34), formula (36) to formula (40), formula (42) to formula (44), and formula (49). A compound represented by the formula (58) and the formula (62) to the formula (64). 201237065 40462pif

(31) (32) (33)

61 201237065 40462pif

The alicyclic tetracarboxylic dianhydride is preferably a compound represented by the formula (25), the formula (36) to the formula (39), the formula (44), the formula (49), and the formula (68), and more preferably A compound represented by the formula (37) and the formula (49). The aliphatic tetracarboxylic dianhydride is a compound having two acid anhydrides formed by two carboxyl groups bonded to an aliphatic compound. Examples of the aliphatic tetracarboxylic acid dianhydride include compounds represented by the following formula (23), formula (45) to formula (48), formula (66), formula (67), and formula (68). 62 201237065

The aliphatic tetracarboxylic dianhydride is preferably a compound represented by the formula (23) and the formula (68). The tetracarboxylic dianhydride may also be substituted with a part of the dicarboxylic acid monoanhydride. Such substitution can cause termination of the polymerization reaction in the formation of poly-proline, and can inhibit the progress of further polymerization. Therefore, the molecular weight of the obtained polymer (polyglycine or a derivative thereof) can be easily controlled by such substitution, and the coating property of the liquid crystal alignment agent can be improved, for example, without impairing the effects of the present invention. The ratio of the dicarboxylic acid monoanhydride to the tetracarboxylic dianhydride is not particularly limited as long as it does not impair the effects of the present invention, and the standard is preferably 10 mol% or less of the total amount of the tetracarboxylic dianhydride. The tetracarboxylic dianhydride which is substituted with the dicarboxylic acid monoanhydride may be one type or two or more types as long as the effects of the present invention are not impaired. Examples of the dicarboxylic acid monoanhydride include maleic anhydride, phthalic anhydride, Yikang 63 201237065 40462pif oxime anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride , n-hexadecyl succinic anhydride, and cyclohexane dicarboxylic anhydride. As the tetracarboxylic dianhydride, a part of the tetracarboxylic dianhydride may be replaced with a di-lower acid in a range of 10 m% or less of the dicarboxylic acid to the tetracarboxylic dianhydride. The tetracarboxylic dianhydride which is substituted with the dicarboxylic acid may be one type or two or more types as long as the effect of the present invention is not impaired. The poly-proline or a derivative thereof of the present invention may further contain a monoisocyanate compound in its monomer. The molecular weight is adjusted by the modification of the terminal of the polyamic acid or the derivative thereof obtained by containing the monoisocyanate compound in the monomer. By using the terminal modified polyglycine or a derivative thereof, for example, the coating properties of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. From the viewpoint of the above, the content of the monoisocyanate compound in the monomer is preferably from 1 mol% to 10 mol% based on the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. The poly-proline or the derivative thereof of the present invention can be produced in the same manner as the known polyglycine or a derivative thereof used for the formation of the polyimide film. Preferably, the total addition amount of the tetracarboxylic dianhydride is approximately equal to the total number of moles of the diamine (the molar ratio is about 0.9 to 1.1). The molecular weight of the polyaminic acid or its derivative of the present invention is preferably 10,000 to 500,000 ', more preferably 20,000 to 200,000, based on the weight average molecular weight (Mw) in terms of polystyrene. The molecular weight of the poly-araminic acid or its derivative can be determined by measurement by a gel permeation chromatography (GPC) method. 64 201237065 40462pif The poly-proline or the derivative thereof of the present invention can be confirmed by the fact that it is precipitated by a large amount of a poor solvent by IR or NMR to obtain a solid matter for analysis. Further, the poly-proline or a derivative thereof is decomposed with an aqueous solution of a strong base such as KOH or NaOH, and the extract extracted from the decomposition product with an organic solvent is analyzed by GC, HPLC or GC-MS. The monomer used can be green. The liquid crystal alignment agent of the present invention may further contain other components than the polyamine or its derivative. The other components may be one type or two or more types. For example, from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display device for a long period of time, the liquid crystal alignment agent of the present invention may further contain an alkenyl substituted imide compound. The alkenyl substituted imide compound may be one type of compound or two or more types of compounds. From the above viewpoints, the content of the alkenyl-substituted ruthenium imine compound is preferably 0.01 to 1.00, more preferably in terms of the weight ratio of the polyaminic acid or the derivative thereof in the liquid crystal alignment agent. 0.01 to 〇70, further more preferably 〇〇1 to 0.50 The alkenyl substituted imide compound is preferably a compound which is soluble in a solvent which dissolves the polyamine used in the present invention. A solvent for an acid or a derivative thereof. The compound represented by the following formula (Ina) is exemplified as an example of such an alkenyl-substituted quinone imine compound. 65 201237065 40462pif

In the calcined formula (Ina), 'LlA L2 is independently hydrogen, an alkenyl group having a base number of 1 to 1 knot, a cycloalkyl group having a carbon number of 5 to 8, and a chiral 1 or 4 2 . Dilute base = Japanese temple, W denotes a carbon number of 1 to 12, a carbon number of 2 to 1 group: a ring number of 5 to 8, an aryl group having a carbon number of 6 to 12, and a base group (f〇) r_Z3_H (Zl, ~Z3 are independently carbons of 2 to 6: q or an integer of rW~30), and the bases of 8 to 8 are independent of carbon atoms of 1 to 4 or carbon. Number of stretched wire, B is phenyl, and 8 is GW). ^ -B_H (B is phenyl), and T is -CH2-, -C(CH3)2-, _S· or A group represented by S(V) or a group in which one to one of these groups is substituted with a hydroxyl group. In this case, preferred W is a carbon group having 1 to 8 carbon atoms and an alkenyl group having 3 to 4 carbon atoms. a cyclohexyl group, a phenyl group, a benzyl group, a poly(ethylideneoxy)ethyl group having a carbon number of 4 to 1 fluorene, a phenyloxysilyl group, a phenylmethyl group, a phenylisopropylidenephenyl group, and A group in which one or two hydrogens of these groups are substituted by a hydroxyl group. In the formula (Ina), when n = 2, w is an alkylene group having a carbon number of 2 to 2 Å, and a carbon number of 5 to 8 a cycloalkyl group, an arylene group having a carbon number of 6 to 12,

66 S 201237065 4U4D2pir (ζ 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ^ ^ ^ B ^ ^ ^ ^ B B B B B B B B B B B B B B B B B B B B B B sB- (Β denotes a phenyl group, Τ is a carbon number 1 to 3 extension group, _〇_ or s〇2_ 's is a base represented by 0 or ο, or 1 to 3 hydrogens of these groups are a group obtained by substituting a hydroxy group. At this time, 'preferred W is an alkylene group having 2 to 12 carbon atoms, a stretched hexyl group, a phenyl group, a phenylene group (toIylene), a benzene dimethyl group (a substance, - C3H6-0-(Z2-〇)r〇-C3H6- (Z2 is a stretching group of carbon number 2~6, 犷 is 1 or 2), _Β_Τ·Β_(Β indicates phenylene, and The group represented by -CH%, -〇- or s〇2-), _b 〇b C3H6 Β 〇Β (Β is a phenyl group), and the two or two hydrogens of these groups are A group substituted with a dilute group. For example, as described in Japanese Patent No. 2729565, an alkenyl-substituted carboxylic acid anhydride derivative and a diamine can be used. 8 (rc~22 (the compound obtained by synthesizing 〇 for 5 hours to 20 hours at rc temperature or commercially available) Specific examples of the thiol-substituted ruthenium-imine compound include the following compounds: N-mercapto-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium imine, N-fluorenyl allyl fluorenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N. fluorenyl-hydrazinopropyl bicyclo [2.2. 1]g·5·ene 2,3—dicarboxy quinone imine, fluorenyl-fluorenyl-methylallyl fluorenylbicyclo[2.2 ^g ^•women-2,3_dicarboxy quinone imine, hydrazine - 〇ethylhexyl)-allyl bicyclic carboxy quinone imine, 67 201237065 40462pif N-(2-ethylhexyl)-allyl (indenyl)bicyclo[2.2.1]hept-5-ene-2, 3_ Dicarboxy quinone imine, N-allyl-allyl bicyclo [2.2.1] hept-5-ene 2,3 · dicarboxy quinone imine, Ν-allyl-allyl fluorenyl double ring [2.2.1]Hept-5-ene-2,3-dicycloheximide, fluorene-dilyl-decylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium imine, oxime-isopropenyl-allyl bicyclo [2.2.1] g _5_ dilute 2,3-di-refenyl imine, Ν-isopropyl-dilyl (fluorenyl) bicyclo [2 2 1] G--5-rare-2,3-di-reborn, imine-isopropenyl-hydrazinyl-propylbicyclo[2.2.1] g--5 - dilute-2,3-di-reactive iodide, fluorene-cyclohexyl-allyl bicyclo [2.2.1] g _5_ dilute _2,3-dicarboxy quinone imine, Ν-cyclohexyl olefin Propyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, fluorene-cyclohexyl-fluorenyl propyl bicyclo [2.2.1] hept-5-ene - 2,3-Dicarboxy quinone imine, phenyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, Ν-styl-allyl (methyl Bicyclo[2.2.1]hept-5-ene-2,3_disuccinimide, fluorenyl-allyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Imineimine, Nf-propyl-propylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-nodyl-mercaptopropyl double ring [2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-(2-hydroxyethyl)-allylbicyclo[2.2.1]heptene_2,3_disuccinimide, N -(2-transethylethyl)-allyl (indenyl)bicyclo[2.2.1]glycol-5-dihydrosulphate, N-(2-ylethylethyl)-fluorenyl Bicyclo[2 2 1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2,2-dimercapto-3-hydroxypropyl)-allyl bicyclo [2.2.1] Gg _5-return _2,3_di-rebel quinone imine, N-(2,2·didecyl-3, propylidene)-allyl ( Methyl)bicyclo[2.2.1]hept-5-ene-2,3-disulfhydrylimine, N-(2,3-dipropylpropyl)-propylpropylbicyclo[2.2.1]g -5-diluted-2,3-dihydrofuranimide, team (2,3_68 201237065 dihydroxypropyl)-allyl (indenyl)bicyclo[2.2.1]hept-5-ene-2, 3-Dicarboxy quinone imine, N-(3-hydroxy-1-propenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4 -hydroxycyclohexyl)-allyl (indenyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-hydroxyphenyl)-allylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-hydroxyphenyl)-allyl(methyl)bicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine, N-(4-hydroxyphenyl)-mercaptopropyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-(4 -hydroxyphenyl)-mercaptoallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(3-hydroxyphenyl)-allylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(3-hydroxyphenyl)-allyl(indenyl)bicyclo[2.2.1]hept-5-ene_2 , 3-dicarboxy quinone imine, N-(p-hydroxybenzyl)-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, hydrazine {2-(2-Hydroxyethoxy)ethylbuallylbicyclo[2.2.1]hept-5-ene-2,3-di-rebasic imine, Ν-{2-(2-hydroxyethyl) Oxy)ethylbuallyl (indenyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, Ν-{2-(2-hydroxyethoxy)ethyl }-Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, :ν_{2-(2-hydroxyethoxy)ethyl}-decyl ally Base bisbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, Ν-[2-{2-(2.hydroxyethoxy)ethoxy}ethyl]-ene Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, Ν-[2_{2-(2-carbethoxyethoxy)ethoxy}ethyl]-allyl (Methyl)bicyclo[2 2 ^heptene·2,3-dicarboxy quinone imine, Ν-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-fluorenyl Allyl bicyclo [2.2.1] hept-5-ene 2,3-dicarboxy quinone imine, Ν-{4-(4-hydroxyphenylisopropylidene)phenyl}-allyl bicyclo [ 2 2丨]g]_5_ 69 201237065 40462pif ene-2,3-dicarboxy quinone imine, N-{4-(4-hydroxyphenylisopropylidene)phenyl}-allyl (fluorenyl) bicyclo [2.2.1] H--5-ene-2,3-dicarboxy quinone imine, N-{4-(4-hydroxyphenyl iso-Asia Phenyl methallyl bicyclo [2 2 hept-5-ene-2,3-dimercaptoquinone imine, and oligomers thereof, N,N'-extended ethyl-bis(allyl bicyclol) [2 2 ene 2,3 · dicarboxy quinone imine), N, NM exemplified ethyl-bis (allyl fluorenylbicyclo[2.2.1]hept-5-ene-2,3-di- ruthenium imine ), n, n, -Extended ethyl-bis(methallylbicyclo[2.2.1]hept-5-lean-2,3-dicarboxyindolide), N,N,_trientylene (Ledylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), n,N,-hexamethylene-bis(allylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), N,N'-hexamethylene-bis(allylmethylbicyclo[2 2丨]hept-5-ene-2,3-dicarboxyl醯imino), N, N'-dodedecyl-bis (propyl propyl bicyclo [2 2 ^ g 5 women_2, 3 - dicarboxy quinone imine), N, N' · dodecanthine Base _ bis (allylmethyl bicyclo [2 21] hept-5-ene-2,3 · dicarboxy quinone imine), N, N, _ ring hexyl bis (allyl bicyclo [2.2. 1] G-5-baked-2,3-dicarboxyindolimine), N,N, Cyclohexyl bis(allylhydrylbicyclo[2.2.1]hept-5-ene-2,3- Two bismuth imines), I2-double Propyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) propoxy} ethene, 1,2 bis {3, propyl propyl bicyclo [2 2H 5 ene - 2,3-dicarboxy quinone imine) propoxy}ethane, hydrazine, 2 bis{3, (mercaptopropyl bismuth [2.2.1] hept-5-ene-2,3-dicarboxy fluorene Imine) propoxy oxirane, bisallyl bicyclo [(2) 士士稀丝丝醯iimide) propoxy}ethyl] test, double [2,-{3,_(propyl propyl) Bicyclo[2.2.1]hept-5P2,3-carboxycarboxyimine)propoxy oxime ethyl]ether, hydrazine, 4 bis{3, (allylbicyclo[2.2.1] g-5 -ene-2,3-dicarboxy quinone imine) propoxy oxetane, hydrazine, 4 pairs 201237065 40462pif P'-(allyl fluorenylbicyclo[2.2.1]hept-5-ene-2,3 -dicarboxy quinone imine) propoxy}butane, N,N'-p-phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine ), hydrazine, hydrazine, - p-phenylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, hydrazine, _ benzene Base-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), fluorene, fluorene,-inter)phenyl-bis(l-propyl fluorenylbicyclo[2.2 .1]hept-5-ene-2,3- Carboxylimine), 忱>^-{(1-indenyl)-2,4-phenylene}-bis(dipropylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxyanimine), hydrazine, hydrazine, p-phenylenediyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), ν, Ν, - P-Phenyldiyl-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3·dicarboxyindolide), anthracene, fluorene,-m-phenylenedifluoryl bis(ene) Propyl bicyclo [2.2.1] hept-5-rare-2,3-dicarboxy quinone imine), hydrazine, hydrazine, m-phenylenedifluoryl-bis(allylhydrazinobicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine Phenoxy}phenyl]propane, 2,2_bis[4-{4-(methylallylbicyclo[2 21]hept-5-ene-2,3-dicarboxyarenimine) }Phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}decane, bis{4-(allyl Indenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenimido)phenylnonane, bis{4-(decylene) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenyl}decane, bis{4-(decylallylhydrylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine)phenyl}decane, bis{4_(dilylbicyclo[2 2 ^hept-5-ene-2,3-dicarboxy quinolinimine)phenyl} Ether, bis 4-(allylhydrazinobicyclo 71 201237065 40462pif [2.2.1]hept-5-ene_2,3-dicarboxy quinone imine)phenyl}bonded bicyclohepta-5-ene-2 , 3-di-resinimide) phenylpropyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenyl sulfone, hydrazine 3 bis- succinimide) benzene & stone wind, (f-propyl propyl bicyclo [2.2.1] hept · 5 · ene bismuth succinimide) base] stone wind, W double (allyl Bicyclo[2_2.1]hept-5-ene_2,3_dicarboxyl=imide) yl group _M, U2_ bis (nonyl allyl bicyclo [2D ng·5_ =, 3-dipropion oxime] Imine)_3,6_二录·12 Hyun, u double (dilute propyl and soil [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) 5_经基_环己Alkane, 15_^{3'-(P-propyl propyl imino) propoxy b 3_ 故 基 · 院 Μ, 双 · bis (allyl bicyclo [2.2.1] G J 2, 3 _ Dicarboxy quinone imine) 2 - hydroxy-benzene, M · double W Propyl fluorenylbicyclo[2_2.lm_5·ene_2,3_di-reduced y-n-benzene, N,N, _p-(2_yl)-phenylene-bis (dilyl propyl) ..1]hept-5-ene-2,3-dicarboxy quinone imine),; ^]^_p-(2_fluorenyl)|monomethyl--bis(allylmethyl qing Alkylamine: N,N_m-(2-carbyl)benzodiazepine-bis(allylbicyclo[221]hept-5-retributed _,3-dicarboxyarenimine), N, N, _ (2-hydroxy) benzodiazepine-bis (mercaptoallyl-cyclo[2.2.1]hept-5-lean-2,3-di-supplemental-enamine), -p-(2 3-dihydroxy)benzodiazepine-bis(allylbicyclo[221]hept-5-ene'3 di-revalence], 2,2-bis[4_{4-( Allyl bicyclo[2.21]hept-5ene-2,3•dicarboxyindolimine)-2-hydroxy-phenoxy}pyridyl]propane, double {4 (allylmethylbicyclic 72 201237065 [2.2 .1] hept-5-ene-2,3-dicarboxyindolimine)-2-hydroxy-phenyl}decane, bis{3-(allylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxyindolimine)-4-hydroxy-phenyl}ether, bis{3-(nonylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine)-5-hydroxy-phenyl}indole, 1,1,1-tris{4-(allylhydrylbicyclo[2.2.1] -5-ene-2,3-dicarboxy quinone imine)}phenoxypurinyl propane, N,N', N"-tris(ethyl decylallylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine) isomeric cyanurate, oligomers of these, and the like. Further, the alkenyl-substituted ruthenium imide compound used in the present invention may also be a compound represented by the following formula containing an asymmetric alkylene-phenylene group.

