TWI596139B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element, which are liquid alignment display elements of a vertical alignment type which are obtained by applying a voltage to liquid crystal molecules and irradiating ultraviolet rays.

A liquid crystal display element in which a liquid crystal molecule whose substrate is vertically aligned responds via an electric field (also referred to as a vertical alignment (VA) mode), in the manufacturing process thereof, is a step of irradiating ultraviolet rays during application of a voltage to liquid crystal molecules. .

In the liquid crystal display device of the vertical alignment type, it is known that a photopolymerizable compound is added to a liquid crystal composition in advance, and a vertical alignment film such as a polyimide film is used to irradiate ultraviolet rays during application of a voltage to a liquid crystal cell. In the method of accelerating the response speed of the liquid crystal (the component of the PSA (Polymer Sustained Alignment) program, for example, Patent Document 1 and Non-Patent Document 1 refer to).

In the PSA program element, generally, the tilt direction of the liquid crystal molecules in response to the electric field is usually subjected to protrusions or settings provided on the substrate. In the liquid crystal cell in which the photopolymerizable compound is added to the liquid crystal composition, when the ultraviolet ray is applied to the liquid crystal alignment film, the polymerization in the oblique direction of the liquid crystal molecules is formed on the liquid crystal alignment film. The structure of the liquid crystal display element will be more responsive when compared to the method of controlling the tilt direction of the liquid crystal molecules using only protrusions or slits.

On the other hand, in the liquid crystal display device of the PSA type, the solubility of the polymerizable compound added to the liquid crystal is low, and the addition amount and the precipitation at low temperatures cause problems such as precipitation, but the addition amount may not be obtained. The problem of good alignment. Further, the unreacted polymerizable compound remaining in the liquid crystal forms impurities (contaminants) in the liquid crystal, which causes problems such as lowering the reliability of the liquid crystal display element. Further, in the UV irradiation treatment necessary for the PSA method, generally, a short-wavelength light having a wavelength of around 313 nm is irradiated. Therefore, when the amount of irradiation is increased, the components in the liquid crystal are decomposed and the reliability is lowered.

In addition, it has been proposed that a photopolymerizable compound is added not only to a liquid crystal composition but also to a liquid crystal alignment film, and the response speed of the liquid crystal display element can be accelerated (SC-PVA type liquid crystal display, for example, non-patent literature) 2 reference).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2003-307720

[Non-patent literature]

[Non-Patent Document 1] K. Hanaoka, SID 04 DIGEST, P.1200-1202

[Non-Patent Document 2] K.H Y.-J.Lee, SID 09 DIGEST, P.666-668

In recent years, with the improvement in the quality of liquid crystal display elements, it has been expected that the response speed to liquid crystals to which voltage is applied is faster, or the reliability thereof can be improved. Therefore, when the ultraviolet light of a long wavelength which does not cause decomposition of the components in the liquid crystal is irradiated, the polymerizable compound can be sufficiently efficiently reacted, and the alignment fixing ability is required. Further, it is also a necessary condition that an unreacted polymerizable compound cannot be present after irradiation with ultraviolet rays, and the reliability of the liquid crystal display element is not adversely affected.

An object of the present invention is to provide a response speed of a liquid crystal display element which can not only solve the above problems but also improve the reaction using a polymerizable compound in a liquid crystal and/or a liquid crystal alignment film, and has a good response speed. A reliable liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element are intended.

The inventors have learned the results through in-depth research. In the polymer of the liquid crystal alignment agent, a specific structure capable of generating a radical by ultraviolet irradiation is introduced, and the above object is achieved, and thus the present invention has been completed.

That is, the present invention is the one having the following technical features.

(1) A liquid crystal alignment agent comprising a polymer having a side chain structure represented by the following formula (I).

In the formula (I), a point indicates a bond to a polymer main chain, and Sp is a single bond, or an unsubstituted or alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom. The alkylene group may have an unsaturated bond, or a branched chain, or a cyclic structure. X represents a single bond or a linking group. Cy represents a cyclic hydrocarbon group having 5 to 14 carbon atoms which has at least one or more unsaturated bonds bonded to a carbonyl carbon bond of a quinone imine group, and a part of a carbon atom constituting the cyclic hydrocarbon group may be a hetero atom The hydrogen atom which is substituted and which constitutes a cyclic hydrocarbon may be substituted by a fluorine atom or a monovalent organic group having a molecular weight of 14 to 100.

(2) The liquid crystal alignment agent according to the above (I), wherein the polymer having the side chain structure represented by the above formula (I) is a polyfluorene having a side chain structure represented by the above formula (I). At least one polymer selected from the group consisting of an imine precursor and a polyimine obtained by hydrazine imidization.

(3) Liquid crystal alignment as described in (1) or (2) above The side chain structure described in the above formula (I) is represented by the following formula (II).

In formula (II), the dots represent the bonds with the polymer backbone, n is an integer selected from 1 to 12, and X represents a single bond, -O-, -COO-, -OCO-, -NHCO-, - CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-. Cy represents a cyclic hydrocarbon group having 5 to 14 carbon atoms which has at least one or more unsaturated bonds bonded to a carbonyl carbon bond of a quinone imine group, and a part of a carbon atom constituting the cyclic hydrocarbon may be a hetero atom. Replaced.

(4) The liquid crystal alignment agent according to the above (3), wherein n in the formula (II) is an integer of 1 to 6, and Cy is a cyclic hydrocarbon group shown below, and two points represent Bonding of an imine carbonyl carbon.

(5) The liquid crystal alignment agent according to the above (3) or (4), wherein n in the formula (II) is an integer of from 1 to 6, X represents -O-, and Cy is cyclohexene or benzene. Naphthalene, biphenyl.

(6) The liquid crystal alignment agent according to any one of the above-mentioned (1), wherein the polymer further has a side chain in which the liquid crystal is vertically aligned.

(7) The liquid crystal alignment agent according to the above (6), wherein the side chain in which the liquid crystal is vertically aligned is at least one selected from the following formulas (III-1) and (III-2).

(X ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. X ² represents a single bond or (CH) ₂ ) _b - (b is an integer from 1 to 15). X ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- Or -OCO-.X ⁴ represents a bivalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom of the cyclic group may be an alkyl group having 1 to 3 carbon atoms. a group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and further, X ⁴ may have a cholesterol skeleton a divalent organic group selected from the organic group having a carbon number of 17 to 51. X ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, and any of the cyclic groups The hydrogen atom may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Substituted. n represents an integer of 0 to 4. X ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a carbon number of 1 to 18 Fluoroalkoxy).

[X5]-X ⁷ -X ⁸ [III-2] (X ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N (CH ₃ )CO-, -COO- or -OCO-. X ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.

The liquid crystal alignment agent according to any one of the above aspects, wherein the polymer further has a side chain containing a photoreactive group in the structure.

(9) The liquid crystal alignment agent according to the above (8), wherein the side chain containing the photoreactive group in the structure is represented by the following (IV) or (V).

[6]-R ⁸ -R ⁹ -R ¹⁰ [IV] (R ⁸ represents a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH -, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-. R ⁹ represents a single bond, the number of carbons which can be replaced by a fluorine atom The alkyl group of ~20, the -CH ₂ - of the alkyl group may be optionally substituted by -CF ₂ - or -CH=CH-, and any of the following groups may not be adjacent, and may be Substituted; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring or a heterocyclic ring. R ¹⁰ represents a photoreactivity selected by the following formula base).

[Chem. 8]-Y ₁ -Y ₂ -Y ₃ -Y ₄ -Y ₅ -Y ₆ [V] (Y ₁ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, or -CO-. Y ₂ is an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring, and an alkyl group, a divalent carbocyclic ring or a heterocyclic ring. one or a plurality of hydrogen atoms by a fluorine atom or an organic group substituted .Y _2, the following group is not the case when the adjacent ground, -CH ₂ - may be substituted with the plurality of groups; -O- , -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. Y ₃ represents -CH ₂ -, -O-, -CONH-, -NHCO-, - COO-, -OCO-, -NH-, -CO-, or a single bond. Y ₄ represents cinnamoyl. Y ₅ is a single bond, an alkyl group having 1 to 30 carbon atoms, and a bivalent carbon ring. Or a heterocyclic ring, one or more hydrogen atoms of the alkylene group, the divalent carbocyclic ring or the heterocyclic ring may be substituted by a fluorine atom or an organic group. Y _{5 is} not adjacent to the following group. In the case, -CH ₂ - may be substituted by these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-.Y ₆ It represents a photopolymerizable group of an acryl group or a methacryl group.

(10) The liquid crystal alignment agent according to any one of the above (1), wherein the polymer contains a polyfluorene having a diamine component represented by the following formula (VI) as a structural unit. At least one polymer of an amine precursor and a polyimine obtained by hydrazine imidization.

The definition of the symbol in the formula is the same as the above formula (I).

(11) The liquid crystal alignment agent according to the above (10), wherein the polymer further contains a polyimine precursor having a diamine component represented by the following formula (VII) as a structural unit and At least one polymer of the polyimine obtained by imidization of hydrazine.

(X represents the structure of the above formula [III-1] or formula [III-2], and n represents an integer of 1 to 4).

(12) The liquid crystal alignment agent according to the above (10) or (11), wherein the polymer further contains The diamine component of the diamine represented by (VIII) or (IX) is at least one of a polyimine precursor of a structural unit and a polyimine obtained by hydrazine imidation.

(The definitions of R ⁸ , R ⁹ and R ¹⁰ are the same as those of the above formula (IV)).

(The definitions of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , and Y ₆ are the same as those of the above formula (V)).

(13) The liquid crystal alignment agent according to any one of the above (10), wherein the diamine represented by the formula (IV) is 10 mol% to 80 mol% of the total diamine component. ear%.

(1) The liquid crystal alignment agent according to any one of the above (1) to (13), which is used in a liquid crystal and/or a liquid crystal alignment film containing a polymerizable compound, and is irradiated with ultraviolet rays at an applied voltage. The polymerizable compound is reacted in a liquid crystal display device.

(15) A liquid crystal alignment film characterized by the above (1) The liquid crystal alignment agent according to any one of (1) to (14).

(16) A liquid crystal display element comprising the liquid crystal alignment film according to (15) above.

(17) The liquid crystal display device of the above-mentioned (16), wherein the liquid crystal display element is obtained by reacting the polymerizable compound with ultraviolet light after application of a voltage.

(18) A polymer characterized by comprising at least one of a polyimine precursor having a side chain structure represented by the following formula (II) and a polyimine obtained by ruthenium imidization .

The dots represent the bonds with the polymer backbone, n is an integer selected from 1 to 12, and X represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH- , -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-. Cy represents a cyclic hydrocarbon group having 5 to 14 carbon atoms which has at least one or more unsaturated bonds bonded to a carbonyl carbon bond of a quinone imine group, and a part of a carbon atom constituting the cyclic hydrocarbon may be a hetero atom. Replaced.

(19) A diamine characterized by the following formula.

According to the present invention, a liquid crystal display element having a vertical alignment mode with a fast response speed can be provided, and in particular, a liquid crystal alignment agent which is more suitable for a PSA type liquid crystal display element. The liquid crystal alignment agent of the present invention can produce a liquid crystal display element which can sufficiently improve the response speed even when irradiated with ultraviolet light of a long wavelength.

[Formation of the Invention]

The liquid crystal alignment agent of the present invention contains a polymer (hereinafter also referred to as a specific polymer) having at least one structure represented by the above formula (I) in a side chain, and a solvent. The liquid crystal alignment agent means a solution for forming a liquid crystal alignment film, and the liquid crystal alignment film means a film which forms a liquid crystal in a specific direction.

The polymer having a structure represented by the above formula (I) in the side chain, for example, a polyacrylate resin, a polymethacrylate resin, and a structure having a side chain having the structure represented by the above formula (I) The amine diamine component may be used as a structural unit of a polyimide intermediate and a ruthenium imidized polyimine or the like, and at least one of the polymers may be used.

<Side chain generated by ultraviolet irradiation or free radicals being chain-transferred>

The specific polymer contained in the liquid crystal alignment agent of the present invention is provided in a side chain There is an organic group represented by the above formula (I). It is presumed that the organic group has a function of generating a radical by ultraviolet irradiation to generate a radical, or a radical generated by another organic group is transferred by a chain, and an effect of the object can be attained.

In the above formula (I), on the two carbonyl carbons of the quinone ring, the bond Cy, that is, the cyclic hydrocarbon group having at least one unsaturated bond, is an important feature, particularly on two carbonyl carbons. The structure of the direct bond unsaturated bond is preferred. In particular, when the number of the unsaturated bonds is increased, it is preferable to increase the absorbance in the ultraviolet region and to increase the wavelength of the absorption wavelength. Further, an aromatic hydrocarbon group or a heterocyclic compound having 6 to 14 carbon atoms is preferable. From the viewpoints of availability of the reagent or ease of synthesis, a cyclic hydrocarbon group containing no hetero atom is preferred. The preferred Cy example is as follows, but is not limited thereto.

On the other hand, the more carbon atoms forming the ring structure, the easier it is to form a rigid structure, and the lack of solubility in a solvent, so that carbon is obtained from the viewpoint of monomer synthesis or ease of handling a monomer. A small number of cyclic hydrocarbon groups are preferred, and particularly preferred are cyclohexene, benzene, naphthalene, biphenyl, and the like. more Jia is the following structure.

The hydrogen atom of the cyclic hydrocarbon group directly bonded to the quinone ring may be substituted by a fluorine atom or the like, or may be substituted by an organic group. The organic group which may be substituted is not particularly limited, and in general, when an organic group having a strong electron supply property or electron acceptability is introduced, it is preferable to have an effect of increasing the wavelength of the absorption wavelength. On the other hand, a radical such as a nitro group or an amine group can be trapped, and is preferably an organic group having a molecular weight of 14 to 100, such as a hydroxy group or a hydroxyl group. An organic group or an alkoxy group having a small molecular weight, an alkyl group or the like, which has the possibility of trapping the radical generated by the introduced substituent, so that it is necessary to pay attention to the selection of the substituent. Sex. For the above reasons, it is most preferred to be unsubstituted.

-X-Sp- in the above formula (I) is a moiety which is bonded to a polymer chain. In the present invention, the structure in which the quinone imine carbonyl bond of the side chain represented by the above formula (I) is bonded is an important feature, so that the joint portion does not have to be particularly limited, and when the structure of -X- is preferred, X represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )- , or -N(CH ₃ )CO-, etc. Further, -Sp- is preferably an alkyl group having 1 to 12 carbon atoms, and the alkyl group may have an unsaturated bond, or a branched chain, or a cyclic structure, and the hydrogen atom in the alkyl group may be fluorine. Replace. From the standpoint of the availability of the reagent or the synthesis, the structure which is most easily synthesized is X is -O-, and the alkyl group is a linear alkyl group having 1 to 6 carbon atoms.

The present invention is a polymer having an organic group represented by the above formula (I) as a side chain, and means for introducing a side chain into the polymer is not particularly limited. For example, a method of obtaining a polymer by polymerization using a monomer having a side chain structure represented by the above formula (I), or a method of introducing it by polymer modification or the like can be mentioned. A method of introducing a monomer having an organic group represented by the above formula (I) into a polymer is preferred.

<Let the side chain of the liquid crystal vertical alignment>

The polymer contained in the liquid crystal alignment agent of the present invention preferably has a side chain which vertically aligns the liquid crystal, in addition to the side chain represented by the above formula (I). The side chain in which the liquid crystal is vertically aligned is represented by the following formula (III-1) or formula (III-2).

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and n are as defined above.

Among them, X ¹ , in terms of the availability of raw materials or the ease of synthesis, etc., a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferred, and a preferred one is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-. Among them, X ^{2 is} preferably represented by a single bond or (CH ₂ ) _b - (b is an integer of 1 to 10). In X ³ , from the viewpoints of easiness of synthesis, etc., a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable. Preferably, the single bond, -(CH ₂ ) _c - (c is an integer from 1 to 10), -O-, -CH ₂ O- or -COO-.

Among them, X ⁴ is preferably an organic group having a carbon number of 17 to 51 having a benzene ring, a cyclohexane ring or a cholesterol skeleton from the viewpoint of easiness of synthesis and the like. Among X ⁵ , a benzene ring or a cyclohexane ring is preferred. Among them, from the viewpoints of the availability of raw materials or the ease of synthesis, it is preferably 0 to 3, more preferably 0 to 2.

Among X ⁶ , an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. . More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred are alkyl groups having 1 to 9 carbon atoms or alkoxy groups having 1 to 9 carbon atoms.

In the formula (III-1), a preferred combination of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n can be exemplified by, for example, the publication of WO2011/132751 (2011.10.27). (2-1) to (2-629) disclosed in Tables 6 to 47 of pages 13 to 34 are the same combinations. Further, in the tables of the international publication, X ¹ to X ⁶ are represented by Y1 to Y6, and therefore Y1 to Y6 are those in which X ¹ to X ⁶ are read.

Further, in the present invention, the organic group having a carbon number of 17 to 51 having a cholesterol skeleton is a carbon having a cholesterol skeleton in (2-605) to (2-629) disclosed in the tables in the international publication. Number 12~25 The organic group is represented by an organic group having a carbon number of 12 to 25 in the cholesterol skeleton, and is an organic group having a carbon number of 17 to 51 having a cholesterol skeleton. Among them, (2-25)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-268)~(2-315 A combination of (2-364)~(2-387), (2-436)~(2-483) or (2-603)~(2-615) is preferred. The combination of the best is (2-49)~(2-96), (2-145)~(2-168), (2-217)~(2-240), (2-603)~(2-606 ), (2-607)~(2-609), (2-611), (2-612) or (2-624).

[化18]-X ⁷ -X ⁸ [III-2]

X ⁷ , X ⁸ are as defined above. Wherein, X ^{7 is} preferably a single bond, -O-, -CH ₂ O-, -CONH-, -CON(CH ₃ )- or -COO-, more preferably a single bond, -O-, -CONH- Or -COO-. Among X ⁸ , an alkyl group having 8 to 18 carbon atoms is preferred.

The viewpoint of obtaining the vertical alignment of the liquid crystal having high stability by obtaining the side chain in which the liquid crystal is vertically aligned is preferable to use the structure shown in the formula [III-1].

Further, a polymer having a side chain which vertically aligns the liquid crystal, the ability to vertically align the liquid crystal differs depending on the structure of the side chain in which the liquid crystal is vertically aligned, and generally, the amount of the side chain which vertically aligns the liquid crystal The more the amount, the higher the ability to align the liquid crystal vertically, and the lower the amount. Moreover, it has a ring structure, and when compared with a person who does not have a ring structure, The ability of liquid crystal vertical alignment has a higher tendency.

<Photoreactive side chain>

The polymer contained in the liquid crystal alignment agent of the present invention may have a photoreactive side chain in addition to the side chain represented by the above formula (I). The photoreactive side chain is a functional group (hereinafter, also referred to as a photoreactive group) which forms a covalent bond by reaction with light such as ultraviolet rays (UV).

The photoreactive side chain may be directly bonded to the main chain of the polymer or may be bonded via a bonding group. The side chain of photoreactivity is, for example, represented by the following formula (IV).

[Chem. 19]-R ⁸ -R ⁹ -R ¹⁰ [IV]

R ⁸ , R ⁹ and R ¹⁰ are as defined above. Wherein R ^{8 is} preferably represented by a single bond, -O-, -COO-, -NHCO-, or -CONH-. R ⁹ can be formed by a usual organic synthesis method, and it is easy to synthesize, and a single bond or an alkylene group having 1 to 12 carbon atoms is preferred.