73 201237065 Among the alkenyl-substituted quinone imine compounds, preferred compounds are shown below. N,N'·Extended ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-extended ethyl-bis(allyl Base bisbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N'-extended ethyl bis(methylallylbicyclo[2.2.1]g-5 -ene-2,3-dicarboxy quinone imine), where 1 <['-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N,N,-hexa-indenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene-based Bis(allyl-decylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), hydrazine, Ν'-dodedecyl-bis(dipropylbicyclo[2.2. 1]hept-5-rare-2,3-dicarboxy quinoid imine), hydrazine, fluorene 1-dodecyl fluorenyl-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine), hydrazine, Ν'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), hydrazine, hydrazine ,-Extend-cyclohexyl-bis(allyl-decyl-bis-2.1]hept-5-lean-2,3-di-rebasic imine), hydrazine, Ν'-p-phenylene-bis(allyl) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, Ν'-p-phenylene - bis (allyl fluorenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), ν, Ν'-meta-phenyl-bis(allylbicyclo[2.2. 1] hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, hydrazine, -interphenylene-bis(allyl fluorenyl double king coat [2.2.1] hept-5-lean- 2,3-diyl-based imine), anthracene, Ν'-{(1-indenyl)-2,4-phenylene}-bis(dil-propylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine), hydrazine, hydrazine, -p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline) ,Ν,Ν'_p-Phenyldiyl-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), ruthenium, osmium, and m-phenylene Mercapto-bis(allylbicyclo[2,2.1]hept-5-ene-2,3-dicarboxyindenine), ^,1^-m-benzoquinone 201237065 40462pif base-bis(allyl Methyl bicyclo [2.2.1] hept-5-ene · 2,3-dicarboxy quinone imine), 2,2- bisallyl bis 2 ring / dimethyl heximide · 2,3 - dicarboxy quinone imine ) oxy}benzina]propane, 2,2-bis[4-{4-(allylmethylbicyclo[22.1]hept-5-ene-2,3-dicarboxyarmineimine)benzene Oxy}phenyl]propane, 2,2-bis[4:{4·(decylallylbicyclodicarboxyl)醯imino) phenoxy}phenyl]propane, bis{4-(allylbicyclo[22...heptylene-2,3_a sulphonyl imine) base} 甲烧,双(4·( Allylmethylbicyclo[2 2 1]hept-5-ene-2,3-dicarboxyindolimine)phenylindole methane, double {4-(methylallylbicyclo) Read the quinone imine) phenyl}methane, bis{4-(decylallylmethylbicyclo[2 2"]hept-5-ene-2,3-carboxycarboxyimine)phenyl hydrazine Decane, biguanide 4_(allylbicyclo[m]hept-5-ene-2,3-dicarboxyindolide)phenyl oxime ether, bis{4_(allylmethylbicyclo[2.2.1] Hg-5-ene·2,3-dixian quinone imine)phenyl}indole, double: bisbicyclo[2.2.1]gly-doped dimercaptoquinone imine) stupid U double^^ propyl double ί Mour [2.2.1] G-5-B 2,3-di-rebelletic imine)phenyl}indole, double {4-(allylmethylbicyclo[2.21]hept-5-ene-2,3_ Two counties of imiline) benzene "wind, double {4_(methallylbicyclo[2.2.1]hept-5-ene-2,3 di-oxime amine) phenyl} sulfone. The harder soil sub-more preferred alkenyl-substituted quinone imine compound is shown below. N, NM-ethyl-bis(allylbicyclo[2 2丨]hept-5-ene-2,3-dicarboxyarenimine), N,NL-extended ethyl-bis(allylmethylbicyclo[2.2 .1]heptane-2,3-dicarboxy quinone imine), ν, ν, _extended ethyl _ bis (mercapto propyl propyl bicyclo [2.2.1] hept-5-ene 2,3-dicarboxyl醯imino), N,N,·trimethylene_bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene基· 75 201237065 ^u^tozpii bis(allylbicyclo[2.2.1]hept-5-rare-2,3-dicarboxyindenine), N,N,-hexamethylene-bis(allyl Base bisbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazomine), hydrazine, Ν·-docamethylene-bis(allylbicyclo[2 2 ηhept-5 _ene_2,3-dicarboxylic acid imine), hydrazine, Ν'-dodecyl fluorenyl-bis(allylhydrylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl醯imino), ν, Ν'-extended cyclohexyl-bis(allylbicyclo[2.2.1]hept-5-rare-2,3-dicarboxyarmine), hydrazine, hydrazine, -extension ring Alkenyl-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), hydrazine, Ν'_p-phenylene-bis(allylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine), hydrazine, Ν'-p-phenylene-bis(allylhydrazinobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), ν,Ν,-... Phenyl-bis(allylbicyclo[2.2.1]hept-5·feto-2,3-dicarboxyindolimine), ν,Ν'-inter)phenyl-bis(allylhydrazinobicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine), ν, Ν, -{(1-indenyl)_2,4·phenylene}-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine), hydrazine, Ν'-p-phenylenediyl-bis(allylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine), N, Nl p-xylylene _ bis (allyl fluorenylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), n, N,-m-phenylenediyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide m-phenylenedi-yl-bis(allylhydrazinobicyclo[ 2.2.1] hept-5-rare-2,3-dicarboxyindolimine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine) phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylhydrazinobicyclo[2·2.1]hept-5-ene_2,3- Dicarboxy quinone imine) phenoxy} phenyl] propane, 2,2-bis[4-{4-(methylallylbicyclo[2.2.1]hept-5- -2,3-dicarboxy quinone imine) phenyloxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) Phenyl}decane, bis{4-(allylhydrylbicyclo[2.2.1]

76 S 201237065 Heptane-^ene~2,3·*dicarboxyarsenazo)phenyl}methane, bis{4-(decylallyl bis=[2.2·1]heptene-2,3-dicarboxyl醯imino)phenyl}decane, bis{4_(methylglycidylbicyclo[2.2.1]hept-5-ene-2,3.dicarboxyindolimide)phenyl} decane. Further, the 'particularly preferred alkenyl-substituted quinone imine compound may be exemplified by the following formula (Ina-Ι) as a double {4-(allylbicyclo[2·2·1 talk·5- _2,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, N,N,-hexa-indenyl-bis(N-consylbicyclo)[2.2.1]g- represented by hept-5-ene-2'3_a sulfhydryl imine) and formula Una-3) 5-ene-2,3-dicarboxy quinone imine).

Further, for example, the liquid crystal alignment agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond from the viewpoint of stabilizing the electrical properties of the liquid crystal display device for a long period of time. The compound having a radical polymerizable unsaturated double bond may be one type of compound or two or more kinds of compounds of 2012 201237065. Further, the weight ratio of the human amino acid having a radical polymerizable unsaturated double bond or a derivative thereof is preferably 0.01 to L00, more preferably 〇〇1. ~〇7〇0.01~0.50. / 丨 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 具有 具有 具有The ratio of the compound to the alkenyl-substituted dysinimide compound is preferably qi~i〇, preferably 0.5 to 5. Further, examples of the compound having a free-synthesis unsaturated double bond include (methacrylic acid ester, (mercapto) acryl 01 amine (such as mercapto) pro-glycolic acid derivative, and bismide. (IV) Freedom The compound of the ketones is more preferably a (methacrylic acid derivative) having two or more radically polymerizable unsaturated double bonds. Specific examples of the (meth) acrylate include, for example, (meth)acrylic acid hexanoic acid , (meth)acrylic acid-2-methylcyclohexanol '(methyl) acrylate dicyclo= ester, (fluorenyl) dicyclopentyloxyethyl acrylate, (meth) acrylate isobornyl Ester, phenyl (mercapto) acrylate, benzyl (meth) acrylate, 2-methyl ethyl methacrylate, and 2-hydroxypropyl (meth) acrylate. Specific examples of the (meth)acrylic acid g include, for example, ethylene glycol dicapcoate, ARONIX M-210, ARONIX M-240, and ARONIX M-6200, which are products of East Asia Synthetic Chemical Co., Ltd. **! 78 201237065 40462pif Products of this chemical company, KAY ARAD HDDA, KAYARAD HX-220, KAY ARAD R-604 and KAY ARAD R-684, large Products of the Organic Chemical Industry Co., Ltd., V260, V312, and V335HP, and products of the company, Light Acrylate BA-4EA, Light Acrylate BP-4PA, and Light Acrylate BP-2PA, which are more than three functional groups. Specific examples of the functional (fluorenyl) acrylate include, for example, 4,4'-fluorenylene bis(N,N-dihydroxyethyl acrylate), and ARONIX M-product of East Asia Synthetic Chemical Co., Ltd. 400, ARONIX M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, products of Nippon Kayaku Co., Ltd. KAYARAD TMPTA, KAYARAD DPCA-20, KAY ARAD DPCA-30, KAY ARAD DPCA-60, KAYARAD DPCA-120, and VGPT of the Osaka Organic Chemical Industry Co., Ltd. As a specific example of the (meth) acrylamide derivative, for example, N-isopropyl acrylamide, N -isopropyl decyl acrylamide, N-n-propyl acrylamide, N-n-propyl decyl acrylamide, N-cyclopropyl acrylamide, N-cyclopropyl decyl acrylamide, N-ethoxyethyl acrylamide, N-ethoxyethyl fluorenyl Enamine, N-tetrahydrofurfuryl decylamine, N-tetrahydrofurfuryl methacrylamide, N-ethyl acrylamide, N-ethyl-N-mercapto acrylamide, N, N -Diethyl acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl~N«isopropyl propyl baking amine, N-propyl butyl base, N-propylene Brewing base ratio. Alkanone, N, N'-methylenebis propylene amide, hydrazine, Ν'-extended ethyl bis acrylamide, 79 201237065 40462pif N, N'-dihydroxyethylidene bis decylamine, N- (4-hydroxyphenyl)mercaptopropenylamine, N-phenylmercaptopropenylamine, N-butylmercaptopropenylamine, N-(isobutoxymethyl)methacrylamide, N -[2-(N,N-Didecylamino)ethyl]nonyl acrylamide, N,N-dimercaptopropenylamine, N-[3-(didecylamino)propene Alkyl acrylamide, N. (decyloxy) decyl acrylamide, N-(hydroxymethyl)-2-methyl acrylamide, N-benzyl-2-mercapto propylene oxime Amine, and hydrazine, Ν'--fluorenylene bis-decyl acrylamide. Among the above (mercapto)acrylic acid derivatives, hydrazine, Ν'-fluorenylene bis acrylamide, hydrazine, Ν'-dihydroxyethylidene bis acrylamide, ethylene diacrylate, and 4 are particularly preferable. 4'-Amidino bis (indole, fluorene-dihydroxyethyl phenyl aniline). Examples of the bismaleimide include BMI-70 and BMI-80 manufactured by Industry Chemical Industry Co., Ltd., and BMI_1000, BMI-3000, BMI-4000, and BMI-5000 manufactured by Daiwa Kasei Kogyo Co., Ltd. And BMI-7000. Further, for example, the liquid crystal alignment agent of the present invention may further contain an oxazine compound from the viewpoint of long-term stability of electrical characteristics in the liquid crystal display device. The oxazine compound may be one type of compound or two or more types of compounds. From the above viewpoints, the content of the oxazine compound is preferably 0.1 wt% to 50 wt%, more preferably 1 wt% to 40 wt%, still more preferably 1 with respect to the poly-aracine acid or a derivative thereof. Wt% ~ 20 wt%. The oxazine compound is preferably a solvent which is soluble in a solution of polylysine or a derivative thereof, and further has a ring-opening polymerizable oxazine compound. 201237065 40462pif Further, the number of oxazine structures in the oxazine compound is not particularly limited. ° The structure of the scorpion is known to have various structures. In the present invention, The gentleman's structure of the oxazine is not particularly limited, and the oxazine structure in the oxazine compound may be an oxazine structure having an aromatic group (including a condensed polycyclic aromatic group) such as an oxazine or a thiazine. . Examples of the agonizing compound include compounds represented by the following formulas (a) to (f). Further, in the following formula, the bond represented by the center of the ring indicates that it is bonded to any carbon constituting the ring and capable of bonding a substituent.