[Chem. 20]-Y ₁ -Y ₂ -Y ₃ -Y ₄ -Y ₅ -Y ₆ [V]

Y ₁ to Y ₆ are as described above.

Further, in the formula [IV], a divalent carbocyclic ring or a heterocyclic ring which is substituted for any -CH ₂ - in R ⁹ is specifically exemplified below.

R ¹⁰ is preferably a methacrylic group, an acrylic group or a vinyl group from the viewpoint of photoreactivity.

The amount of the side chain of the photoreactivity is such that the reaction can be carried out by irradiation of ultraviolet rays to form a covalent bond, and the range of the response speed of the liquid crystal is accelerated, so that the response speed of the liquid crystal can be accelerated, and the other effects are not affected. The range of features, as much as possible, is better.

<Polymer forming a liquid crystal alignment agent>

A method of producing a polyimine precursor having a specific side chain and a polyimine obtained by imidating the polyimine precursor ruthenium is not particularly limited. For example, a method of polymerizing a diamine having a specific side chain and a tetracarboxylic dianhydride, a method of polymerizing a diamine having a specific side chain and a tetracarboxylic acid diester, and a tetracarboxylic dianhydride containing a specific side chain. A method of polymerizing a diamine compound, a method of polymerizing a tetracarboxylic dianhydride and a diamine, and then performing a reaction with a compound containing a specific side chain to modify the polymer. Among them, it is easy to manufacture From the viewpoint, it is preferred to use a method in which a diamine compound having a specific side chain is mixed with a tetracarboxylic dianhydride or a tetracarboxylic acid diester.

In addition to the method of producing a specific side chain, another polyimine precursor having a side chain and/or a photoreactive side chain which vertically aligns the liquid crystal is produced, and the polyimide precursor precursor is imidized. For the method of polyimine, for example, the same method as described above or the like can be used. In this preferred method, a diamine compound containing a side chain vertically aligned with a liquid crystal and/or a diamine compound containing a photoreactive side chain, and a tetracarboxylic dianhydride or a tetracarboxylic acid diester are similarly used. The method of carrying out the polymerization is preferred.

<specific diamine>

A diamine (hereinafter also referred to as a specific diamine) used in the method for producing the above-mentioned polymer for forming a liquid crystal alignment agent of the present invention, which is characterized in that it generates radicals or other sites by irradiation with ultraviolet rays. The generated free radical is used as a side chain by the function of the chain transfer function.

In the structure of the diamine, the diamine having the organic group represented by the above formula (I) as a side chain can be represented by the following formula (VI).

The definition of the symbol in the formula (VI) is the same as the above formula (I) content.

The diaminobenzene in the formula (VI) may be any one of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine, and is reactive with acid dianhydride. Preferably, m-phenylenediamine or p-phenylenediamine is preferred. A preferred structure of the formula (VI) is a diamine represented by the following formula (X). (where n is an integer from 1 to 6)

More preferably, the structure represented by the following formula (XI) is optimal in terms of ease of synthesis, high versatility, and properties.

(where m is an integer from 1 to 3)

<Synthesis of specific diamines>

In the present invention, the specific diamine is a mononitro group having an amine group which can be removed by a reduction step through a dinitro group, or a reduction step can be used to remove a protecting group. Alternatively, after a diamine is synthesized, a nitro group can be used in a usual reduction reaction. Conversion to an amine group or deprotection of the protecting group.

As the synthesis method of the diamine precursor, various methods can be used. For example, a method of preparing a diamine precursor by reacting an alcohol or an alkylamine having a quinone imine structure, an alkyl halide or the like with dinitrobenzene, or introducing an alkylamine and an acid anhydride completely introduced into dinitrobenzene a method obtained by the reaction, or a light extension reaction of a dinitrobenzene alcohol completely substituted with a non-substituted fluorene imine on N, an alkyl halide which is completely introduced into dinitrobenzene, and a substituent which is not substituted on N A method in which an amine is condensed in the presence of a base or a metal catalyst.

The above is a synthesis example in which an ether bond is bonded to a dinitrogen bond, and the other may be based on the above method, and the synthetic bond group is an ester bond or a guanamine bond.

The method for reducing the dinitro compound of the diamine precursor is not particularly limited. Usually, palladium carbon, platinum oxide, Raney nickel, platinum carbon, rhodium-alumina, platinum sulfide carbon or the like can be used as a catalyst. A method of reducing by a hydrogen gas, hydrazine, hydrogen chloride or the like in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol. An autoclave or the like can be used as necessary.

On the other hand, in the case where the structure contains an unsaturated bonding site, when palladium carbon or platinum carbon or the like is used, the unsaturated bonding site is reduced, and a saturated bonding is formed, so that the preferable conditions are used. It is preferably doped with a transition metal such as reduced iron, tin or tin chloride, or a poisoned palladium carbon, platinum carbon, or platinum such as iron as a catalyst.

Further, the diaminobenzene derivative protected by a benzyl group or the like can be similarly deprotected according to the above reduction step to obtain the diamine of the present invention.

The specific diamine is preferably used in an amount of 10 to 80 mol%, more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol%, as the diamine component for the synthesis of polylysine. .

<Diamine having a side chain which vertically aligns the liquid crystal>

A method of introducing a side chain of a liquid crystal perpendicular alignment into a polyamidene-based polymer is preferred to use a diamine having a specific side chain structure as a part of a diamine component.

R ⁸ , R ⁹ and R ¹⁰ are as defined above.

Y ₁ to Y ₆ are as described above.

Specific examples of the specific side chain type diamine include a structure represented by the following formula [2a-1] to formula [2a-31].

(R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and R ² is a linear or branched alkyl group having 1 to 22 carbon atoms; a linear or branched alkoxy group of 1 to 22, a linear or branched fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.

(R ³ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or -CH ₂ -, R ⁴ is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms or Fluoroalkoxy).

(R ⁵ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -O- Or -NH-, R ⁶ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxy group).

(R ⁷ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of the 1,4-cyclohexene is a trans isomer).

(R ⁸ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of the 1,4-cyclohexene is a trans isomer).

(A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group, and A ₂ is an oxygen atom. Or COO-* (however, the bond key with "*" is bonded to A ₃ ), A ₁ is an oxygen atom or COO-* (however, the bond key with "*" is attached with (CH ₂ ) a ₂ ) Bonding). Further, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.

In the above formula [2a-1] to [2a-31], it is particularly preferable that the formula [2a-1]~form [2a-6], the formula [2a-9]~form [2a-13] or the formula [2a-- 22]~[2a-31].

In addition, examples of the diamine having a specific side chain structure represented by the above formula [III-2] include diamines represented by the following formulas [2b-1] to [2b-10].

(A ¹ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

In the above formula [2b-5]~form [2b-10], A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH -, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

The diamine may be used in combination with one or two or more kinds of the liquid crystal alignment property, the pretilt angle, the voltage holding property, and the charge accumulation when the liquid crystal alignment film is used.

The above diamine having a side chain for vertically aligning the liquid crystal is preferably used in an amount of 5 to 50 mol% of the diamine component used for the synthesis of the polylysine, and more preferably 10 to 40 of the diamine component. Moer%, especially good for 15~30%.

When a diamine having a side chain in which the liquid crystal is vertically aligned is used, it has an excellent viewpoint of improving the response speed or the alignment of the liquid crystal.

<Diamine containing photoreactive side chain>

The method of introducing a photoreactive side chain into a polyamidene-based polymer is preferred to use a diamine having a specific side chain structure as a part of the diamine component. The diamine having a photoreactive side chain is a diamine having a side chain represented by the formula [VIII] or the formula [IX].

(The definitions of R ⁸ , R ⁹ and R ¹⁰ in [VIII] are the same as those in the above formula (IV)).

(The definitions of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , and Y _{6 in} the formula [IX] are the same as those in the above formula (V)).

The bonding position of the two amine groups (-NH ₂ ) in the formula [VIII] and the formula [IX] is not particularly limited. Specifically, for example, the bonding group with respect to the side chain is a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, and a position of 3, 4 Location, location 3, 5. Among them, in view of the reactivity in synthesizing polyamic acid, the position of 2, 4, the position of 2, 5, or the position of 3, 5 is preferred. Further, in view of easiness in synthesizing a diamine or the like, a position of 2, 4 or a position of 3, 5 is preferable.

The diamine having a photoreactive side chain is specifically exemplified below, but is not limited thereto.

(X ⁹ , X ¹⁰ , each independently a single bond, -O-, -COO-, -NHCO-, or -NH- linkage group, Y represents a carbon number of 1 to 20 which can be replaced by a fluorine atom alkyl).

In addition, examples of the diamine having a photoreactive side chain include a diamine which causes a photodimerization reaction represented by the following formula and a group which causes a photopolymerization reaction.

In the above formula, Y ₁ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, or -CO-. Y ₂ is an alkylene group having a carbon number of 1 to 30, a divalent carbon ring or a heterocyclic ring, and one or more hydrogen atoms of the alkyl group, the divalent carbocyclic ring or the heterocyclic ring may be a fluorine atom or Replaced by an organic base. Y ₂ , when the following groups are not adjacent, -CH ₂ - may be substituted by the groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, - NH-, -NHCONH-, -CO-. Y ₃ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, or a single bond. Y ₄ represents cinnamoyl. Y ₅ is a single bond, a C 1~30 alkyl group, a divalent carbocyclic ring or a heterocyclic ring, and one or more hydrogen atoms of the alkyl group, the divalent carbocyclic ring or the heterocyclic ring may be Substituted by a fluorine atom or an organic group. Y ₅ , when the following groups are not adjacent, -CH ₂ - may be substituted by the groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, - NH-, -NHCONH-, -CO-. Y ₆ represents an acryl group or a methacryl group.

The diamine having a photoreactive side chain can be blended with a liquid crystal alignment film as a liquid crystal alignment film, a pretilt angle, a voltage holding property, a charge accumulation property, and the like, and a response speed of a liquid crystal when used as a liquid crystal display element. It can be used in combination of two types or more.