In the formula (〇~ (c), r1 and R2 are an organic group having a carbon number of 1 to 30. And 'in the formula (a) to the formula (f) t, R3 to R6 represent hydrogen or a carbon number of 1:6. Further, in the formula (〇, formula (4) and formula (1), X is a single bond, ·0_, -S·,, s, s, qing,•, ―c〇NH_, _NHC0_, -C(CH3)2 -, -C(CF3)2-, _(cii2)m_, -〇_(CH2)m_〇_, each (CH2)m_S-. Here, m is an integer of 丨~6. Equation 201237065 IV < ^ Λ.Λ. (6) and (in the middle, 丫 independent as a single bond, -0-, -8-, - (: 0-, -匚 ((: 113)2-, - C(CF3)2- or an alkylene group having a carbon number of 1 to 3. Further, the hydrogen bonded to the benzene ring or the naphthalene ring in the formulae (a) to (f) may be independently -F, - Further, CH3, -OH, -COOH, -S03H, -Ρ03Η2 are substituted. Moreover, the oxazide compound includes an oligomer or a polymer having a structure in the side chain, and an oligomer having an oxazine structure in the main chain. The substance or the polymer. The noisy compound represented by the formula (a) is exemplified by the following compounds.

(a-1) (a-2) In the formula, R1 is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. The oxazin compound represented by the formula (b) is exemplified by the following acetonide compound.

S 82 201237065 40462pif

In the formula, R1 is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. The evil expressed by the formula (c). The Qin compound may be exemplified by the following formula (c〇 represents the oxime compound. 83 201237065 40462pif

In the formula (c'), 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, and X represents a single bond, -CH2-, -C(CH3)2 -, -CO-, -〇-, -so2- or C(CF3)2-. The oxazine compound represented by the formula (C') is exemplified by the following anthraazine compound.

84 201237065 40462pif

/ R1

(c-13) (c-10)

(〇14)

In the above formula, R1 is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having a carbon number of 1 to 20. The oxazine compound represented by the formula (d) includes, for example, the following oxazine compounds. 85 201237065 40462pif

(d-7) . (d-8)

(d-9)

(d-10)

Expressed by formula (e). evil. Examples of the Qin compound include the following oxime compounds.

86 S 201237065

The oxime compound represented by the formula (f) is exemplified by the following oxime compound. 87 201237065 40462pif

88 s 201237065 40462pif Among the ruthenium compounds, the formula (b, formula (5)), formula (4), formula (... to formula (1: formula U-3), formula (e_4), formula (4)) to formula (4) are more preferable. The oxazide compound can be produced by the same method as that described in the Japanese Patent Publication No. H20__8_, Japanese Patent Application Laid-Open No. Hei No. 5-58, No. 4-3526. The pyridazine compound represented by the example 11) can be obtained by reacting a desired compound with a --stage makeup (refer to the International Publication No.). Further, the (tetrazine) compound represented by the formula (b) can be obtained by adding a compound having a methicone group to the reaction after the reaction is gradually added to the method of (4). Reaction (refer to International Publication No. 2004/009708). And, the oxazine compound represented by the formula (c) can be obtained by: in the presence of an aliphatic secondary amine, an aliphatic tertiary amine or a basic nitrogen-containing heterocyclic compound in an organic solvent. The phenolic compound is a molar amount of at least 2 moles of aldehyde and 1 mole of primary amine relative to the hetero 1 mole of the desired compound (refer to International Publication No. 2004/009708 and Japanese Patent Laid-Open No. 11-- Bulletin 12258). Further, the oxindole compound represented by the formula (d) to the formula (f) can be obtained by using 4, 4, "diamine-based diphenyl" in n-butanol at a temperature of 90 ° C or higher. A polyamine having a plurality of benzene rings and an organic group bonded to the benzene ring, an aldehyde such as formalin, and a phenol are subjected to a dehydration condensation reaction (refer to Japanese Patent Application Laid-Open No. 2004-352670). Further, the liquid crystal alignment agent of the present invention may further contain an oxazole compound, for example, from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be a compound ' or two or more compounds. From the above viewpoints, the content of the oxazoline compound is preferably 0.1 wt ° / 〇 50 50 ° ° / 〇 ' more preferably 1 〜 40 wt ° / relative to the poly phthalic acid or its derivative. Further, it is preferably from 1 wt% to 20 wt%. Alternatively, from the above viewpoint, when the oxazoline structure in the oxazoline compound is converted to an oxazoline, it is preferred that the content of the oxazoline compound is relative to the polylysine or its derivative. It is 0.1 wt% to 40 wt% 6 ° evil " sitin compound may have only one oxazoline structure in one compound' or may have two or more oxazoline structures. Further, the compound having the oxazoline structure in one compound preferably has two or more of the 嗔β sitting structure in one compound. Further, the β 恶 坐 , compound may be a polymer having an oxazoline structure in a side chain, or may be a polymer. The polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer of a side chain I, a sitin structure, or a malignant bond 3 in a side chain, a monomer of a '° structure and a non-malignant A copolymer of monomers of oxazoline structure. On the side of ^ there. The copolymer of the ruthenium structure may be a copolymer of a monomer having more than one type of oxazoline structure in the side chain, or may have a ruthenium in the side chain, a monomer or more. a copolymer of monomers of the sputum structure. The structure of the oxalate is preferably a structure in which the oxygen in the oxazoline structure and the nitrogen of a 201237065 40462pif or both are reacted with the carbonyl group of the poly-proline to form the structure in the oxazole compound. Examples of the oxazoline compound include 2,2,_bis(2- oxazoline), 丨2 4 bis(L-salt-2-yl)-benzene, and 4 吱-2-yl-Asian Base_2_stupyl_4H_'d^-5-ketone, bis(4,5-dihydro-2-oxazolyl)benzene, bis(6)dihydrodiindenyl)benzene, 2,3- Bis(4-isopropenyl-2-oxazoline-2-yl)butane, 2 2,-bis-benzyl-2-oxazoline, 2,6-bis(isopropyl-2-oxazole啉_2_yl)pyridine, 2 2, isopropylidene bis(4_t-butyl-2-oxazoline), 2,2, isopropylidene bis (4'-phenyl-2-oxazole Porphyrin), 2,2,-methylenebis(4_t-butyloxazoline) and ??-indenyl bis(4-phenyl-2-indene). In addition to these compounds, Columns, such as EPOCROS (commodity 纟, manufactured by Nippon Shokubai Co., Ltd.), have a thiol group-containing polymer or oligomer. More preferred oxazoline compounds include, for example, 2, 2, _ double (2 _ chew Saliva and 1,3-bis(4,5-dihydro-2-oxazolyl)benzene. "In addition, the liquid crystal alignment agent of the present invention is also considered, for example, from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element. It may further contain an epoxy compound. The compound may be a ruthenium compound or a compound of two or more kinds. Since the above, the content of the oxygenated compound is superior to that of the polyfluorene or its derivative by Q丨wt%~5〇. The wt% is more preferably from 1 wt% to 4 G wt%, and more preferably from i wt% to 20 wt%. The s% oxygen compound may be one having one or two or more epoxy rings in the molecule. Examples of the compound having an epoxy ring in the molecule include, for example, phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl 201237065 40462pif epoxidation, phenyl benzene, Hexafluoroepoxypropane, cyclopropyltrimethoxyoxide, 2pepoxycyclocentric; Ethylene sulphate, N-glycidyl phthalate, and imine, (Daji J·s) ring Oxide, perfluoroethylglycidyl-N,N-di-glycidyl, yam dynasty remedy, alcohol, epoxy = basic amine, and 3 fluorohexyl) ethoxy]-U- Examples of the compound having a reduced oxygen ring include ethylene glycol neopentyl glycol (II); polypropylene glycol diglycidyl, diglycidyl hydrate, and 21 hexamethylene alcohol diglycidyl glycerol. Base group _3, bis-hydrazin _, 3,4-epoxy glyceryl thief (4) 3 paste · condensed water 2-[4 (=, two with # 3 epoxy ring compounds, for example, can be cited - stupid Methylamine ittNN4, Yetan tetraglycidyl, N, taken, this tetraglycidylaminomethyl)cyclohexane β 1 ηντ ^ glycidyl_4,4'·diaminodiphenylmethane,除 In addition to ^ Ν · Ν 'glycidyl) aminopropyl trimethoxy sulphur. Elieb, an example of a compound having an epoxy ring in the molecule may also be a ring oligomer or polymer. Monomer having an epoxy ring

S 92 201237065 40462pif = (meth) glycidyl acrylate, decyl cyclohexyl (meth) acrylate, and decyl glycidyl (mercapto) acrylate. Examples of the other monomer copolymerized with the monomer having an epoxy ring include (meth)acrylic acid, (mercapto)acrylic acid vinegar, (mercapto)acrylic acid vinegar, and (meth)acrylic acid. Isopropyl vinegar, (meth) propionic acid butyl vinegar, (meth) acrylic acid isobutyl hydrazine (mercapto) propylene @ 夂 second vinegar, (mercapto) propylene 酉 环 环 vinegar, (a Base) acrylic acid-based vinegar, (meth)acrylic acid-2-ylidene, (mercapto)acrylic acid-2-pyridyl vinegar, styrene, mercaptostyrene, methacrylic acid Dilute, (meth) propylene, _ (3_ethyl_3_epoxypropyl) vinegar, N-cyclohexylmaleimine, and N-local mazene. Preferable specific examples of the polymer of the monomer having a chlorine oxide include poly(mercaptopropene glycerin). Further, preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include Ν 笨 笨 马 马 马 酿 酿 酿 酿 曱 曱 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环· Mercaptoacrylic acid glycidyl S copolymer, methacrylic acid-methyl methic acid, 1 gram of methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate Woven ethylene I glycidyl methacrylate copolymer, methyl propyl _(3_ethyl_3_epoxypropyl) methyl methacrylic acid glycidyl (tetra) fine and styrene · methyl silk _ glycidol Ester copolymer. In these cases, it is preferred to Ν, Ν, Ν, Ν, -tetraglycidyl _ benzophenone, 1,3 bis (indole, Ν-diglycidylaminomethyl) cyclohexanone , Ν, Ν, Ν', Ν, glycidyl _4,4, _diaminodiphenyl ketone "Te_ VG hire L", 3,4·epoxycyclohexylmethyl _3, 4, _ epoxy ring 93 201237065 40462pif = fine, N stupid mala brewing iminopropyl propylene glycol acetoxy co-epoxycyclohexyl) ethyl trimethoxy zebra. Μ,丨5, the epoxy compound, for example, may be exemplified by glycidol r, 7 bis day 1 glycidylamine, an epoxy group-containing acetoin-type tree-type oxidized 2 amine, glycidyl iso-tris Polycyanate, chain fat and cyclic aliphatic epoxy compound. In addition, a compound having a mercapto group is shown in the ring, and the epoxy resin is represented by a compound having a ring of a ring = ^^=^, a double test, a hydrogenation of a double-type epoxidized oxygen, a double-aged epoxy compound, and a double bond.纷-s type epoxidized character"1 _ _F type epoxy compound, hydrogen age - A 峨 ° 双 system double _ epoxy compound, desertified double varnish type ring ^hyri stinky double hope 'f ring Oxygen compounds, various aging varnish-type epoxy compounds, desertified granules, bismuth a varnish, oxygen varnish-type epoxidized compound, aromatic polycondensate μ if epoxidized oxygen compound containing naphthalene, fat The 'dicyclopentadiene benzene-cyclodecene compound, the compound 'aliphatic polycondensation succinyl-type epoxy compound.—, the water-glycine compound, and the biphenyl glycidyl ester are exemplified by a diglycidyl acetal epoxy compound. Examples of the glycerin compound and the condensed polyglycidylamine compound include a polyglycidylamine compound. Examples of the benzoate compound of the oxonite include a homopolymer and a copolymer of a monomer having an epoxy 94 201237065 ethane group. The amine may, for example, be a glycidyl-brown amine-type epoxidized (1) chain grease. The group epoxy compound may, for example, be an epoxy group-containing compound obtained by oxidizing a slave-carbon double bond of an olefin compound. The hetero(tetra) group epoxy compound may, for example, oxidize a carbon-carbon double bond of a cycloolefin compound. Examples of the epoxy group-containing compound. Examples of the bisphenol A type epoxy compound include 828, 1〇〇1, 1002, 1003, 1^) 4, 1007, and 1〇1〇 (all manufactured by Japan Epoxy Resin Co., Ltd.). (now available in the form of jER series products of Mitsubishi Chemical Co., Ltd.), Epotohto YD-128 (manufactured by Dongdu Chemical Co., Ltd.), DER_331 'DER-332, DER-324 (all are Dow Chemical Manufacturing),

Epiclon 840, Epiclon 850, Epiclon 1050 (both manufactured by DIC Stock Co., Ltd.), EPOMIK R-140, EPOMIK R-301, and EPOMIKR-304 (all manufactured by Mitsui Chemicals, Inc.). Examples of the biguanide F-type epoxy compound include 8〇6, 807, and 4004P (all manufactured by Sakamoto Epoxy Co., Ltd.), Epotohto YDF-170, Epotohto YDF-175S, and Epotohto YDF-2001 (all of which are Dongdu Chemical Co., Ltd.). Manufactured by the company), DER-354 (manufactured by Dow Chemical), Epiclon 830, and Epiclon 835 (all manufactured by DIC Corporation). The bisphenol type epoxy compound is, for example, an epoxidized product of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane. Examples of the hydrogenated bisphenol-A type epoxy compound include Sun Tohto ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Ricaresin HBE-100 (new 曰 95 201237065 40462pif), and DENACOL EX-252 (manufactured by Nagasechemte X Corporation). The hydrogenated bisphenol type epoxy compound may, for example, be an epoxide of hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane. Examples of the brominated bisphenol-quinone type epoxy compound include 5050 and 5051 (all manufactured by Sakamoto Epoxy Co., Ltd.), Epotohto YDB-360, and Epotohto YDB-400 (all manufactured by Tohto Kasei Co., Ltd.), DER_53〇. DER-538 (all manufactured by Dow Chemical), Epiclon® 52, and Epiclon 153 (all manufactured by DIC Corporation). Examples of the phenolic novolak-type epoxy compound include 152 and 154 (both manufactured by Sakamoto Epoxy Co., Ltd.), YDPN_638 (manufactured by Tohto Kasei Co., Ltd.), DEN431 and DEN438 (all manufactured by Dow Chemical), and Epiclon N. -770 (Manufactured by DIC Corporation), EPPN-201, and EPPN-202 (all manufactured by Sakamoto Chemical Co., Ltd.). Examples of the phenolic phenolic acid/varnish-type epoxy compound include i8〇S75 (manufactured by Sakamoto Epoxy Co., Ltd.), YDCN-7 (H, YDCN-702 (both manufactured by Tohto Kasei Co., Ltd.), and Epiclon N-665. , Epiclon N-695 (both manufactured by DIC Corporation), e〇CN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all are Nippon Chemical Co., Ltd.) For the varnish-type epoxy compound, for example, i57S70 (manufactured by Sakamoto Epoxy Co., Ltd.) and Epiclon N-880 (manufactured by DIC Corporation) can be cited. Examples of the epoxy compound containing a naphthalene skeleton include Epicl. 〇n

S 96 201237065 4U462pif HP-4032, Epiclon HP-4700, Epiclon HP-4770 (both manufactured by DIC Corporation), and NC-7000 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (Formula E101 below), catechol diglycidyl ether (Formula E102 below), and resorcinol diglycidyl ether (bottom) E103), tris(4-glycidoxyphenyl)methane (formula E105 below), 1031S, 1032H60 (all manufactured by Sakamoto Epoxy Co., Ltd.), TACTIX-742 (Tao

Chemical Manufacturing), DENACOL EX-201 (Nagase chemteX

(manufactured by Corporation), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), Tecmoa VG3101L (manufactured by Mitsui Chemicals, Inc.), a compound represented by the following formula E106, and Compound represented by the following formula E107° 97 201237065 -TV/'TVA, wii

Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (manufactured by Dow Chemical Co., Ltd.) and Epici〇n HP-7200 (manufactured by DIC Corporation). Examples of the alicyclic diglycidyl ether compound include a cyclohexanedimethyl diglycidyl hydrazine compound and Ricaresin DME-100 (manufactured by Shin-Nihon Chemical Co., Ltd.). Examples of the t-glycidyl hydrazine compound include ethylene glycol diglycidyl ether (the lower juice bucket, cim?, > ^ type 9), 2 formula E1〇8i, and diethylene bis-dihydrate. A ethyl alcohol monoglycidyl ether, propylene glycol diglycidyl ether 98 201237065 40462pif (E110 below), tripropylene glycol diglycidyl ether (Bill), polypropylene glycol diglycidyl ether neopentyl glycol diglycidyl Ether (Formula E112 below), 1,4-butanediol diglycidyl ether (E113 below), 1,6-hexanediol diglycidyl ether (E114 below), dibromo neopentyl glycol Glycidyl ether (Eflip E15 below), DENACOLEX-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 (all manufactured by Nagase chemteX Corporation), DD-503 (made by ADEKA Co., Ltd.), Ricaresin W-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.), 1,3,5,6-tetraglycidyl- 2,4-hexanediol (Formula E116 below), glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trioxindole Propane polyglycidyl ether, pentaerythritol polyglycidyl ether, DENACOL EX-313 'DENACOL EX-611' DENACOL EX-321, and DENACOL EX-411 (Nagase chemteX Corporation are manufactured).

S 99 201237065 40462pif

(E110)

(E111) (E112)

(E113)

(E114) /Br

(E115)

(E116) The polysulfide type diglycidyl ether compound may, for example, be FLDP-50 or FLDP-60 (all manufactured by Toray Thi〇k〇1 c〇, Ltd.). Examples of the biphenyldiol-based epoxy compound include γχ_4〇〇〇, YL-6121H (all manufactured by Nippon Epoxy Co., Ltd.), NC-3000P, and NC-3000S (all manufactured by Nippon Kayaku Co., Ltd.). Examples of the diglycidyl ester compound include diglycidyl terephthalate (formula 7 below), diglycidyl phthalate (formula Ε 118 below), and bis(2-methyl phthalate). a compound represented by the following formula: 121, a compound represented by the following formula Ε121, or a formula Ε122

S 100 201237065 40462pif The compound represented by the following formula and the compound represented by the following formula E123.

(E122) Ο

(E123) Examples of the glycidyl ester epoxy compound include 871, 872 (both manufactured by Sakamoto Epoxy Co., Ltd.), Epiclon 200, Epiclon 400 (all manufactured by DIC Corporation), and DEnac® L EX-711, and DENACOL EX-721 (both manufactured by Nagase chemteX Corporation). Examples of the polyglycidylamine compound include hydrazine, hydrazine-diglycidylaniline (hereinafter referred to as Ε124), hydrazine, hydrazine-diglycidyl-o-anilide (the following formula Ε125), hydrazine, hydrazine-diglycidylglycerol. Base-m-toluidine (formula 126 below), hydrazine, hydrazine-diglycidyl 2,4,6-tribromoaniline (E127 below), 3-(Ν,Ν- 101 201237065 diglycidyl Aminopropyl dimethoxy group (*E128), hydrazine, hydrazine, 0-triglycidyl-p-aminobenzene (E129 below), hydrazine, hydrazine, 0-tri-shrink Glyceryl-m-aminobenzene (hereinafter, 3 〇), N, N, N', N'_tetraglycidyl-m-benzoic acid (TETRAD_X (Mitsubishi Gas Chemical Co., Ltd.), under Illustrative formula E132), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), the following formula E133), 丨, 4 - bis(N,N diglycidylamino fluorenyl)cyclohexane (Formula E134 below), 込3-bis(N,N-diglycidylamino)cyclohexane (Formula E135 below) , hydrazine, 4-bis(N,N-diglycidylamino)cyclohexane (Formula E136 below), , 3-bis(N,N-diglycidylamino)benzene (Formula E137 below), hydrazine, 4·bis(N,N-diglycidylamino)benzene (Formula E138 below), 2 , 6-bis(N,N-diglycidylaminoindenyl)bicyclo[2.2.1]heptane (Formula E139 below), N,N,N',N'-tetraglycidyl-4, 4,-Diaminodicyclohexyldecane (Formula E140 below), 2,2'-Dimethyl-(N,N,N,,N,-tetraglycidyldiaminebiphenyl (described below) Formula E141), N,N,N',N'-tetraglycidyl_4,4'-diaminodiphenylanthracene (E142 below), 1,3,5-tri (4- (art > 1- diglycidyl)aminophenoxy) benzene (Formula E143 below), 2,4,4,-Tris(Ν,Ν-diglycidylamino)diphenyl ether (described below) Ε144), tris(4-(Ν, Ν-diglycidyl)aminophenyl)methanthine (the following formula Ε145), 3,4,3',4'-four (>^- condensed water a compound represented by the following formula: 148, glycerylamino)biphenyl (the following formula: 146), ^, ^, tetrakis(9)- diglycidylamino) diphenyl ether (hereinafter, Ε 147), And a compound represented by the following formula 149.

S 102 201237065

(E124) (E125) (E126)

Br

(Ε128) (Ε129)

(Ε136) (Ε137) 103 201237065 40462pif

(E140) (E141)

s 201237065 40462pif

(E148) /-4 A homopolymer of a monomer having an oxiranyl group is exemplified by poly(glycidyl methacrylate). The copolymer of the monomer having the oxiranyl group may, for example, be N-phenylmaleimide-mercaptoacrylic acid glycidyl brew copolymer, N-cyclohexylmaleimide-mercaptoacrylic acid shrinkage Glyceride copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl glycerol Ester copolymer, methyl acrylate (3-ethyl-3-epoxypropyl) oxime S - methacrylic acid glycidyl cool copolymer, and styrene-glycidyl methacrylate copolymer. 105 201237065 ΗΌΗΌΔρίΙ * i The oxyethylene group-containing monomer may, for example, be (meth)acrylic acid-reduced methyl)acrylic acid-3,4-epoxycyclohexanoic acid, and (meth)acrylic acid-based fine glycerin vinegar. Examples of the monomer other than the monomer having an ethylene oxide group in the common (IV) of the monomer having an epoxy group are exemplified by (mercapto)acrylic acid, (meth)acrylic acid 曱K fluorenyl group. W olefinic acid, isopropyl (hydrazino) isopropyl H hydrazide butyl acrylate, (butyl) methacrylate, (fluorenyl) propylene oxime, second butyl, (meth) acrylate Purpose, (meth)acrylic acid-based vinegar, (mercapto)acrylic acid-2-ylaminoacetate@(,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Stupid ethylene, (mercapto)acrylic acid (3_ethyl methoxypropyl) 曱S day, N·% hexylmaleimide, and N 醯 醯 脍. , 妓 水 水 异 异 异 例如 例如 例如 例如 例如 例如 例如 例如 1 1 1 1 1 1 1 1 1 1, 1, 3, 3 (Formula E150 below) 1"3 glycidyl.5-allyl_13,5-triazine_2, knowing m, 3H, with the following formula E151), and glycidyl isocyanuric acid Oxygenated resin.

The epoxidized polybutylene

S 106 201237065 Women, and Ep〇leadPB3_ (Dasailu Chemical Industry Co., Ltd.). Examples of the cyclic aliphatic epoxy compound include 2-methyl-4-oxocyclohexylmethyl-2'-methyl-3', 4'-epoxycyclohexylcarboxylate (described below = E153). 2,3_epoxy ring New 2,3,_epoxycyclopentane (tetra) (described below Ε 154), ε·caprolactone modified 3,4_epoxycyclohexylmethyl_3,, 4, _ Epoxy ring " 竣 竣 竣 vinegar, 1,2:8,9-diepoxy limonene (cell 〇xide3〇00 (manufactured by Dazu Chemical Industry Co., Ltd.), 3,4-epoxy ring Alkenylmethyl-3,4,-epoxycyclohexenecarboxylate (Celloxide 2021P (manufactured by Daicel Chemical Industries, Ltd.), the following formula E155), a compound represented by the following formula E156, CY- 175, CY-177, CY-179 (constructed by The Ciba-Geigy Chemical Corp. (available from Huntsman Japan KK), EHPD·3150 (Manufactured by Daicel Chemical Industry Co., Ltd.) and a cyclic aliphatic epoxy resin.

Further, for example, the liquid crystal alignment agent of the present invention has < r ' y - each having 107 201237065 kinds of additives. Examples of the various additives include a polymer compound and a low molecular compound other than polyglycine and a derivative thereof, and can be selected and used according to the respective purposes. For example, the polymer compound may be a polymer compound which is soluble in an organic solvent. From the viewpoint of controlling the electrical characteristics or the alignment property of the liquid crystal alignment film formed, it is preferred to add such a polymer compound to the liquid alignment agent of the present invention. The S-way molecular compound may, for example, be a polystyrene, a 1; a female, a urea, a polyepoxide, a polyacetate, a polyoxyl modified polyurethane, and a polyoxygen modified polyester. . Further, as the low molecular compound, for example, a surfactant which is used for achieving the object when it is desired to improve coatability, 2) an antistatic agent when it is necessary to improve antistatic property, and 3) when it is desired to improve The adhesion to the substrate is a sulphur coupling agent or a titanium coupling agent, and 4) when the hydrazine imidization is carried out at a low temperature, it is a ruthenium-based catalyst. Examples of the decane coupling agent include vinyl trimethoxy decane, vinyl triethoxy decane, N-(2-aminoethyl)-3-aminopropylmethyl decyloxy decane, and N-( 2-Aminoethyl)_3_aminopropylmercaptotrimethoxydecane, p-aminophenyltrimethoxyoxane, p-aminophenyltriethoxydecane, m-aminophenyltrioxane Base decane, m-aminophenyl triethoxy decane, 3-aminopropyl dimethoxy oxime, 3-aminopropyl triethoxy pulverization, 3-glycidoxy propyl tri Oxydecane, 3-glycidoxypropylmethyldimethoxysulfonium, 3-apropylpropylmercaptodimethoxydecane, 3-chloropropyltrimethoxyoxyzole, 3-mercapto Propylene methoxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxy decane, N-(l,3-dimercaptobutylene)-3-(triethoxydecane