Further, the diamine having a photoreactive side chain is preferably used in an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, of the diamine component used for the synthesis of the polyamic acid. Very good for 30~50%.

<Other diamines>

Further, when a polyimide precursor and/or a polyimide is produced, it can be used as a diamine component in combination with a diamine other than the above diamine, without impairing the effects of the present invention. Specifically, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-extension Phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diamine toluene, 2,6-diamine toluene, 2,5-diaminophenol , 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol , 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diamino Biphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4 , 4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4' -diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-di Aminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyl Diphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)anthracene , dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine , 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'- Diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl (3 , 4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine , 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2 , 2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diamino Naphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-di Amino naphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl) Ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene , 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4 - bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methyl)diphenylamine , 4,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,4'-[1,4-phenylenebis(methyl)diphenylamine, 3,4 '-[1,3-phenylene bis(methyl))diphenylamine, 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3,3'-[1 , 3-phenylphenyl bis(methyl)diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3-amine) Phenyl phenyl) ketone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylphenylbis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoic acid) Ester), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl) Terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate Dicarboxylate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-amine Benzobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis (3) -aminobenzamide, N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl) pair Benzoguanamine, N,N'-bis(4-aminophenyl)m-xylyleneamine, N,N'-bis(3-aminophenyl)m-xylyleneamine, 9, 10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy) Phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2 , 2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-amine Phenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 3,5-diamino Benzoic acid, 2,5-diamino benzoic acid, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-double (4-Aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5- Bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7 - bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8 - bis(3-aminophenoxy) Alkane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxy)anthracene Alkane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy)11 An aromatic diamine such as alkane, 1,12-(4-aminophenoxy)dodecane or 1,12-(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl) An alicyclic diamine such as methane or bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminepropane, 1,4-diaminobutane, 1,5-diaminopentane Alkane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminoguanidine alkyl, An aliphatic diamine such as 1,11-diaminoundecane or 1,12-diaminododecane.

The other diamines may be used in combination with one or two or more types in combination with characteristics such as liquid crystal alignment, pretilt angle, voltage holding characteristics, and charge accumulation when the liquid crystal alignment film is used.

<tetracarboxylic dianhydride>

The tetracarboxylic dianhydride component which can be reacted with the above diamine component is not particularly limited. Specific examples thereof include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, and 1,4,5,8-naphthalenetetracarboxylic acid. Acid, 2,3,6,7-nonanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3,4,4'-biphenyltetracarboxylic acid, 2,3,3,4 -biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3,4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)fluorene, Bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-dual (3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyloxane, bis(3,4-dicarboxyphenyl)diphenylnonane, 2,3,4, 5-pyridyltetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10- Terpene tetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxybisphthalic acid, 1,2,3,4-cyclobutane tetracarboxylate Acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3, 4-cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutyl Alkane tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3, 4-dicarboxy-1-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, two Ring [3,3,0]octane- 2,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2, 4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2,6>]undecane- 3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-dioxatetrahydrofuran-3-yl)-1,2,3,4 - tetrahydronaphthalene-1,2-dicarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxa Tetrahydrofuranyl-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0,2,7]dodecane-4,5,9, 10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2: 3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and the like. Of course, the tetracarboxylic dianhydride may be used in combination with one type or two or more types in combination with characteristics such as liquid crystal alignment property, voltage holding property, and charge accumulation when the liquid crystal alignment film is used.

<Polymerizable compound>

The liquid crystal alignment agent of the present invention may contain, if necessary, two or more polymerizable compounds having a photopolymerization or photocrosslinking group at the terminal. The polymerizable compound is a compound having two or more photopolymerization or photocrosslinking groups at the terminal. Among them, the polymerizable compound having a photopolymerizable group is a compound having a functional group capable of generating polymerization upon irradiation with light. Further, the compound having a photocrosslinking group is obtained by irradiating light, and is polymerizable with a polymer of a polymerizable compound, or a polyimide precursor, and the polyimide precursor is imidized by hydrazine. A polymer of at least one selected from the group consisting of polyamidiamines, and a compound capable of producing a crosslinked functional group therewith. Further, a compound having a photocrosslinking group can react with each other with a compound having a photocrosslinking group.

When the liquid crystal alignment agent of the present invention containing the above polymerizable compound is used in a liquid crystal display device of a vertical alignment type such as an SC-PVA liquid crystal display, a side chain having a side chain and a photoreactivity which is perpendicular to the liquid crystal is used. When the polymer is used alone or in the case of using the polymerizable compound alone, the response speed can be remarkably increased upward, so that even if the amount of the lower polymerizable compound is added, the response speed can be sufficiently increased.

The photopolymerization or photocrosslinking group may, for example, be a group having a valence represented by the following formula (X).

(R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z ¹ represents a divalent aromatic ring or a heterocyclic group which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Ring: Z ² represents an aromatic ring or a heterocyclic ring which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

Specific examples of the polymerizable compound include a compound having a photopolymerizable group at two terminals represented by the following formula (XI), and a terminal having a photopolymerizable group represented by the following formula (XII). A compound having a terminal of a photocrosslinking group or a compound having a photocrosslinking group at both terminals represented by the following formula (XIII).

Further, the following formula (XI) ~ (XIII) in, R ^12, Z ¹ and Z ² as in the above-described formula (X) R ^12, Z ¹ and Z ² are the same contents, Q ¹ is a divalent organic group of . Q ¹ is a ring structure having a stretching phenyl group (-C ₆ H ₄ -), a biphenyl group (-C ₆ H ₄ -C ₆ H ₄ -), a cyclohexenyl group (-C ₆ H ₁₀ -) It is better. The reason is that it is easy to increase the interaction between the liquid crystals and the liquid crystal.

Specific examples of the polymerizable compound represented by the formula (XI) include a polymerizable compound represented by the following formula (4). In the following formula (4), V and W represent a single bond, or -R ¹ O-, and R ¹ is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably -R ¹ O -, R ¹ is a linear or branched alkyl group having 2 to 6 carbon atoms. Moreover, V and W can be the same or different, and, when they are the same, will be easier to synthesize.

Further, a photopolymerization or photocrosslinking group is produced, and the acrylate group or the methyl group is used in addition to the α-methyl-γ-butyrolactone group and the polymerizable compound having an acrylate group or a methacrylate group. The acrylate group has a polymerizable compound having a structure in which a spacer such as an oxygen-extension alkyl group is bonded to a phenyl group, and is the same as the polymerizable compound having an α-methyl-γ-butyrolactone group at both ends. In particular, the response speed can be greatly improved. Further, the acrylate group or the methacrylate group has a polymerizable compound having a structure in which a spacer such as an oxygen-extension alkyl group and a phenyl group are bonded, and the heat stability can be improved, for example, a high temperature, for example, can be sufficiently withstood Sintering temperature above 200 °C.

The method for producing the above polymerizable compound is not particularly limited, and for example, it can be produced by the following synthesis example. For example, the polymerizable compound represented by the above formula (4) is represented by the following reaction formula proposed by Talaga et al., P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990). Synthesized by reaction with aldehyde or ketone using SnCl ₂ and 2-(bromomethyl)propenoic acid. Further, Amberlyst 15 is a strong acid ion exchange resin manufactured by Rohm and Haas Company.

(wherein R' represents a monovalent organic group).

Further, 2-(bromomethyl)acrylic acid can be as follows according to Ramarajan et al., K. Ramarajan, K. Kamalingam, DJO'Donnell and KDBerlin, Organic Synthesis, vol. 61, 56-59 (1983). It can be synthesized by the method represented by the formula.

Specifically, when the synthesis of V is -R ¹ O- and W is -OR ² -, and R ¹ and R ² are the same polymerizable compound represented by the above formula (1), the following reaction formula is exemplified. Show 2 methods.

In the case of synthesizing the polymerizable compound represented by the above formula (4) in which R ¹ and R ^{2 are} different, a method represented by the following reaction formula may be mentioned.

In the above formula (4), in the case of synthesizing a polymerizable compound in which V and W are a single bond, a method represented by the following reaction formula may be mentioned.

<Synthesis of polyaminic acid>

A method of producing a poly-proline by reacting a diamine component with a tetracarboxylic dianhydride can be carried out by a known synthesis method. In general, a method for reacting a diamine component with a tetracarboxylic dianhydride component in an organic solvent. It is advantageous that the reaction of the diamine component with the tetracarboxylic dianhydride is relatively easy in an organic solvent and does not produce by-products.

The organic solvent used in the above reaction is not particularly limited as long as it is a solvent capable of dissolving the produced polyamic acid. Further, even if the organic solvent of polylysine is not dissolved, it may be used in combination with the above solvent as long as the range of the produced polyamic acid is not precipitated. Further, the water in the organic solvent hinders the polymerization reaction and causes the hydrolysis of the produced polylysine, so that the organic solvent is preferably dried by dehydration.

The organic solvent used in the above reaction, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide , N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-tetrahydroimidazolone, 3-methoxy- N,N-dimethylpropanamide, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, different Propyl alcohol, methoxymethylpentanol, dipentene, ethyl pentanone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, Ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol Monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert- Butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol single B Acid ester monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methyl Oxybutyl butyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutyl butyl ester, pentyl acetate, butyl Butyrate, dibutyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, ring Hexone, ethyl acrylate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, pyruvic acid Ester, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropane Acid propyl ester, butyl 3-methoxypropionate, diglyme, 4- Hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, and the like. These organic solvents may be used singly or in combination.

a method in which a diamine component and a tetracarboxylic dianhydride component are reacted in an organic solvent, for example, a solution obtained by dispersing or dissolving a diamine component in an organic solvent with stirring, and the tetracarboxylic dianhydride component is not treated, or a method of dispersing or dissolving in an organic solvent and then adding it, and conversely adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent, and a tetracarboxylic dianhydride component and two A method of alternately adding an amine component can be used. Further, the diamine component or the tetracarboxylic dianhydride component is formed by a plurality of compounds, and the reaction may be carried out in a state of being premixed, and the respective reactions may be carried out in sequence, or the respective reactions may be further carried out. Low molecular The mixed reaction may be carried out as a high molecular weight body.

The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted is, for example, -20 ° C to 150 ° C, preferably -5 ° C to 100 ° C. In the reaction, for example, the total concentration of the diamine component and the tetracarboxylic dianhydride component is preferably from 1 to 50% by mass, and preferably from 5 to 30% by mass, based on the reaction liquid.

In the above polymerization reaction, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic dianhydride component can be selected in accordance with the molecular weight of the polyamic acid to be obtained. As with the usual polycondensation reaction, the molecular weight of the polyglycine produced by the closer the molar ratio is closer to 1.0, the more preferable range is 0.8 to 1.2.

The method for synthesizing the poly-proline used in the present invention is not limited to the above method, and it can be used in the same manner as the general method for synthesizing poly-proline, using a tetracarboxylic acid or a tetracarboxylic acid dihalide having a corresponding structure. When the tetracarboxylic acid derivative is substituted for the above tetracarboxylic dianhydride and reacted by a known method, the corresponding polyglycolic acid can also be obtained.

A method for forming a polyimine by hydrazine imidization of the polyamic acid, for example, heating a solution of poly-proline to be thermally imidized, and adding a catalyst to a solution of poly-proline A method such as imidization of a catalyst. Further, the ruthenium imidization ratio of the polyaminic acid to the polyimine is not necessarily required to be 100%.

The temperature at which the polyaminic acid is thermally imidized in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water formed by the ruthenium imidization reaction is continuously excluded from the reaction system. The way outside is good.

The catalyst of poly-proline is imidized, and a basic catalyst and an acid anhydride are added to the solution of poly-proline, and the mixture is stirred at -20 to 250 ° C, preferably 0 to 180 ° C. Way to proceed. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to the prolyl group. 30 moles. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferably carried out during the reaction, and it is preferred to maintain an appropriate basicity. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, when acetic anhydride is used, it is preferred to carry out purification after completion of the reaction. The imidization rate of the imidization of the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

Further, the polyphthalate may be a reaction of synthesizing a tetracarboxylic acid diester dichloride with the same diamine as the above polyamine, or synthesizing a tetracarboxylic acid diester with the above polyamic acid. It can be obtained by reacting the same diamine in the presence of a suitable condensing agent or a base. Further, poly-proline can be synthesized in advance by the above method, and a polymer reaction can be used to esterify a carboxylic acid in proline to form an ester. Specific examples include, for example, a tetracarboxylic acid diester dichloride and a diamine in the presence of a base and an organic solvent, in the range of -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C. The polyglycolate can be synthesized by reacting for 30 minutes to 24 hours, preferably 1 hour to 4 hours. Subsequently, the polyamidimide can be obtained by heating the polyglycolate at a high temperature to promote the dealcoholization to carry out a ring closure reaction.

Recovering the produced poly-proline from the reaction solution, and collecting When a polyimide precursor such as a phthalate precursor or a polyimide is used, the reaction solution may be poured into a poor solvent to precipitate. Examples of the poor solvent used for the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The precipitated polymer is introduced into a poor solvent, filtered, and recovered, and then dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, when the recovered polymer is subjected to an operation of re-dissolving the organic solvent and reprecipitating and recovering 2 to 10 times, the impurities in the polymer can be reduced. In the case of the poor solvent at this time, for example, alcohols, ketones, hydrocarbons, and the like, when three or more kinds of poor solvents selected from the above are used, the purification efficiency of one layer can be further increased, and good.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention contains a polymer having at least one structure represented by the above formula (I) in a side chain, and the content of the polymer is preferably from 1 to 20% by mass, more preferably from 3 to 15%. The mass% is particularly preferably 3 to 10% by mass. Further, in the case of a polymerizable compound having two or more terminal groups each having a photopolymerization or photocrosslinking group, the content thereof is preferably from 1 to 50 parts by mass, more preferably from 5 parts by mass to 100 parts by mass of the polymer. ~30 parts by mass.

Further, the liquid crystal alignment agent of the present invention may contain other polymers than the above polymers. In this case, the content of the other polymer in the entire polymer component is preferably from 0.5 to 80% by mass, more preferably from 20 to 50% by mass.

The molecular weight of the polymer of the liquid crystal alignment agent is considered to be the GPC (Gel Permeation Chromatography) in consideration of the strength of the liquid crystal alignment film obtained by coating the liquid crystal alignment agent, the workability at the time of formation of the coating film, and the uniformity of the coating film. The weight average molecular weight measured by the method is preferably 5,000 to 1,000,000, preferably 10,000 to 150,000.

The solvent to be contained in the liquid crystal alignment agent is not particularly limited as long as it can dissolve or disperse a polymer having a structure represented by the above formula (I) in a side chain, and two or more kinds of terminals contained in the necessity of blending. Any component such as a polymerizable compound having a photopolymerization or photocrosslinking group may be used. For example, an organic solvent exemplified as the synthesis of the above polyamic acid may be mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-tetrazolidine, 3-methoxy The base-N,N-dimethylpropanamide is preferred from the viewpoint of solubility. Of course, a mixed solvent of two or more types may be used.

Further, it is preferred to use a solvent which improves the uniformity or smoothness of the coating film and a highly soluble solvent which is a component of the liquid crystal alignment agent. The solvent, for example, isopropanol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl Cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether , ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoethyl Acid ester, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol single ethyl Acid ester monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene , pentyl acetate, butyl butyrate, dibutyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3 -ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl , 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate , propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, 2-ethyl-1-hexanol, etc. . These solvents can mix a plurality of species. The solvent is preferably from 5 to 80% by mass, and preferably from 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.

The liquid crystal alignment agent may contain components other than the above. For example, when a liquid crystal alignment agent is applied, a compound which can improve film thickness uniformity or surface smoothness, a compound which improves adhesion between a liquid crystal alignment film and a substrate, and the like can be mentioned.

Examples of the compound which improves the film thickness uniformity or the surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic It is a surfactant and the like. More specifically, for example, F-TOP EF301, EF303, EF352 (manufactured by The Dow Chemical Co., Ltd.), Megfried F171, F173, R-30 (manufactured by Dainippon Paint Co., Ltd.), and Fradado FC430 FC431 (manufactured by Sumitomo 3M Co., Ltd.), Ashamig AG710, Shaflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The proportion of the surfactant to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total amount of the polymer contained in the liquid crystal alignment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include a compound containing a functional decane or a compound containing an epoxy group. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-amine Benzyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminepropanyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3- Ureapropyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyltrimethoxy decane, N-ethoxycarbonyl-3-aminopropyltriethoxy decane, N-triethoxy Mercaptopropyltriethylamine, N-trimethoxysulfonylpropyltriethylamine, 10-trimethoxydecyl-1,4,7-triazanonane, 10-triethoxy Base alkyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3,6- Diazepine acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyl Trimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyvinyl)-3-aminopropyltrimethoxydecane, N-bis(oxyvinyl)-3 -aminopropyltriethoxy Decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexyl Glycol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminemethyl)cyclohexane, N,N,N ',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane, 3-(N,N- Diglycidyl) Aminopropyltrimethoxydecane, and the like.

Further, in order to further improve the film strength of the liquid crystal alignment film, 2,2'-bis(4-hydroxy-3,5-dimethylol)propane and tetrakis(methoxymethyl)bisphenol may be added. Phenolic compounds. The compound is preferably used in an amount of 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of the total of the polymer contained in the liquid crystal alignment agent.

Further, in the liquid crystal alignment agent, a dielectric or a conductive material for the purpose of changing electrical characteristics such as a dielectric constant or conductivity of the liquid crystal alignment film may be added in addition to the above-described effects of the present invention.

By coating and sintering the liquid crystal alignment agent on the substrate, a liquid crystal alignment film that vertically aligns the liquid crystal can be formed. When the liquid crystal alignment agent of the present invention is used, the response speed of the liquid crystal display element using the obtained liquid crystal alignment film can be accelerated. Further, the polymerizable compound having two or more terminal groups respectively contained in the liquid crystal alignment agent of the present invention having a photopolymerization or photocrosslinking group is not contained in the liquid crystal alignment agent or is contained in the liquid crystal alignment agent. In the liquid crystal, it can be used in the so-called PSA mode. The reaction is highly sensitive, and the inclination angle can be given even under a small amount of ultraviolet rays.

For example, the liquid crystal alignment agent of the present invention can be used as a liquid crystal alignment film without being processed, after being applied to a substrate and then dried and sintered as necessary. In addition, the liquid crystal display element in which the liquid crystal is filled as a PSA alignment film by rubbing the cured film, irradiating a polarized light or a light having a specific wavelength, and the like, can be irradiated with UV in a state where a voltage is applied. In particular, it is suitable as a user of an alignment film for PSA.

In this case, the substrate to be used is not particularly limited as long as it has a substrate having high transparency, and a glass plate, polycarbonate, poly(meth)acrylate, polyether oxime, polyacrylate, or the like can be used. Polyurethane, polybenzazole, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triethylenesulfonyl cellulose, diethyl A plastic substrate such as fluorenyl cellulose or acetate butyrate cellulose. Moreover, it is preferable from the viewpoint of simplifying the process, using a substrate on which an ITO electrode or the like used for liquid crystal driving is used. Further, in the reflective liquid crystal display device, when it is only a single-sided substrate, an opaque such as a germanium wafer may be used. In this case, a material such as aluminum which can reflect light may be used.

The coating method of the liquid crystal alignment agent is not particularly limited, and examples thereof include a printing method such as screen printing, lithography, and flexo printing, an inkjet method, a spray method, a roll coating method, or a dipping roller. Coating method, slit coating method, spin coating method, and the like. From the viewpoint of productivity to industrial viewpoint, a transfer printing method is generally widely used, and the method is also suitably used in the present invention.