S 108 201237065 40462pif)-1-propylamine, and N,N'-bis[3-(tridecyloxydecyl)propyl]ethylenediamine. A preferred decane coupling agent is 3-aminopropyltriethoxydecane. Examples of the ruthenium-based catalyst include aliphatic amines such as tridecylamine, triethylamine, tripropylamine, and tributylamine; N,N-dimercaptoaniline, anthracene, fluorene-diethylaniline, and mercapto group. Aromatic amines such as substituted anilines, hydroxy-substituted anilines; pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, fluorenyl-substituted quinoline, hydroxy-substituted quinoline, iso-quinoline a porphyrin, a hydrazino-substituted isoquineline, a hydroxy-substituted isoquinoline, an imidazole, a mercapto-substituted imidazole, a hydroxy-substituted imidazole, and the like. The quinone imidization catalyst is preferably selected from the group consisting of hydrazine, hydrazine-dimercaptoalkylamine, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine, and isoquinoline. One or more of them. The decane coupling agent is usually added in an amount of from 0 wt% to 20 wt% per total weight of the polyaminic acid or its derivative. , preferably 〇.! wt%~1〇 wt%. The amount of the ruthenium-imidation catalyst to be added is usually 0.01 equivalent to 5 equivalents, preferably 0 5 equivalents to 3 equivalents, per mole of the carbonyl group of the poly-proline or its derivative. The amount of the other additives to be added varies depending on the use thereof, but is usually 〇 wt% to 1% by weight based on the total weight of the polyglycine or a derivative thereof, preferably 〇% to 50% by weight. Further, for example, the liquid crystal alignment agent of the present invention may further contain an acrylic polymer in a range (preferably within an amount of 2% by weight of the polyamido acid or a derivative thereof) without impairing the effects of the present invention. Acrylate polymer, and a reaction product of a tetranuclear acid, a second thief or a derivative thereof and a diamine

S 109 201237065 40462pif Other polymer components such as polyamidoximine. Further, the liquid crystal alignment agent of the present invention may further contain a solvent, for example, from the viewpoint of applicability of the liquid crystal alignment agent or adjustment of the concentration of the polyamic acid or a derivative thereof. The solvent is not particularly limited as long as it has a solvent having the ability to dissolve a polymer component. The solvent widely 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 one type or a mixture of two or more types. The solvent may, for example, be a solvophilic agent of the polyaminic acid or a derivative thereof or another solvent for the purpose of improving coatability. Examples of the aprotic polar organic solvent which is a solvating solvent with respect to polyamic acid or a derivative thereof include N-methyl-2-pyrrolidone, diterpene sulphonin, and N-methyl hexanone. Amine, N-methyl-amine, NN_di-amine: dimethyl sulfoxide, n, n-dimethylformamide, tert-diethylamine, ethylethylamine, butyrolactone, etc. Lactone. Examples of the other solvent for the acid burning include milk, calcined hydrazine (ethylene glycol monobutyl sulfonate, etc.), diethylene glycol ethyl alcohol monoethyl ether, etc., and ethylene glycol soil k (didiol generation 栌m) Pre-alkyl or benzyl ether acetate, :r monopropyl, alkyl ether (propylene glycol monomethyl bond, C 1 ^ secret), malonic acid dialkyl vinegar (malonate di-internal alkyl)趟 (dipropylene glycol monomethyst, etc., two-and-a-half-day buccal ester compounds, etc. - acetic acid 201237065 40462pif in these compounds, the solvent is particularly preferably N-mercapto-2-isopropanone, Dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol monoterpene scale. In the present invention, liquid crystal The concentration of the polymer component containing the polyamic acid or a derivative thereof in the alignment agent is not particularly limited, but is preferably 0.1 wt% to 40 wt%. When the liquid crystal alignment agent is applied onto a substrate, In order to adjust the film thickness, it is necessary to perform an operation of diluting the polymer component contained in the solvent with a solvent in advance. The viscosity of the agent is adjusted to a viscosity suitable for easily mixing the solvent in the liquid crystal alignment agent, and the concentration of the polymer component is preferably 40% by weight or less. Further, there is also a method of adjusting the coating method according to the liquid crystal alignment agent. The concentration of the polymer component in the liquid crystal alignment agent. When the method of applying the liquid crystal alignment agent is a spin coating method or a printing method, in order to maintain the film thickness favorably, the concentration of the polymer component is usually usually 1〇wt% or less. Also ~7 is further reduced by other coating methods such as dipping or ink jet method. On the other hand, if the concentration of the local molecular 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 wt% or more, preferably 〇5 wt% to 10 wt%, in a usual spin coating method, printing method, or the like. However, it can also be used at a lower concentration according to the coating method of the liquid crystal alignment agent. Further, in the case of being used in the production of a liquid crystal alignment film, the viscosity of the liquid crystal alignment agent of the present invention can be determined according to the shape. In the case of forming a liquid crystal alignment agent film 111 201237065 using a printing machine, it is preferably 5 mPa·s or more from the viewpoint of obtaining a sufficient film thickness, and From the viewpoint of suppressing printing unevenness, it is preferably 1 μmPa·s or less, and more preferably 1 μmPa·s to 80 mPa·s. In the case where a liquid crystal alignment agent is applied by spin coating to form a liquid crystal alignment agent film. From the same viewpoint, it is preferably 5 mPa·s to 200 mPa·s, more preferably 10 mPa·s~i〇〇mPa·s. The viscosity of the liquid crystal alignment agent can be diluted by using a solvent or ripening with stirring. (curing) and lower. The liquid crystal alignment agent of the present invention may be in the form of a polyglycine or a derivative thereof, or a form of a so-called polymer blend in which two or more kinds of polyaminic acid or a derivative thereof are mixed. The liquid crystal alignment film of the present invention is a film formed by heating a coating film of the liquid crystal alignment agent of the present invention, and as described above, linearly polarized light which is irradiated with ultraviolet rays before or after heating the coating film. 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. The substrate may be a glass substrate such as an electrode such as an IT (Indium Tin Oxide) electrode or a color filter. A method of applying a liquid crystal alignment agent onto a substrate is generally known as a spin coating method, a printing method, a dipping method, a dropping method, an ink jet method, or the like, and is similarly applied to the present invention. The water H can be carried out in the condition (4) (4) or in the case where the projectile exhibits a condition 2 of detachment. The infrared μ is subjected to a heat treatment, and the material is heated on the raft. This age method can also be applied to

112 S 201237065

=: 3 medium and small: Changyou _ boots ~ boots around the temperature at the temperature! Other than the other = can be further included by the above steps to lift the coating film. Such other steps may be omitted, although it is not necessary to use 1, the soil γL, the liquid crystal alignment film washing step of the present invention, and (4) the drying of the burdock tray to prevent the setting of the cleaning step. Or the infrared furnace ΐ-, / burning step _# is generally known to have a heat treatment in an oven, and a method of heating on a hot plate. These methods are equally applicable to the drying. The drying step is preferably carried out at a temperature (10) at which the solvent can evaporate, and more preferably at a relatively low temperature relative to the temperature in the burn-in step. ^ Cleaning methods using cleaning liquids include: bmshing, jet spray, steam cleaning or ultrasonic cleaning. These methods can be carried out either alone or in combination. The cleaning liquid may be pure water, or various alcohols such as decyl alcohol, ethanol, and isopropanol, aromatic hydrocarbons such as benzene, toluene, and diphenylbenzene, halogen solvents such as dimethyl ketone, acetone, and glycerol. However, it is not limited to these cleaning solutions. Of course, these cleaning fluids require the use of a cleaning fluid that is sufficiently purified with less impurities. This cleaning method can also be applied to the cleaning step in the formation of 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 10 nm to 300 nm, and more preferably 30 nm to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by using a known film thickness measuring device such as a profilometer or a sugar meter 113 201237065 wwzpxt (ellipsometer). A 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 for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film for aligning the liquid crystal molecules in a predetermined direction . The liquid crystal alignment film uses the aforementioned liquid crystal alignment film of the present invention. The substrate may be a glass substrate as described in the liquid crystal alignment film of the present invention. The electrode may 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 in a gap between a pair of substrates opposed to each other, wherein a surface of one of the pair of substrates on which the liquid crystal alignment film is formed faces the other substrate. The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. A preferred liquid crystal composition having a positive dielectric anisotropy is exemplified by Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, Japanese Patent Laid-Open No. Hei No. Hei 8-157826, and Japanese Patent. Japanese Unexamined Patent Publication No. 8_23, Japanese Patent Special Openance = a4243^=Em5272A1, and Japanese Patent Laid-Open No. 9-302346旎 (10)〇64_ Sakai Kaihe No. 8 Bulletin (EP722998A1, 9-235552, Japan, Japan) Patent special open umbrella Μ 日 日 日 ; ; ; 日 日 日 日 日 ; ; ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ ΕΡ 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰The liquid crystal composition patent disclosed in Japanese Patent Laid-Open Publication No. 2000-087040, No. 2000-48822, and the like, and the liquid crystal composition patents disclosed in Japanese Patent Laid-Open Publication No. 2000-087040, and the like. Ship number bulletin, Japanese patent special Kaiping 2 milk No. 5 咐利特开平专#ίο μ本本制平8韵869号, Japan = two: =:, 曰本专利专开平心平平10-23699 , 八二'Ί6989 *Gazette, Japanese Patent Special Report, 曰本专利特门^^,^ This patent special open flat W marriage 92 No. 1 〇-_4 public "This special: t bulletin, 曰本 patent special open patent Special Kaiping 1.-Two newspapers Patent Special Publication No. 10-237076, n Shishiben Patent Special Kaiping (EP967261A1 Description 开) Kaiping 1〇-237448 Gazette, 曰本专利专开平平::号公1〇 _2 just 45th bulletin, koushikui can report this patent special open flat patent special report newspaper special open Kaiping 11-029581 bulletin, Japanese patent special open Nag 〇 72626 special ^ temple open 2 〇 01 彻 65 bulletin Japanese Laid-Open Patent Publication No. P discloses that the optically anisotropic composition is a positive or negative crystal composition. The addition of 1 201237065 4〇462pif or more optically active compound can be used. The device can be obtained by forming a liquid crystal alignment film of the present invention on at least one of a pair of substrates, and causing the pair of substrates to be opposed to each other with the spacer facing inward with the liquid crystal alignment film facing inward, between the substrates A liquid crystal composition is sealed in the formed gap to form a liquid crystal layer. In the production of the liquid crystal display device of the invention, a further step of attaching a polarizing film to the substrate may be included as needed. A liquid crystal display element of the present invention can form various liquid crystal display elements for electric field mode. The liquid crystal display element may be a liquid crystal display element for applying a voltage to the liquid crystal layer with the electrode in a horizontal direction with respect to a surface of the substrate, or with respect to a surface of the substrate A liquid crystal display element is used in the vertical direction in which a voltage is applied to the liquid crystal layer by the electrodes in the vertical direction. The liquid crystal alignment film produced by using the liquid crystal alignment agent of the present invention as a raw material can be suitably used in liquid crystal display elements of various display driving methods by appropriately selecting a polymer as a polymer. The liquid crystal display element of the present invention may further have the above-described constitution and elements other than the above. As such other constituent elements, the liquid crystal display device of the present invention can also be used in a liquid crystal display device such as a polarizing wire (partial wire), a wave plate optical optical film, and a driving circuit. Elements. [Examples] The secondization == invention is explained. In addition' in the example

S 116 201237065 <tetracarboxylic dianhydride> Acid dianhydride (Al): 1,2,3,4-cyclobutanetetracarboxylic dianhydride dianhydride (A2): pyromellitic dianhydride dianhydride Anhydride (A3): 1,2,3,4-tetradecyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride <Diamine> Diamine (Dl): N, N'- Bis(4-Aminophenyl)-NV-dimercaptoethylenediaminediamine (D2): N,N'-bis(4-aminophenyl)pyridazinediamine (D3): 4,4· -diaminodiphenyldecanediamine (D4) : 3,3'-diaminodiphenyldecanediamine (D5) : 1,4-phenylenediamine diamine (D6) : 4,4 '-Diaminoazobenzenediamine (D7) : 4,4'-Diaminodiphenylamine <Solvent> N-Mercapto-2-pyrrolidone: NMP Butyl Cellulite (Ethylene Glycol Monobutyl) Ether): BC <Additives> Additives (Adi): bis[4-(allylbicyclo[2.2_1]hept-5-ene-2,3-dicarboxyindenimido)phenyl]decane additive ( Ad2) : N, N, NW-tetraglycidyl-4,4'-diaminodiphenyl decane additive (Ad3): 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Decane 117 201237065 Additive (Ad4): 3-Aminopropyltriethoxydecane <1. Synthesis of Polylysine> [Synthesis Example 1] A 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet was charged with diamine (D1) 3 397 g and dehydrated NMP 40.0 g, which were stirred and dissolved under a dry nitrogen stream. Next, 1.232 g of acid dianhydride (Al), 137 〇g of acid dianhydride (A2), and dehydrated stomach 卩 4〇.〇g were added, and stirring was continued for 24 hours at room temperature. BC 14_0 g was added to the reaction solution to obtain a polyglycine solution having a polymer solid concentration of 6 wt%. The polyaminic acid solution was used as PA1. The polyamine acid contained in pA1 has a weight average molecular weight of 1 〇 4,5 Å. The weight average molecular weight of poly-aracine was determined by a GPC method using a 2695 separation module-2414 differential refractometer (manufactured by Waters), and was obtained by polystyrene conversion. The obtained polylysine was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = = 〇.6 / l 〇〇 : weight ratio) to a polyglycine concentration of about 2 wt%. The column was HSPgel RT MB_M (manufactured by Waters), and the mixed solution was used as a developing solvent at a column temperature of 5 Torr. The measurement was carried out under conditions of a flow rate of 0.40 mL/min. The standard polystyrene uses TSK standard polystyrene manufactured by Japan Tosoh Corporation. [Synthesis Example 2 to Synthesis Example 19] The polyamic acid having a polymer solid concentration of 6 wt% was prepared based on Synthesis Example 1 except that the tetracarboxylic dianhydride and the diamine were changed as shown in Table 1. Solution (PA2)~polyproline solution (PA19) ^Including the results of Synthesis Example 1 'Measurement of the weight average molecular weight of the obtained polylysine (/) 118 201237065 4〇462pif The results are summarized in the table

Diamine (mol%) Weight average D2 D3 D4 D5 D6 ΰΓ amount) 104,500 50 87,500 50 90,000 50 78,500 100 112,600 50 50 96,800 50 50 89,000 50 86,800 20 20 91,000 60 20 93,900 50 91,700 50 72,400 50 bO 70,700 ) 10 .102,700 54,300 1 90 90 1U 100,900 10 90 53,800 100 63,400 100 52,400 <2. Preparation of substrate for transmittance evaluation> [Example 1] The polymer solid concentration prepared in Synthesis Example 1 was 6 wt% To the polyaminic acid solution (pAl), a mixed solvent of NMP/BC = 4/1 (weight ratio) was added, and the mixture was diluted to a polymer solid concentration of 4 wt%, and the obtained liquid crystal alignment agent was used as a liquid crystal alignment at ° as follows. A substrate for transmittance evaluation was produced as shown. <Method for Producing Transmissivity Evaluation Substrate 1> A liquid crystal alignment agent was applied onto a glass substrate by a spinner. In addition, the rotational speed of the rotator was adjusted according to the viscosity of the liquid crystal alignment agent, including the subsequent examples and comparative examples, so that the alignment film had the following film thickness. After the film was applied, after 7 minutes of heating and drying at TC, the ML-501C/B manufactured by Ushio Inc. was used in a vertical direction with respect to the substrate. A linearly polarized light that is irradiated with ultraviolet rays through a polarizing plate. The exposure energy at this time is measured using an ultraviolet ray cumulative photometer UIT-150 (photodetector UVD_S365) manufactured by Ushio Inc., and is 3.0±〇 at a wavelength of 365 nm. The exposure time is adjusted by the method of lj/cm2. The ultraviolet light can be irradiated with ultraviolet rays to prevent the film from covering the entire device, and it is carried out in the air at room temperature. Secondly, the film thickness is 1 在 under 23 (TC for 15 minutes).配±1〇nm alignment film [Example 2 to Example 17] A polyglycine solution (PA2 to pA17) having a polymer solid concentration of 6 wt〇/〇 prepared in Synthesis Example 2 to Synthesis Example π, respectively. A mixed solvent of NMP/BC = 4/1 (weight ratio) was added and diluted to a polymer solid concentration of 4 wt% to obtain a liquid crystal alignment agent. The obtained liquid crystal alignment agent was produced by the method based on Example 1. Substrate for transmittance evaluation. [Example 18] In the polyaminic acid solution (PAl〇) having a polymer solidification sensitivity of 6 in the synthesis example 10, the additive was added in an amount of 20 sensations per unit weight of the polymer (Adn. Thereafter, Adding this solvent of NMp/Bc 4 'diluted to the polymer solids concentration is

Wt / o as a liquid crystal alignment agent. In addition, including the following examples, ί = use: the concentration of the polymer solids at the time of dosing does not include the amount of the additive. Using the obtained liquid crystal alignment agent, the transmission is made by the method based on the example 120 201237065 40462pif method. The substrate for evaluation. [Example 19] In a polyaminic acid solution (PA1()) having a polymer solid concentration of 6 prepared in Synthesis Example 10, a ratio of 20 wt% of hemp additive per unit weight of the polymer ( Ad2). Thereafter, a mixed solvent of NMp/Bc = 4 A (weight ratio) was added, and the mixture was diluted to a polymer solid concentration of 4 wt% to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a substrate for transmittance evaluation was produced by the method of Example 1. [Example 20] In a polyglycine solution (PA1G) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 1 , an additive (Ad3) was added in a ratio of H) w (10) per unit weight of the polymer. ). Thereafter, a mixture of NMp/Bc = 4 Λ (by weight) was added and diluted to a polymer concentration of 4 wt% to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a substrate for transmittance evaluation was produced by the method of Example 1. [Example 21] The polymer solid matter prepared in Synthesis Example 1 was subjected to a ratio of 6 wt% of poly-aracine solution (PA1G), and was added in a ratio of 5. 5 wt% per unit polymer by weight. Additive (Ad4). Thereafter, a mixed solvent of NMp/Bc = 4/1 (weight ratio) was added, and the mixture was diluted to a polymer solid concentration of 4 wt% to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a substrate for transmittance evaluation was produced by the method of Example 1. [Example 22] NMp/BC = 4/i (weight ratio), mixed solvent was added to the polyglycine solution (pA1〇) of the polymer solids prepared in Synthesis Example 10, which was 6 _ 121 201237065 HUHOZpii Diluted to a polymer solids concentration of 4 Wt% and as liquid BB to η j. Using the obtained liquid crystal alignment agent, a substrate for transmittance evaluation was produced as follows. <Method for Producing Transmissivity Evaluation Substrate 2> A liquid crystal alignment agent was applied onto a glass substrate by using a square crucible. After coating, the film was heated and dried at 1 hour C for 1 minute, and then heat treated at 230 ° C for 15 minutes. This glass substrate is used. The Rayby color lamp MLWIC/B manufactured by Zhan Kee Inc. is a linear polarized light that is irradiated with ultraviolet light through a polarizing plate in a direction perpendicular to the substrate (exposure energy: 3.0±〇.i J at 365 nm) /cm2), an alignment film having a film thickness of 1 〇〇 ± 1 〇 nm was formed. The conditions of the ultraviolet irradiation and the adjustment of the exposure energy were based on the method of Example i. [Comparative Example 1 and Comparative Example 2] NMP/BC = 4/ was added to the polystyroic acid solution (pA18& pAi9) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 18 and Synthesis Example 19, respectively. A mixed solvent of 1 (weight ratio) was diluted to a polymer solid concentration of 4 wt% to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a substrate for transmittance evaluation was produced by the method of Example 1. [Comparative Example 3] A mixed solvent of NMp/BC = 4/1 (weight ratio) was added to a polyamic acid solution (pA19) having a polymer solid concentration of 6 mg prepared in Synthesis Example 19, and diluted to polymerization. The solid matter concentration was 4 sides and used as a liquid crystal alignment agent. The substrate for transmittance evaluation was prepared according to the method of Example 22, 2012, pp. <3. Evaluation of Transmittance> The transmittance of the alignment film was measured using a UV-Vis spectrometer (V_660 manufactured by JASCO Corporation). A glass substrate on which an alignment film was not formed was used as a reference. The measurement was carried out at a scanning speed of 400 nm/min per 1 nm to a wavelength range of 380 nm to 780 nm; The average value of the transmittance in the wavelength region is taken as the transmittance of the alignment film. = The more the transmittance is, the better. The measurement results are shown in Table 2, and the value is larger ‘T 0 Table 2

123 201237065 40462pif The table indicates that no additives were added. It is understood that Comparative Example 1 uses polyamine which is synthesized from a diamine having an azobenzene structure as a raw material, and thus the transmittance is remarkably inferior. The alignment films of the present invention of Examples i to 22 have good transmittance and little coloration. &lt;4. Preparation of liquid crystal display element&gt; [Example 23] The polymer solid concentration prepared in Synthesis Example 1 was 6 to (% added in polyacrylic acid solution (PA1)] snviP/BC = 4 a mixed solvent of /l (weight ratio) was diluted to a polymer solid concentration of 4 wt% to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal cell was produced as follows. <Production Method of Liquid Crystal Display Element 1 &gt; A liquid crystal alignment agent was applied to two glass substrates with an IT crucible electrode by a spinner, and after being coated with a film, it was heated and dried at 7 (rc for about 丨 minutes) using Ushio Inc. The RUBI color lamp ML-501C/B is a linearly polarized light (exposure energy: 3.0 ± 0.1 J/cm 2 at 365 nm) which is a vertical direction with respect to the substrate and is irradiated with ultraviolet rays through a polarizing plate. The conditions for adjusting the ultraviolet irradiation and the method for adjusting the exposure energy were based on Example 1. Next, heat treatment was performed for 15 minutes at 2,302⁄4 to form an alignment film having a film thickness of 100 nm and 10 nm. Two aligning films were formed on the ιτο electrode. The substrate is formed with the facing of the alignment film to each Film irradiated ultraviolet rays polarized parallel to the direction change mode, for further formed liquid crystal composition is injected into voids between which the film is bonded to the ligand, the cell thickness of the assembly 4 μιη

124 S 201237065 40462pif empty unit. Further, the injection port for injecting the liquid crystal into the empty cell is not placed at a position where the direction in which the liquid crystal flows during the injection and the direction in which the ultraviolet light irradiated to the alignment film is substantially parallel. The liquid crystal cell was formed by vacuum-injecting the liquid crystal composition A' shown below into the empty cell fabricated as described above. <Liquid crystal composition A &gt;

17 wt% 17 wt% 16 wt% 10 wt% 5 wt% 10 Wt% 6 wt% 6 wt% 13 wt% n-CsH^ [Example 24 to Example 39] respectively prepared in Synthesis Example 2 to Synthesis Example Polymer solids 125 201237065 40462pif A 6 wt% poly-araminic acid solution (pA2~pAl7) was added with a mixed solvent of NMP/BC-4/1 (heavy ratio) and diluted to a polymer solid concentration of 4 wt. % as a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, the empty unit was assembled by the method of Example 23. Next, a liquid crystal cell is formed by vacuum injecting a liquid crystal composition A' into this empty cell. [Example 40] In a polyglycine solution (PA1G) having a polymer solid concentration of 6 wt% prepared in Synthesis Example ί, an additive was added in an amount of 20 wt% (four) per unit polymer weight (Adl) ). Thereafter, a mixed solvent of NMp/Bc = 4 / 丨 (by weight) was added, and the mixture was diluted to have a polymer solid concentration of 4 wt / 〇 as a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, the "component" was assembled by the method based on Example 23. Next, the liquid crystal composition A was vacuum-injected into the unit to prepare a liquid crystal cell. [Example 41] Modulated in Synthesis Example H) A polymer solids concentration of 6% by weight of a poly(IV) solution (PA1G) towel is added to the additive (5) 2) per unit of polymer weight. Thereafter, nmp/bc = 4/i (heavy (d)) is added. The mixed solvent ' _ spliced as a liquid crystal alignment agent. The empty unit was assembled using the obtained method based on the actual method. Next, the liquid crystal composition A was injected into the space 3 to form a liquid crystal cell. [Example 42]

S 126 201237065 40462pif Example added to add kad 3d). Thereafter, NMp/Bc 7 _ to polymer concentration was added as its two tf agent. Using the obtained liquid crystal alignment agent, a solid, 23-based square shirt unit was used. Next, the liquid crystal composition A was vacuum-injected into the empty cell to prepare a liquid crystal cell. [Example 43] The concentration of the polymer solid matter prepared in (4) was 6 swim. In the poly = gluten solution (PA1G), to add 0 to 5 pain per unit of polymer weight, for example, add an additive (application). Thereafter, a mixed solvent of 4 We»/weight ratio was added and diluted to a polymer solid concentration of 4 wt/o as a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, the empty single core was assembled by the method of Example 23, and the liquid crystal composition A was vacuum-injected into the empty cell to prepare a liquid crystal cell. [Example 44] The polymer solid concentration prepared in Example 10 was 6 gram. In the polyamic acid solution (PA1G), a mixed solvent of NMp/Bc = 4/i (weight ratio) was added, and the concentration of the mixture was 4 swim. As an aligning agent. The obtained liquid crystal alignment agent was used to prepare a day and night as described below. &lt;Manufacturing Method 2 of Liquid Crystal Display Element&gt; The liquid crystal alignment agent was applied onto two glass substrates with a ruthenium electrode by the rotation 11. . After coating, the film was heat-dried at 7 (TC for 丨 minutes, and then heat-treated at 23 (TC for 15 minutes). For the glass substrate on which the alignment film was formed, RUBI color produced by Ushi〇 Inc. was used. Lamp 127 201237065 40462pif ML-501C/B, linearly polarized light that is irradiated with ultraviolet light through a polarizing plate in a direction perpendicular to the substrate (exposure energy: energy at 365 ηιη is 3. 〇±〇. Ij/cm2) 'Forming an alignment film having a film thickness of 1 〇〇 ± 1 〇 nm. The conditions for adjusting the ultraviolet ray irradiation and the exposure energy are based on the example i. The formation of two substrates on which the alignment film is formed on the ITO electrode is formed. In the direction in which the alignment film is faced, the polarization direction of the ultraviolet ray irradiated on each of the alignment ridges is paralleled. Further, a gap for injecting the liquid crystal composition is formed between the opposing alignment films, and the assembly unit is bonded. The thickness is 4 μm = empty cells. Moreover, the injection port for injecting liquid crystal into the empty cell is disposed at a position where the direction in which the liquid crystal flows during injection is substantially parallel to the polarization direction of the ultraviolet light irradiated to the alignment film. True in the unit The liquid crystal composition A was injected into the liquid crystal cell to make a liquid crystal cell. [Comparative Example 4] MNMp/BC was added to a polyglycine solution (pA12) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 19. = 4/1 (weight ratio) of the mixed solvent, the solid concentration of the converted silk compound was 4, and the obtained liquid crystal alignment agent was used as the liquid crystal alignment agent L, and the empty unit was assembled by the method of Example 23. Next, in the empty A liquid crystal cell was prepared by vacuum-injecting the liquid crystal composition A into the cell. [Comparative Example 5] NMP/ was added to the polystyrene acid (pAl2) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 19. A mixed solvent of BC = 4/1 (weight ratio) was diluted to a polymer solid concentration of 4 wt% to serve as a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, an empty unit was assembled using the method of Example 44, No. 128 201237065 40462pif method. Next, the liquid crystal composition A was vacuum-injected into the empty cell to form a liquid crystal cell. <5. Observation of Flow Orientation> The liquid crystal cell fabricated as described above was sandwiched and arranged in crossed Nicols (crossed nicols) of two polarizers, by mesh In the liquid crystal cell, 'the ultraviolet ray irradiated to the liquid crystal alignment film' is cut along the cyclobutane skeleton of the polymer main chain in the polarization direction of the ultraviolet ray. Therefore, the liquid crystal composition is aligned with respect to ultraviolet rays. In the liquid crystal cell in which the alignment film having good alignment property is used, the so-called flow alignment is not observed at all, that is, the liquid crystal is aligned along the direction in which the liquid crystal flows from the injection port. On the other hand, in the liquid crystal cell using the alignment film having poor alignment, flow alignment was observed. The observation results of the flow alignment are shown in Table 3. &lt;6. Observation of alignment defects&gt; The liquid crystal cell in which the flow alignment was observed was subjected to isotropic treatment at 11 ° C for 3 Torr and cooled to room temperature. When the polarizing microscope was placed in a crossed Nicols state and the liquid crystal cell was observed again, no alignment defect of the liquid crystal was observed in the liquid crystal cell using the alignment film having good alignment. On the other hand, in the liquid crystal cell using the alignment film having poor alignment, the alignment defect of the liquid crystal was observed. The observation results of the alignment defects are shown in Table 3. 》 , 129 201237065 4U402pit Table 3 Example No, Polyproline solution No. Additive flow alignment alignment defect Example 23 PA1 No example 24 PA2 No example 25 PA3 There are instances 26 PA4 There are instances 27 PA5 No example 28 PA6 _ There are examples 29 PA7 There are instances 30 PA8 No instances 31 PA9 No instances 32 ΡΑΙΟ No examples 33 ΡΑ11 No examples 34 PA12 No examples 35 PA13 No examples 36 PA14 No examples 37 PA15 . Example 38 PA16 . No examples 39 PA17 There are instances 40 ΡΑΙΟ Adi There are instances 41 ΡΑΙΟ Ad2 There are instances 42 ΡΑΙΟ Ad3 There are instances 43 ΡΑΙΟ Ad4 There are instances 44 ΡΑΙΟ No ΡΑ 19 There are Comparative Examples 5 ΡΑ 19 - There are tables The middle one indicates that no additive is added. When the exposure energy of ultraviolet rays was 3. 〇±〇.1 j/cm 2 B, the cases of Examples 23 to 44 were observed to have defects, and in any of Comparative Example 4 and Comparative Example 5, flow defects and alignment were observed. defect. [Example 45 to Example 61] NMP/BCy/l (weight ratio) was added to a polyglycine solution (pA1 to pA17) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 1 to Synthesis Example 17, respectively. The mixed solvent was diluted to a polymer solid concentration of 4 wt% to serve as a liquid crystal alignment agent. Using the obtained liquid 曰曰 _ / '&quot;Hid 130 201237065 40462pif 2 change the irradiation energy of the line to 365 _ τ is J/cm 'except for this _ based on the method of Example 23, the secret sound is 4 哗Empty unit. Further, in these compositions, a liquid crystal cell is produced. The main working day of the work was carried out [Example 62] The polymer solid solution of the polyamic acid solution prepared in Synthesis Example 10 was added to add the addition agent Udl in each single compound. Thereafter, a mixed solvent of VBC 4/1 (heavy ratio) was added, and the mixture was diluted to a liquid crystal alignment agent. The resulting liquid crystal alignment 2 was used to assemble the empty cells based on the method of Example 45. Next, the liquid crystal composition A was injected into the vacuum in the space to form a liquid crystal cell. [Example 63] In a polyterpene solution (PA1G) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 10, an additive (Ad2) was added in an amount of 20 per unit. Thereafter, a mixed solvent of MN-3/1 (heavy ratio) was added, and the mixture was diluted until the polymerization was carried out according to the method of Example 45. The empty cell n was vacuum-injected into the liquid crystal composition A to form a liquid crystal cell. 64] In the polyamic acid solution (PAU) of the polymer solid matter prepared in Synthesis Example 10, the ratio of Wt% per unit was added to the additive (5) 3). Thereafter, the surface was added. 131 201237065 40462pif -4/1 (weight ratio of 1) of the mixing shaft, diluted wire blended material concentration of 4, as a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, the empty unit was assembled by the method based on Example 45. Secondly, Liquid crystal composition A was vacuum-injected into the empty cell to prepare a liquid crystal cell. [Example 65] In a polyglycine solution (PA1〇) having a polymer solid concentration of 6 wt% prepared in Synthesis Example ίο, The additive (Ad4) is added in an amount of OJwt per unit weight of the polymer. Thereafter, a mixture of NMp/Bc -4/1 (weight ratio) is added, and the concentration of the converted compound is wt%. As a liquid crystal alignment agent, the obtained liquid crystal alignment agent was used to assemble empty using the method of Example 45. Next, a liquid crystal cell was prepared by vacuum-injecting the liquid crystal composition A into the empty cell. [Example 66] The polymer solid concentration prepared in Synthesis Example 10 was 6 ^, and only the proline solution (pA1〇) In the addition of NMp/BCH (remixed solvent, the concentration of the spectroscopy polymer is 4 wt% and the di- aligning agent. Using the obtained liquid crystal alignment agent, the ultraviolet Z is more than 5 at 365 nm. 〇±〇u/cm2, except that the empty cell was assembled by the method of Example 44. Next, the liquid crystal cell A was formed by hollowing into the empty cell. [Comparative Example 6] = Synthesis The concentration of the polymer solids prepared in Example 19 was 6, and in the amine acid solution (PA19), the mixture of nmp/bc;:=4/1 (weight ratio) was added, and the solid concentration of the silk compound was 4 And