The coating film formed by coating the liquid crystal alignment agent according to the above method can be used as a cured film after sintering. The drying step after the application of the liquid crystal alignment agent is not necessarily required, but the time from the application to the sintering is not fixed depending on the substrate, or the sintering is not performed immediately after the application. The drying step is preferred. This drying is not particularly limited as long as the solvent can be removed to such an extent that the shape of the coating film is not deformed when the substrate or the like is transported. For example, it is dried on a hot plate having a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes.

The sintering temperature of the coating film formed by coating the liquid crystal alignment agent is not particularly limited, and is, for example, 100 to 350 ° C, preferably 120 to 300 ° C, more preferably 150 ° C to 250 ° C. The sintering time is from 5 minutes to 240 minutes, preferably from 10 minutes to 90 minutes, more preferably from 20 minutes to 90 minutes. The heating can be carried out by a generally known method, for example, using a hot plate, a hot air circulating furnace, an infrared furnace or the like.

Further, the thickness of the liquid crystal alignment film obtained by sintering is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 100 nm.

<Liquid crystal display element>

In the liquid crystal display device of the present invention, after the liquid crystal alignment film is formed on the substrate by the above method, the liquid crystal cell is produced by a known method. Specific examples of the liquid crystal display device include, for example, two substrates arranged in a facing manner, a liquid crystal layer provided between the substrates, and a liquid crystal alignment agent of the present invention provided between the substrate and the liquid crystal layer. The above liquid crystal alignment film A liquid crystal display element of a vertical alignment mode of a liquid crystal cell. Specifically, the liquid crystal alignment agent of the present invention is applied onto two substrates, and is sintered to form a liquid crystal alignment film, and the liquid crystal alignment film is disposed on the substrate in two opposite directions. A liquid crystal layer composed of liquid crystal is sandwiched between two substrates, that is, a liquid crystal layer is provided in contact with the liquid crystal alignment film, and a liquid crystal cell obtained by irradiating ultraviolet rays is applied to a liquid crystal alignment film and a liquid crystal layer. Vertical alignment type liquid crystal display element.

The liquid crystal alignment film formed by using the liquid crystal alignment agent of the present invention irradiates ultraviolet rays by applying a voltage to the liquid crystal alignment film and the liquid crystal layer to polymerize the polymerizable compound, and the photoreactive side chains of the polymer are mutually Further, as a result of the reaction between the photoreactive side chain of the polymer and the polymerizable compound, the alignment of the liquid crystal can be more efficiently immobilized, and a liquid crystal display element having a remarkably excellent response speed can be formed.

The substrate used in the liquid crystal display device of the present invention is not particularly limited as long as it is a substrate having high transparency. Usually, a substrate on which a transparent electrode for driving a liquid crystal is formed is formed on a substrate. Specific examples include the same contents as those of the substrate described in the liquid crystal alignment film. It is possible to use a conventional electrode pattern or a substrate having a projection pattern. In the liquid crystal display device of the present invention, since the liquid crystal alignment agent of the present invention described above is used, a line/slot of, for example, 1 to 10 μm is formed on the single-sided substrate. In the electrode pattern, the structure in which the slit pattern or the protrusion pattern is not formed in the opposite substrate can also be activated. Therefore, when the liquid crystal display element of the structure is used, the manufacturing process can be simplified, and high transmittance can be obtained. .

Moreover, in a high-performance element like a TFT type element, A member such as a transistor-like element is formed between an electrode for driving a liquid crystal and a substrate.

In the case of a transmissive liquid crystal display device, a substrate such as the above-described substrate is generally used. In the case of a reflective liquid crystal display device, when only a single-sided substrate is used, an opaque substrate such as a germanium wafer may be used. At this time, as the electrode formed on the substrate, a material such as aluminum which reflects light can be used.

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display device of the present invention is not particularly limited, and a liquid crystal material used in a conventional vertical alignment method can be used. For example, MLC-6608 or MLC-6609 manufactured by Meike Co., Ltd. can be used. Negative liquid crystal. Further, in the PSA mode, for example, a liquid crystal containing a polymerizable compound represented by the following formula can be used.

In the present invention, a method of sandwiching the liquid crystal layer between the two substrates may be, for example, a known method or the like. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a spacer such as a particle is spread on a liquid crystal alignment film of one substrate to form an inner side of the side on which the liquid crystal alignment film is formed, and is bonded to the substrate on the other side. Then, the liquid crystal is injected under reduced pressure, and a method of sealing is performed. Further, a pair of substrates for forming a liquid crystal alignment film are prepared, and a spacer such as a particle is spread on a liquid crystal alignment film of a substrate on one side, and then a liquid crystal is dropped. Thereafter, a liquid crystal cell can be obtained by laminating the substrate on the side of the liquid crystal alignment film and bonding it to the substrate on the other side. The thickness of the spacer is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

a step of applying a voltage to a liquid crystal alignment film and a liquid crystal layer to irradiate ultraviolet rays to obtain a liquid crystal cell, for example, inputting a voltage between electrodes provided on a substrate, and applying an electric field to the liquid crystal alignment film and the liquid crystal layer to maintain the electric field In the state of being irradiated with ultraviolet rays, etc. The voltage between the input electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The amount of ultraviolet light irradiation is, for example, 1 to 60 J, preferably 40 J or less. When the amount of ultraviolet irradiation is small, the reliability of the member constituting the liquid crystal display element is suppressed from being lowered, and the time for ultraviolet irradiation can be reduced. Therefore, it is preferable in terms of manufacturing efficiency.

As described above, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer, when the ultraviolet ray is irradiated, the polymerizable compound can be reacted to form a polymer, and the tilt direction of the liquid crystal molecules can be stored through the polymer, whereby the obtained liquid crystal display element can be accelerated. The speed of response. Further, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer, when the ultraviolet ray is irradiated, a side chain in which the liquid crystal is vertically aligned, a polyimide intermediate precursor which is adjacent to the photoreactive side chain, and the polyimide precursor precursor are passed through the ruthenium. The photoreactive side chains of the at least one selected from the imidized polyimine, or the photoreactive side chains of the polymer, react with the polymerizable compound, and The response speed of the resulting liquid crystal display element can be accelerated.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples.

<Synthesis of diamine> (Synthesis Example 1) 2-(2-(2,4-Diaminophenoxy)ethyl)-4,5,6,7-tetrahydro-1H-isoindole-1,3-(2H) -dione synthesis

Step 1: Synthesis of N-(2-hydroxyethyl)-2,3,4,5-tetrahydrobenzonitrile.

A stirrer, a nitrogen gas introduction tube, and a Dean-Stark apparatus were placed in a 500-ml four-necked flask, and 1-cyclohexene-1,2-dicarboxylic anhydride (50.00 g: 328.6 mmol) was weighed, and 500 g of toluene was added thereto. The mixture was heated and stirred at 50 ° C to dissolve. Next, 2-ethanolamine (20.0 g: 328.6 mmol) was gradually added and stirred for 30 minutes, and then the temperature was raised to 120 ° C, and the mixture was refluxed for 6 hours to carry out a dehydration reaction to remove the produced water.

After the completion of the reaction, 200 g of ethyl acetate was added to carry out liquid separation treatment, and then the organic phase was washed with 300 ml of an aqueous potassium carbonate solution (10%), 300 ml of purified water, and 300 ml of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent is removed using a rotary evaporator and vacuum dried. The thin yellow clay of the desired product was 52.6 g (269.4 mmol: yield 82%).

Step 2: 2-(2-(2,4-Dinitrophenoxy)ethyl)-4,5,6,7-tetrahydro-1H-isoindole-1,3-(2H)- Synthesis of diketones.

A stirrer, a nitrogen introduction tube, and a reflux tube were placed in a 500 ml four-necked flask, and 2,4-dinitrofluorobenzene (43.8 g: 235.6 mmol) was weighed and the N-(2-hydroxyethyl group) obtained in the first step was weighed. -2,3,4,5-tetrahydrobenzimidine (46.0 g: 235.6 mmol), dissolved in 500 g of THF, and added potassium carbonate (42.3 g: 306.3 mmol) in a nitrogen atmosphere at 60 ° C The reaction was carried out for 24 hours.

After the completion of the reaction, the potassium carbonate was removed by filtration, and 200 ml of ethyl acetate was added to the reaction solution to carry out a liquid separation treatment. The organic phase was washed with 300 g of pure water, 300 g of saturated brine, and dried over anhydrous magnesium sulfate. .

After filtration, the solvent was removed using a rotary evaporator, and recrystallization was carried out using methanol, and the obtained solid was washed with 300 ml of methanol, and dried under vacuum to obtain 68.0 g (188.5 mmol: yield 80%) of the object. ).

Step 3: 2-(2-(2,4-Diaminophenoxy)ethyl)-4,5,6,7-tetrahydro-1H-isoindole-1,3-(2H)- Synthesis of diketones.

A nitrogen introduction tube, a reflux tube, and a mechanical stirrer were placed in a 2000 ml four-necked flask, and the dinitrogen (50.0 g: 138.0 mmol) obtained in the second step, 500 g of toluene, and reduced iron (77.3 g: 1.38 mol) were added. , 10% ammonium chloride aqueous solution 500g, under nitrogen atmosphere, 60 ° C Reaction for 24 hours.

After completion of the reaction, the reaction solution was filtered using a glass filter, and 300 g of ethyl acetate was added to the reaction solution, and the mixture was washed five times with 300 g of pure water, and dried over anhydrous magnesium sulfate. After removing magnesium sulfate by filtration, the solvent was removed using a rotary evaporator, and the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / N-hexane = 3:1) to obtain the desired diamine. The thin brown color of the slime was 33.0 g (109.5 mmol: yield 79%).