S 132 201237065 40462pif is a liquid helium a aligning agent. Using the obtained liquid crystal alignment agent, the unit was shouted by the method based on the example Μ. Next, the liquid crystal cell is made into the liquid crystal composition A' to form a liquid crystal cell. [Comparative Example 7] In a polyglycine solution (pA19) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 19, a mixed solution of NMp/BC = 4/1 (weight ratio) was added. The agent was diluted to a polymer solid concentration of 4 to serve as a liquid crystal alignment agent. Using the resulting liquid crystal alignment agent, an empty cell is shouted using an example based method. Next, a liquid crystal cell was formed by vacuum-injecting the liquid crystal composition A' into the unit cell. &lt;Observation of Flow Arrangement&gt; In the same manner as described above, the liquid crystal cell was sandwiched between the crossed Nicols: ==! 2, and the flow alignment was visually observed. Each crystal unit of the flow alignment &lt;observation of alignment defects&gt; was treated at ll (rc for 3 〇min Π丨m, cold room temperature. It: owed, polarized microscopy] Re-observation results for the immersion of the crystal unit (4) are shown in Table 4. 133 201237065 40462pif Table 4 Example No. Polyamide Degradation Solution No. — Additive Flow Alignment Defect Example 45 PA1 No Example 46 PA2 'One Nothing Instance 47 PA3 • No Instance 48 PA4 • M. No Instance 49 PA5 _ No Instance 50 PA6 _ No Instance 51 PA7 _ No Instance 52 PA8 No Instance 53 rAy _ No Instance 54 ΡΑΙΟ — no instance 55 PAll - no instance 56 PA12 _ no instance 57 PA13 no instance 58 PA14 no instance 59 PA15 no instance 60 PA16 '- no instance 61 PA17 no instance 62 ΡΑΙΟ Adi no Example 63 ΡΑΙΟ Ad2 No instance 64 ΡΑΙΟ Ad3 No instance 65 ΡΑΙΟ &quot; Ad4 None - Example 66 ΡΑΙΟ - No Pu^Cly'J 〇γΑ19 • There is Comparative Example 7 ΡΑ1 9 - There is a table - indicating that no additive is added. If the exposure energy of ultraviolet light is 5 〇 ± 〇丨 J / cm 2 , flow deficiencies and alignment defects are found in any of Comparative Example 6 and Comparative Example 7, in the example A defect was observed in only Example 63 in 45 to Example 66. [Example 67 to Example 83] A polyglycine solution (pA1~) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 1 to Synthesis Example 17, respectively. A mixed solvent of NMP/BC = 4/1 (weight ratio) was added to pA17), and diluted to a polymer solid concentration of 4 wt% to obtain a liquid crystal alignment agent.

S 201237065 40462pif agent, the irradiation energy of ultraviolet rays was changed to 10.0 ± 0.1 J/cm 2 at 365 nm, except that the empty cell was assembled by the method of Example 23. Further, a liquid crystal composition A was vacuum-injected into these empty cells to form a liquid crystal cell. [Example 84] The polyglycine solution (ΡΑΙΟ) having a polymer solid concentration of 6 wt 〇 /0 prepared in Synthesis Example 10 was used per unit weight of the polymer.

The additive (Adi) was added in a ratio of 20 wt%. Thereafter, a mixed solvent of NMP/BC = 4/1 (weight ratio) was added, and the mixture was diluted to a polymer solid concentration of 4 wt% to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, the empty unit was assembled by the method based on Example 67. Next, the liquid crystal composition A was vacuum-injected into the empty cell to prepare a liquid crystal cell. [Example 85] In a polyglycine solution (PA1G) having a polymer solid concentration of 6 wt% prepared in Synthesis Example ί, added in an amount of 2 to 0 wt% per weight of the monofilament Additive (Ad2). Thereafter, a mixed solvent of NMp/Bc = 4/1 (weight ratio) was added and diluted to a polymer solid concentration of w as a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, the method based on Example 67 was used, and 奘* was left a 廿 ancient assembly. Next, the liquid crystal composition A was vacuum-injected into the empty cell to prepare a liquid crystal cell. [Example 86] In the polymerized polyaminic acid solution (PAl〇) prepared in Synthesis Example 10, in the weight of the mother early polymer in the weight / morning intensity of 6 Wt / 〇 10 ) 〇 Add _ Additives (Ad3). After that, add the dirty 135

201237065 4U^fOZpiI = 4/i (by weight) mixed solvent was diluted to a polymer solid concentration of 4 wt% as a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, the empty unit was assembled by the method based on Example 67. Next, the liquid crystal composition A was vacuum-injected into the empty cell to prepare a liquid crystal cell. [Example 87] In the polyglycine solution (PA10) having a polymer solid concentration of 6 pain prepared in Synthesis Example 10, an additive was added in a ratio of 0.5% by weight per unit weight of the polymer ( Ad4). Thereafter, a mixed solvent having a surface of 4 / U by weight was added, and the polymer solid concentration was diluted to 4 wt% to obtain a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, the empty unit was assembled by the method based on Example 67. Next, the liquid crystal composition A was vacuum-injected into the empty cell to prepare a liquid crystal cell. [Example 88] In a polyaminic acid solution (PA1 〇) having a polymer solid concentration of 6 (4) prepared in Synthesis Example 10, a mixed axis of NMP/BC = 4/1 (heavy edge ratio) was added to be diluted to The polymer_concentration was 4 wt% and f was a liquid crystal alignment agent. The obtained liquid daily and daily alignment agent, «the external body energy was changed to 1 〇 Λ J/cm 2 at 365 nm, and the other unit was assembled according to the method of Example 44, and the thickness of the unit was 4, (4). ^ -People's vacuum injection of liquid crystal composition A into a work order, making a liquid crystal cell [Comparative Example 8] Polymeric solid concentration of 6 wt〇/polyamide prepared in Example 19 ^^ liquid (PA19), add = W (heavy. ratio) H agent, diluted to a polymer solid concentration of "good and seven

S 136 201237065 40462pif is a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, the empty sheet 70 was assembled by the method of Example 67. Next, a liquid crystal cell is formed by vacuum-injecting the liquid crystal composition A' into the empty unit. [Comparative Example 9] In a polyglycine solution (PA19) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 19, a mixed solvent of NMP/BC 2/1 (weight ratio) was added. The concentration of the polymer solid is 4 (four) as a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, empty cells were assembled using the method based on Example 88. It is: owed, vacuum injection of the liquid crystal composition A into the m unit towel to prepare a liquid crystal cell. &lt;Observation of Flow Orientation&gt; In the same manner as described above, the liquid crystal cell was sandwiched between two polarizing plates arranged in a crossed Nicols prism, and the flow alignment was visually observed. The observation results of the flow alignment are shown in Table 5. &lt;Observation of alignment defects&gt; The liquid crystal cell of the flow alignment was observed at 11 Å. The same process was carried out for 3 minutes in the armpits and cooled to room temperature. It: owed, so that the partial micromirror becomes the state of the father Nikule prism and then: the liquid crystal money is obsolete. The observation results of the alignment defects are shown in Table 5. 137 201237065 40462pif Table 5_Example No. Polyas Amino Acid Solution No. Additive Example 67 Example 68 Example 69 Example 70 Example 71 Example 72 Example 73 Example 74 Example 75 Example 76 Example 77 Example 78 Example 79 Example 80 Example 81 Example 82 Example 83 Example 84 Example 85 Example 86 Example 87 Example 88 Comparative Example 8 Comparative Example 9 PA1ΎΑ2 ΤΑ3 ΡΑ4ΎΑ5^Α6 1PA7^Α8^Α9 ΡΑΙΟ ΡΑ11 ΡΑ12 ΡΑ13 ΡΑ14 ΡΑ15 ΡΑ16 ΡΑ17 ΡΑΙΟ ΡΑΙΟ ΡΑΙΟ ΡΑΙΟ ΡΑΙΟ ΡΑ19 ΡΑ19

Adl_ Ad2 Ad3 Ad4

The table indicates that no additives were added. If the exposure energy of the ultraviolet ray was further increased to 10.0 ± 〇 1 J/cm, no defects were observed at all in Examples 67 to 88. On the other hand, the alignment defect was found in Comparative Example 8. According to the results of the examples 23 to 88 and the comparative examples 4 to 9, the alignment film of the present invention is excellent in the alignment property even under low-energy ultraviolet irradiation, and the sensitivity due to the chemical change of the light irradiation is good. As described above, it is known that when the alignment film of the present invention is applied to a liquid crystal display 138

S 201237065 40462pif The component is equipped with a matching sensation, and it has the characteristics of translucent and fine-spraying. Further, the alignment film of the present invention can be sufficiently subjected to a tack treatment by ultraviolet rays of a general-purpose wavelength, and * can be subjected to photoalignment treatment even if it is irradiated with ultraviolet rays of lower energy than a known photo-alignment film. [Simple description of the diagram] [Explanation of main component symbols] 139

Claims (1)