(Synthesis Example 2) Synthesis of 2-(2-(2,4-diaminophenoxy)ethyl)isoindole-1,3-dione

First step: synthesis of 2-(2,4-dinitrophenoxy)bromoethane

A stirrer, a nitrogen introduction tube, and a reflux tube were placed in a 500 ml four-necked flask, and 2,4-dinitrofluorobenzene (50.0 g: 268.73 mmol) and 2-bromoethanol (41.7 g: 322.4 mmol) were weighed and added. 300 g of THF and triethylamine (32.6 g: 322.4 mmol) were reacted under a nitrogen atmosphere at 60 ° C for 24 hours.

After the reaction, ethyl acetate was added to the reaction solution. 200 g of the organic phase was washed three times with 300 g of pure water and 300 g of saturated brine, and dried with anhydrous magnesium sulfate.

After filtration, the solvent was removed using a rotary evaporator, and the result was purified using a cerium oxide gel using a flash column (developing solvent: ethyl acetate / N-hexane = 5:1) to obtain a thin orange of the object. Viscosity (72.74 g: yield 92%).

Step 2: Synthesis of 2-(2-(2,4-dinitrophenoxy)ethyl)isoindole-1,3-dione.

A stirrer, a nitrogen introduction tube, and a reflux tube were placed in a 500 ml four-necked flask, and 2-(2,4-dinitrophenoxy)bromoethane (50.0 g: 171.8 mmol) obtained in the first step was weighed. Potassium xylene sulfoxide (31.8 g: 171.8 mmol) was added to 300 ml of DMF, and the mixture was reacted at 80 ° C for 3 hours under a nitrogen atmosphere.

After completion of the reaction, the reaction solution was poured into a mixed solvent of water:methanol (1000 g:weight ratio:1:1) to precipitate a solid. The obtained crude product was collected by filtration, and washed with 300 ml of methanol to give a white solid (57.1 g: yield 93%).

Step 3: Synthesis of 2-(2-(2,4-diaminophenoxy)ethyl)isoindole-1,3-dione

A three-way cock and a stirrer were placed in a 1000 ml four-necked flask, and the dinitrogen (50.0 g: 140.0 mmol) obtained in the second step and 5.0 g of 10% palladium carbon were weighed, and 500 g of THF was added thereto, and nitrogen substitution was performed several times. The reaction was further carried out in a hydrogen atmosphere at 60 ° C for 24 hours.

After confirming the completion of the reaction, a film of 1 μm mesh was used. The filter was subjected to removal of palladium carbon, and the solvent was removed by a rotary evaporator. The crude product was washed with methanol (300 ml) to give an orange solid (31.2 g: yield: 75%).

(Synthesis Example 3) Synthesis of 2-(2-(2,4-diaminophenoxy)ethyl)-1H-benzoisoquinoline-1,3-dione

First step: 2-(2-hydroxyethyl)-1H-benzoisoquinoline-1,3(2H)-dione

A stirrer, a nitrogen introduction tube, and a Dean-Stark apparatus were placed in a 300-ml four-necked flask, and naphthalene-1,8-dicarboxylic anhydride (25.0 g: 126.2 mmol) was weighed, and toluene (200 g) was added thereto, and then, 2 was slowly added. After stirring ethanolamine (7.7 g: 126.2 mmol) for 30 minutes, pyridine (5.0 g: 63.1 mmol) was added, and the reaction was carried out for 20 hours.

After completion of the reaction, the reaction solution was poured into a mixed solvent of pure water and methanol (500 g (weight ratio: 1:1), and the solid was precipitated and stirred briefly. The crude product was filtered, washed with 300 g of methanol, and the solid was dried in vacuo to yield 30.0 g (124.4 mmol: yield: 99%) of the desired product.

Second step: 2-(2-(2,4-dinitrophenoxy)B -1H-benzoisoquinoline-1,3-dione

A stirrer, a nitrogen introduction tube, and a reflux tube were placed in a 300 ml four-necked flask, and 2,4-dinitrofluorobenzene (11.6 g: 62.2 mmol) and 2-(2-hydroxyethyl group) obtained in the first step were weighed. -1H-benzoisoquinoline-1,3(2H)-dione (15.0 g: 62.2 mmol), dissolved in 200 g of THF, and added triethylamine (9.4 g: 93.3 mmol) under nitrogen atmosphere Reflux for 24 hours. A solid precipitated as the reaction progressed. After confirming the disappearance of the raw material, the reaction solution was filtered, and the crude solid was recovered. The crude solid was washed with 300 ml of methanol, and dried under vacuum to give a white solid (22.3 g, 88.0%).

Third step: synthesis of 2-(2-(2,4-diaminophenoxy)ethyl)-1H-benzoisoquinoline-1,3-dione

A three-way cock and a stir bar were placed in a 500 mL four-necked flask, and the dinitrogen (20.0 g: 49.1 mmol) obtained in the second step and 2.0 g of 10% palladium carbon were weighed, and 300 g of DMF was added thereto, and nitrogen substitution was performed several times. The reaction was carried out for 24 hours under a hydrogen atmosphere at room temperature.

After confirming the completion of the reaction, palladium carbon was removed using a 1 μm mesh membrane filter, and the filtrate was poured into 1000 g of methanol to precipitate a solid. The obtained crude solid was collected by filtration and washed twice with 200 ml of methanol to give an orange solid of the desired diamine (12.3 g: yield 72%).

<Manufacture of liquid crystal alignment agent>

The following abbreviations are as follows.

(acid dianhydride)

BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

PMDA: pyromellitic anhydride

TCA: 2,3,5-tricarboxycyclopentyl acetic acid-1,4,2,3-dianhydride

(diamine)

p-PDA: p-phenylenediamine

DBA: 3,5-diamino benzoic acid

3AMPDA: 3,5-Diamino-N-(pyridin-3-methyl)benzamide

4DABP: a diamine having the benzophenone skeleton shown below

BABP: a diamine having the benzophenone skeleton shown below

DA-1~DA-3: the following free radical generating diamine obtained in Synthesis Examples 1 to 3

DA-4: The following free radical generating diamine

DA-5: photoreactive diamines described below

DA-6~DA-9: The following vertical alignment diamine

<solvent>

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve (cellosolve)

<additive>

3AMP: 3-methylpyridinium

<Polymerizable compound>

Polymerizable compound represented by the following formulas RM1 and RM2

<Measurement of molecular weight of polyimine]

Device: SENSHU Scientific Co., Ltd. Normal temperature gel chromatography (GPC) device (SSC-7200), column: Shodex column (KD-803, KD-805)

Column temperature: 50 ° C

Dissolution: N, N'-dimethylformamide (additive, lithium bromide-water and (LiBr‧H ₂ O) 30 mmol / L, phosphoric acid ‧ anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10ml/L)

Flow rate: 1.0ml/min

Standard sample used for making the calibration line: TSK standard made by Tosoh Corporation Polyethylene oxide (molecular weight: about 9,000, 150,000, 100,000, 30,000) and polyethylene glycol (molecular weight of about 12,000, 4,000, 1,000) manufactured by Polymer Research.

<Measurement of imidization ratio of polythenimine>

20 mg of polyimine powder was placed in an NMR sample tube (NMR sample tube standard manufactured by Kusano Scientific Co., Ltd.) In 5), 1.0 ml of dimethyl hydrazine (DMSO-d ₆ , 0.05% TMS mixture) was added, and ultrasonic waves were applied to completely dissolve it. This solution was measured for proton NMR at 500 MHz using a NMR measuring instrument (JNW-ECA500) manufactured by JEOL Ltd. The sulfhydrylation rate is determined by using protons generated by structures that have not changed before and after imidization as a reference proton, and is the peak value of the proton and the proline acid present in the vicinity of 9.5 to 10.0 ppm. The peak value of the proton wave generated by the NH group is obtained by the following calculation formula. Further, in the following formula, x is a proton peak product value generated by the NH group of the proline, y is the peak total value of the reference proton, and α is a polyproline (the imidization ratio is 0%). The ratio of the number of reference protons to the proton of the NH group of one proline.

醯 imidization rate (%) = (1-α‧x/y) × 100

(Example 1)

BODA (4.50 g, 18.0 mmol), p-PDA (0.97, 9 mmol), DA-1 (2.71 g, 9 mmol), DA-6 (4.57 g, 12.0) Methyl) was dissolved in NMP (51.0 g) and reacted at 60 ° C for 4 hours. Then, CBDA (2.31 g, 11.8 mmol) and NMP (9.3 g) were added and reacted at 40 ° C for 10 hours to obtain a polyamidonic acid solution. .

In this polyamic acid solution (50 g), NMP was added, and after diluting to 6.5% by mass, acetic anhydride (10.1 g) as a ruthenium amide catalyst and pyridine (7.9 g) were added and reacted at 80 ° C. 4 hours. The reaction solution was poured into methanol (600 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A). The polyamidimide had a ruthenium iodide ratio of 75%, a number average molecular weight of 17,800, and a weight average molecular weight of 40,300.

To the obtained polyimine powder (A) (6.0 g), NMP (44.0 g) was added, and the mixture was stirred at 70 ° C for 15 hours to dissolve. To the solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (A1).

(Example 2)

BODA (4.50 g, 18.0 mmol), p-PDA (0.97, 9 mmol), DA-2 (2.68 g, 9 mmol), DA-6 (4.57 g, 12.0 mmol) were dissolved in NMP (51.3 g) at 60 After reacting at ° C for 4 hours, CBDA (2.31 g, 11.8 mmol) and NMP (8.8 g) were added, and the mixture was reacted at 40 ° C for 10 hours to obtain a polyaminic acid solution.

In this polyamic acid solution (50 g), NMP was added, and after diluting to 6.5% by mass, acetic anhydride as a ruthenium catalyst was added. (10.2 g) and pyridine (7.9 g) were reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (600 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (B). The polyimine had a hydrazine imidization ratio of 75%, a number average molecular weight of 16,600, and a weight average molecular weight of 39,300.

NMP (44.0 g) was added to the obtained polyimine powder (B) (6.0 g), and the mixture was stirred at 70 ° C for 15 hours to be dissolved. To the solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (B1).