201237065 40462pif VII. Patent application scope: 1. A liquid crystal alignment agent containing polyamic acid or a derivative thereof obtained by reacting tetracarboxylic dianhydride with a diamine, and used for forming a liquid crystal alignment film for photoalignment. The tetracarboxylic dianhydride comprises a tetracarboxylic dianhydride represented by the following formula (I); the diamine contains a diamine selected from the following formula (N-1) and formula (N-2) At least one of the groups; (I) In the formula (I), RA to RD are independently hydrogen or an alkyl group having 1 to 4 carbon atoms; h2n Re·^^ (N-1) NH, in the formula (N-1), RE is independently a monovalent organic group; RF is independently hydrogen, a monovalent organic group or a halogen; and Z is a carbon number of 1 to 5. a divalent group of an alkyl group; 140 S 201237065 40462pif In the formula (N-2), R° is independently a monovalent organic group or a halogen; RH is independently a monovalent organic group; m is independently an integer of 0 to 3; and η is an integer of 0 to 4. 2. The liquid crystal alignment agent according to Item 1, wherein the RE is independently an alkyl group having a carbon number of 1 to 3, and the RF is independently hydrogen, an alkyl group having 1 to 3 carbon atoms, fluorine, chlorine, or A poly-proline or a derivative thereof obtained by reacting a diamine represented by the formula (N-1) or a diamine mixture containing the diamine with a tetracarboxylic dianhydride. 3. The liquid crystal alignment agent according to claim 1, which comprises or contains the diamine represented by the formula (N-1) having an amine group in each of the phenyl groups at both ends of the molecule. Polylysine or a derivative thereof obtained by reacting a diamine mixture of an amine with a tetracarboxylic dianhydride. 4. The liquid crystal alignment agent according to claim 1, which contains at least a group selected from the group consisting of diamines represented by the following formulas (N-1-1) to (N-1-20) a poly-proline or a derivative thereof obtained by reacting a diamine mixture containing the diamine with a tetracarboxylic dianhydride; 141 201237065 4U462pit /=\ ch3 CH \v ~N-CH CH3 CH H2N H2n H2n-^ H2n N—(ch2 CH3 CH N-(CH2 CH3 CH N-(CH; CH3 CH hJ-(CH; h2n H2n H2n H2n H2n C2H5 C, H d1 c2h5 ?2H5 C3H7 C3H7 n-ch2 * 1 -(CH2): h2n (Nl-1) (Nl-2) (Nl-3) (Nl-4) (Nl-5) (Nl-6) (Nl-7) (Nl-8) (Nl-9) (Nl-10) (Nl-11) (Nl-12) (Nl-13) (Nl-14) (Nl-15) C3H7 N-iCH2)-N- ^&gt;==\-\J-^ C3H7 〇3Ητ^ N— (CH2)HSI—~N_ 〒3H7 C3H7_ h2n H2n H2 h2 h2n^^-n^ch2)Jj-Q)-nh2 142 s 201237065 40462pif (Nl-16) (Nl-17) (Nl-18) (Nl-19) (Nl-20) 5. The liquid crystal alignment agent of claim i, which contains RG independently as carbon number 1 a diamine or a derivative represented by the formula (N-2) in which an alkyl group having 10 to 10 carbon atoms, an alkoxy group having a carbon number, an amidino group, a fluorine, a gas, or a bromine, and RH is independently an alkyl group having 1 to 3 carbon atoms; Polylysine or a derivative thereof obtained by reacting a diamine mixture of the diamine with a tetracarboxylic dianhydride. 6. The liquid crystal alignment agent according to claim 1, which contains a diamine represented by the formula (N_2) having an amine group in the phenyl group at both ends of the molecule, or a diamine containing the same. Polylysine or a derivative thereof obtained by reacting a diamine mixture with a tetracarboxylic dianhydride. 7. The liquid crystal alignment agent according to the invention, which contains at least one selected from the group consisting of diamines represented by the following formulas (Ν·2·1) to (10) (7). Or a poly-deuterated acid or a derivative thereof containing a diamine compound and a di-anthracene; 143 20123706540462pif (N-2-1) (N-2-2) (N-2-3) (N-2-4) (N-2-5) (N-2-6) (N-2-7) (N-2-8) 144 s 201237065 40462pif H2N H2 h2n H2 Η3^〇^OCH3 H3CO OCH3 H2N-^Q)^^_M_Nh2 (N-2-9) (N-2-10) (N-2-12) (N-2-13) (N-2-14) (N-2-15) The liquid crystal alignment agent according to claim 1, which contains the formula (N-2-1) and the formula (N- as described in claim 7 of the scope of the patent application. 2-2) Polyamine or a derivative thereof obtained by reacting at least one of the diamines represented by the diamines or the diamine mixture containing the diamines with two needles of tetrazolium. 9. The liquid crystal alignment agent of the first aspect of the invention, wherein the liquid crystal alignment agent contains at least 1 group further comprising a diamine selected from the group consisting of the following formulas (III) to (IX) and (XV); Kind of diamine mixture reacted with tetracarboxylic dianhydride 145 201237065 40462pif obtained polyglycine or its derivative; H2N-~A1-NH2 H2N v~~b NH, H2N h2n H2n 〇-y-(^y-〇Nh2 33 R, H2N-G-(-Si-0-R34 R 33 Si-G_ 丄34 -NH2 (III) (IV) (V) (VI) (VII) ( VIII) (IX) (XV) In the formula (III), A1 is -(CH2)m-, and m is an integer of 1 to 6; in the formula (V), the formula (VII) and the formula (IX), X Is a single bond, -0-, -S-, -SS-, -S〇2_, -C〇-, -NH-, -N(CH3)-, -C(CH3)2_, _C(CF3)2_, -(CH2)m-, -CKCH2)m-0-, or -S-(CH2)mS-, m is an integer from 1 to 6; in formula (VII), L1 and L2 are -Η, but when x When -NH-, -N(CH3)-, -CHr, -C(CH3)2-, or -C(CF3)2- may also be bonded to each other to form a single bond; in formula (VIII) and formula ( In IX), Y is a single bond, _〇-, _s_, _ca, s 146 201237065 40462pif _(:(0Ή3)2_, _C(CF3)r, or an alkylene group having a carbon number of 33; Wherein R33&amp;R34 is independently alkyl or phenyl having a carbon number of 丨~3, and G is independently an alkylene group having a carbon number of 丨~6, a phenyl group or a phenyl group substituted by an alkyl group; m is 1~ An integer of 1 ;; and in the above formulas, the -H of the cyclohexane ring or the benzene ring may also be -F, -CH3, -OH, -COOH, -S03H, -P〇3H2, agglomerate, or Base section 10. The liquid crystal alignment agent according to claim 1, which comprises a polyaminic acid obtained by reacting a diamine mixture further comprising a diamine having a side chain structure with tetra-baric acid dianhydride or 11. The liquid crystal alignment agent of the invention of claim 10, wherein the diamine having a side chain structure is a diamine selected from the group consisting of the following formula (x) to formula (XIV) At least one of the groups; r In the formula (X), Z1 is a single bond, ·〇...C〇_, _C〇〇_, _〇c〇·, _c〇NH_, CH2〇, _(ΧΉ2_' ' _〇CFr, or -(CH2 M-, m is an integer of 1 to 6, and any _CHr in the extended alkyl group may be substituted by -〇-, -CH=CH- or -C ξ C-; R3 is a group having a steroid skeleton, carbon a phenyl group having 3 to 30 alkyl groups, 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 following formula (Xa), wherein the carbon number is 1 Any -CH2- 147 201237065 40462pif of the alkyl group of 〜30 may also be substituted by -Ο-, -CH=CH- or -CeC-; [[[馋 __ C [〇] -fA3V d -R6 (Xa e In the formula (Xa), A2 and A3 are independently a single bond, -Ο-, -COO-, -OCO-, -CONH-, -CH=CH-, or an alkylene group having a carbon number of 1 to 12, a and b are independently an integer of 0 to 4; ring B and ring C are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxin-2,5-diyl, . Bite -2,5-diyl, 11 to β-deno-2,5-diyl, nai-1,5-diyl, qin-2,7-diyl, or -9,10-diyl R4 and R5 are independently -F or CH3, f and g are independent integers of 〇~2; R6 is -F -OH, -CN, 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, in the alkyl group, alkoxy group, alkoxy group In the alkyl group, any -H may be substituted by -F, and any -CHr may be substituted by -CFr or a divalent group represented by the following formula (s); In the formula (s), R35 and R36 are independently an alkyl group having 1 to 3 carbon atoms, m is an integer of 1 to 6; c, d and e are independently an integer of 〇~3, and c + d+eg 1 ; 148 S (XI)201237065 40462pif (XII) In the formula (XI) and the formula (XII), R7 is independently -Η or -CH3; R8 is -Η, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms; a single bond, -CO- or -CH2-; in the formula (XII), R9 and R1G are independently an alkyl group having 1 to 20 carbon atoms or a phenyl group; 149 201237065 40462pif R11 In the formulae (XIII) and (XIV), A5 is independently -0- or an alkylene group having 1 to 6 carbon atoms; in the formula (XIII), R11 is -H or an alkyl group having 1 to 30 carbon atoms. Any -CHr of the alkyl group may also be substituted by -0, -CH=CH- or -CeC-; A6 is a single bond or a C 1 to 3 alkyl group; ring T is 1,4-phenylene Or 1,4-cyclohexylene; h is 0 or 1; in the formula (XIV), R12 is an alkyl group having 6 to 22 carbon atoms; and R13 is a alkyl group having 1 to 22 carbon atoms. The liquid crystal alignment agent of any one of the above-mentioned formula (An-Ι)~ (An-6) is further used. Group of at least 1 mus as tetrare-acid dianhydride reacted with diamine; 150 201237065 40462pif (An-1) (An-2) In the formula (An-1), the formula (An-4), and the formula (An-5), X1 is independently a single bond or -CH2-; in the formula (An-2), G1 is a single bond, and the carbon number is 1. -20 alkyl, _Ca, -0-, _S-, -S02-, -C(CH3)r, or -C(CF3)r; in the formula (An-2) to (An-4) Y1 is independently one selected from the group consisting of the following trivalent groups; each of the valleys; &gt;&gt; In the formula (Αη·3) to (An-5), the ring Ε represents the carbon number of 3 to 1 151 151 201237065 40462pif The monocyclic hydrocarbon group or the carbon number 6~2〇 can also be nailed or ethyl wire. The bonds connected to any ring of the job can be linked to each other. - on carbon; #成痛任狄上'2 keys can also be Π, :), Χ11 is a carbon number 2~6 stretching base; Me is not methyl, and ph means phenyl. The liquid formula () and the aromatic acid represented by the formula (17) according to any one of the first to the fifth paragraphs of the patent range 2 to the above are the four Wei Wei livers which react with the diamine; Worship, and The liquid crystal alignment agent according to any one of the items 1 to 5, wherein the liquid crystal alignment agent is further selected from the group consisting of the following formula (23), formula (25), and formula (36) to 39), at least one of the group of the alicyclic tetrazoic acid dianhydride and the aliphatic tetradecanoic acid dihepatic represented by the formula (44), the formula (49), and the formula (68) as a reaction with the diamine Carboxylic dianhydride; S 152 201237065 40462pif The liquid crystal alignment agent according to any one of the preceding claims, wherein the aromatic four shouting group selected from the thirteenth item of the patent application scope is further used. At least one species selected from the group consisting of an alicyclic four-second needle and a linoleic acid group of at least one of the alicyclic group as described in the fourteenth application of the patent (four), as a continuous acid dihepatic reaction with a diamine. The liquid crystal alignment agent of any one of the above-mentioned items of the present invention, wherein the liquid crystal alignment agent further comprises an oxyalkylene compound-containing oxygen compound selected from the group consisting of an alkenyl group, and a calcining coupler. At least one. 17. The liquid crystal alignment agent according to claim 16, wherein the alkenyl-substituted ruthenium imine compound is selected from the group consisting of bis[4_(allylbicyclo[2.2.1]g _5 _ene_2,3_dicarboxy quinone imine) phenyl]methane, ν, Ν'-m-phenylenedifluoryl-bis (weld propyl bicyclo [2.2.1] hept-5-ene-2,3- Group consisting of dicarboxy quinone imine), and hydrazine, hydrazine, hexamethylene fluorenyl-bis(dipropylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline) At least one of them. 18. The liquid crystal alignment agent according to claim 16, wherein 153 201237065 40462pif the alkenyl-substituted ruthenium imine compound is bis[4-(allylbicyclo[2.2.1]g -5-rare-2,3-di-supplemental imine) phenyl] oxime. 19. The liquid crystal alignment agent according to claim 16, wherein the olefin is contained in an amount of from 〇. 〇1 wt% to 50% by weight based on the total amount of the polyaminic acid or a derivative thereof. A substituted quinone imine compound. 20. The liquid crystal alignment agent according to claim 16, wherein the epoxy compound is selected from the group consisting of N, N, N', N'-tetraglycidyl-m-xylylenediamine, I, 3 - bis(N,N-diglycidylaminomethyl)cyclohexane, n,N,N,,N,-tetraglycidyl-4,4'-diaminodiphenylnonane, 2 -[4-(2,3-epoxypropoxy)phenyl]-2·[4-[ 1,1 -bis[4-([2,3-epoxypropoxy]phenyl) Ethyl]phenyl]propane, 3,4-epoxycyclohexenylmethyl_3,,4'-epoxycyclohexenecarboxylate, fluorenyl-phenylmaleimide-fluorenyl At least one of the group consisting of a glycidyl acrylate copolymer and 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. The liquid crystal alignment agent according to claim 16, wherein the epoxy compound is N, N, N, N, -tetraglycidyl-4,4'-diaminodiphenyl Decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane. The liquid crystal alignment agent according to claim 16, wherein the epoxy compound is contained in an amount of 1 wt% to 40 wt% based on the total amount of the polyamic acid or a derivative thereof. The liquid crystal alignment agent according to claim 16, wherein the decane coupling agent is selected from the group consisting of vinyl trimethoxy decane, vinyl triethoxy sulphur, and N-(2-amino B 3-aminopropylmercapto quinone oxime, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-aminophenyltrimethoxy methoxy Decane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxysulfonium S 154 201237065 40462pif alkane, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxydecane , 3_Aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldi-methoxyoxydecane, 3-propylmethylmethyl Oxime, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-Whylpropyltrimethoxydecane, and (6)-dimethylbutylene At least one of the group consisting of -3-(triethoxy oxalate) propylamine and N,N,·bis[3_(trimethoxysulfenyl)propyl]ethylenediamine . The liquid crystal alignment agent according to claim 16, wherein the ceramsite coupling agent is 3-aminopropyltriethoxy sulphur. 25. The liquid crystal alignment agent according to claim 16, wherein the amount of 〇1 wt% to 10% by weight is less than the total amount of the polyaminic acid or a derivative thereof; Coupling agent. A liquid crystal alignment agent of at least two of the liquid crystal alignment agents according to any one of claims 1 to 15. 27. A liquid crystal alignment film for photo-alignment, wherein the step of applying a liquid crystal alignment agent according to any one of claims 1 to 26 to a substrate is applied to an agent coated with an alignment agent. The step of heating and drying the substrate is performed by a step of irradiating the film with polarized ultraviolet rays. A liquid crystal alignment film for photo-alignment, which comprises the step of applying an alignment agent to a substrate by applying the liquid crystal alignment agent according to any one of claims 1 to 26 The step of heating and drying the substrate, the step of irradiating the dried film with polarized ultraviolet rays, and then the step of heating and calcining the film. A liquid crystal alignment film according to any one of the items 1 to 26, wherein the liquid crystal alignment agent according to any one of the first to twenty-sixth aspects of the present invention is applied to the liquid crystal alignment film according to the application of the patent specification 155 201237065 40462pif On the substrate = step 'the step of heating and drying the substrate coated with the alignment agent, and the step-by-step display element for the dry-lined fine-grained material, which is read into the surface of the polarized material line, is the _ box of the 29th item #,+, has a liquid crystal alignment film for light alignment as in the 27th item of the patent application. S 156 201237065 40462pif 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: (N-1) (N-2) 3