In addition, 0.06 g of the polymerizable compound RM1 (10% by mass based on the solid content) was added to 10.0 g of the liquid crystal alignment agent (B1), and the mixture was stirred at room temperature for 3 hours to be dissolved, thereby preparing a liquid crystal alignment agent ( B2).

In addition, 0.06 g of the polymerizable compound RM2 (10% by mass based on the solid content) was added to 10.0 g of the liquid crystal alignment agent (B1), and the mixture was stirred at room temperature for 3 hours to be dissolved, thereby preparing a liquid crystal alignment agent ( B3).

(Example 3)

BODA (4.50 g, 18.0 mmol), p-PDA (0.97, 9 mmol), DA-3 (3.13 g, 9 mmol), DA-6 (4.57 g, 12.0 mmol) were dissolved in NMP (52.6 g) at 60 After reacting at ° C for 4 hours, CBDA (2.31 g, 11.8 mmol) and NMP (9.3 g) were added. The reaction was carried out at 40 ° C for 10 hours to obtain a polyamic acid solution.

In this polyamic acid solution (50 g), NMP was added, and after diluting to 6.5% by mass, acetic anhydride (9.9 g) as a ruthenium amide catalyst and pyridine (7.6 g) were added, and the reaction was carried out at 80 ° C. 4 hours. The reaction solution was poured into methanol (600 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (C). The polyamidimide had a ruthenium iodide ratio of 74%, a number average molecular weight of 16,300, and a weight average molecular weight of 37,600.

To the obtained polyimine powder (C) (6.0 g), NMP (44.0 g) was added, and the mixture was stirred at 70 ° C for 15 hours to dissolve. To the solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (C1).

In addition, 0.06 g of the polymerizable compound RM1 (10% by mass based on the solid content) was added to 10.0 g of the liquid crystal alignment agent (C1), and the mixture was stirred at room temperature for 3 hours to be dissolved, thereby preparing a liquid crystal alignment agent ( C2).

(Example 4)

BODA (1.5 g, 6 mmol), DBA (1.83, 12 mmol), 3AMPDA (2.18 g, 9 mmol), DA-6 (3.43 g, 9 mmol) were dissolved in NMP (35.7 g), and reacted at 60 ° C for 4 hours. CBD (3.46 g, 17.6 mmol) and NMP (10.0 g) were added, and the mixture was reacted at 40 ° C for 2 hours. Subsequently, add PMDA (1.31g, 0.06 Methyl) and NMP (9.1 g) were stirred at room temperature for 10 hours to give a polyamine acid solution.

In this polyamic acid solution (50 g), NMP was added, and after diluting to 6.5% by mass, acetic anhydride (11.1 g) as a ruthenium amide catalyst and pyridine (3.4 g) were added and reacted at 50 ° C. 3 hours. The reaction solution was poured into methanol (590 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (D). The polyimine had a hydrazine imidation ratio of 78%, a number average molecular weight of 21,300, and a weight average molecular weight of 5,1600.

To the obtained polyimine powder (D) (6.0 g), NMP (44.0 g) was added, and the mixture was stirred at 70 ° C for 15 hours to be dissolved. To the solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (D1).

In addition, 5.0 g of the liquid crystal alignment agent (D1) was mixed with 5.0 g of the liquid crystal alignment agent (B1), and the mixture was stirred for 3 hours to obtain a liquid crystal alignment agent (D2).

(Example 5)

TCA (3.4 g, 15.0 mmol), 3AMPDA (2.54 g, 10.5 mmol), DA-2 (3.57 g, 12.0 mmol), DA-8 (3.92 g, 7.5 mmol) were dissolved in NMP (56.4 g), After reacting at 80 ° C for 5 hours, CBDA (2.89 g, 14.8 mmol) and NMP (8.8 g) were added, and the mixture was reacted at 40 ° C for 10 hours to obtain a polyaminic acid solution.

To the polyamic acid solution (45 g), NMP was added, and after diluting to 6 mass%, acetic anhydride (5.5 g) as a ruthenium amide catalyst and pyridine (2.9 g) were added, and the reaction was carried out at 50 ° C. 3 hours. The reaction solution was poured into methanol (550 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (E). The polyimine had a hydrazine imidization ratio of 49%, a number average molecular weight of 16,200, and a weight average molecular weight of 33,000.

To the obtained polyimine powder (E) (6.0 g), NMP (44.0 g) was added, and the mixture was stirred at 70 ° C for 15 hours to dissolve. To the solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (E1).

(Embodiment 6) BEM-S

BODA (2.0 g, 8.0 mmol), DA-5 (1.6 g, 6.0 mmol), DA-2 (2.4 g, 8.0 mmol), DA-7 (2.6 g, 6.0 mmol) were dissolved in NMP (34.3 g) After reacting at 60 ° C for 3 hours, CBDA (2.3 g, 11.8 mmol) and NMP (9.3 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyaminic acid solution.

To the polyamic acid solution (30 g), NMP was added, and after diluting to 6 mass%, acetic anhydride (5.6 g) as a ruthenium amide catalyst and pyridine (8.7 g) were added, and the reaction was carried out at 50 ° C. 3 hours. The reaction solution was poured into methanol (400 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C to obtain a polyimide powder. End (F). The polyamidimide had a ruthenium iodide ratio of 51%, a number average molecular weight of 2,1200, and a weight average molecular weight of 53,000.

NMP (22.0 g) was added to the obtained polyimine powder (F) (3.0 g), and the mixture was stirred at 50 ° C for 5 hours to dissolve. To the solution, 3.0 g of 3AMP (1 wt% NMP solution), NMP (2.0 g), and BCS (20.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (F1). In addition, 0.06 g of the polymerizable compound RM1 (10% by mass based on the solid content) was added to 10.0 g of the liquid crystal alignment agent (F1), and the mixture was stirred at room temperature for 3 hours to be dissolved, thereby preparing a liquid crystal alignment agent ( F2).

(Example 7)

BODA (3.5 g, 12.0 mmol), 3AMPDA (1.2, 5.0 mmol), DA-2 (2.4 g, 8.0 mmol), DA-9 (2.8 g, 7.0 mmol) were dissolved in NMP (37.6 g) at 60 After reacting at ° C for 4 hours, CBDA (3.0 g, 7.7 mmol) and NMP (5.9 g) were added, and the mixture was reacted at 40 ° C for 10 hours to obtain a polyaminic acid solution.

To the polyamic acid solution (30 g), NMP was added, and after diluting to 6.5% by mass, acetic anhydride (5.7 g) as a ruthenium-imiding catalyst, and pyridine (4.4 g) were added, and the reaction was carried out at 80 ° C. 4 hours. The reaction solution was poured into methanol (400 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (C). The polyamidimide had a ruthenium iodide ratio of 73%, a number average molecular weight of 21,300, and a weight average molecular weight of 45,600.

To the obtained polyimine powder (G) (3.0 g), NMP (22.0 g) was added, and the mixture was stirred at 70 ° C for 15 hours to be dissolved. To the solution, 3.0 g of 3AMP (1 wt% NMP solution), NMP (2.0 g), and BCS (20.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (G1).

(Comparative Example 1)

BODA (4.50 g, 18.0 mmol), p-PDA (1.95, 18 mmol), DA-6 (4.57 g, 12.0 mmol) were dissolved in NMP (44.0 g), and reacted at 40 ° C for 3 hours, then CBDA was added ( 2.28 g, 11.6 mmol) and NMP (9.3 g) were reacted at 40 ° C for 10 hours to obtain a polyaminic acid solution.

To the polyamic acid solution (50 g), NMP was added, and after diluting to 6.5% by mass, acetic anhydride (11.5 g) as a ruthenium amide catalyst and pyridine (8.9 g) were added and reacted at 80 ° C. 4 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A). The polyimine had a ruthenium iodide ratio of 73%, a number average molecular weight of 17,200, and a weight average molecular weight of 39,300.

To the obtained polyimine powder (H) (6.0 g), NMP (44.0 g) was added, and the mixture was stirred at 70 ° C for 15 hours to dissolve. To the solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (H1).

In addition, 0.06 g of the polymerizable compound RM1 (10% by mass based on the solid content) was added to 10.0 g of the liquid crystal alignment agent (H1), and the mixture was stirred at room temperature for 3 hours to be dissolved, thereby preparing a liquid crystal alignment agent ( H2).

(Comparative Example 2)

BODA (4.50 g, 18.0 mmol), p-PDA (0.97, 9 mmol), DA-4 (2.97, 9 mmol), DA-6 (4.57 g, 12.0 mmol) were dissolved in NMP (50.8 g) at 60 ° C After 4 hours of the reaction, CBDA (2.31 g, 11.8 mmol) and NMP (10.5 g) were added, and the mixture was reacted at 40 ° C for 10 hours to obtain a polyamidonic acid solution.

In this polyamic acid solution (50 g), NMP was added, and after diluting to 6.5% by mass, acetic anhydride (10.0 g) as a ruthenium amide catalyst and pyridine (7.7 g) were added, and the reaction was carried out at 80 ° C. 4 hours. The reaction solution was poured into methanol (600 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (B). The polyimine had a hydrazine imidation ratio of 76%, a number average molecular weight of 18,300, and a weight average molecular weight of 51,300.

To the obtained polyimine powder (I) (6.0 g), NMP (44.0 g) was added, and the mixture was stirred at 70 ° C for 15 hours to dissolve. To the solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (I1).

(Comparative Example 3)

BODA (3.5 g, 12.0 mmol), p-PDA (0.6 g, 6.0 mmol), 4DABP (1.3 g, 6.0 mmol), DA-6 (3.0 g, 8.0 mmol) were dissolved in NMP (32.0 g), After reacting at 60 ° C for 4 hours, CBDA (1.5 g, 7.7 mmol) and NMP (6.0 g) were added, and the mixture was reacted at 40 ° C for 10 hours to obtain a polyaminic acid solution.

To the polyamic acid solution (30 g), NMP was added, and after diluting to 6.5% by mass, acetic anhydride (6.4 g) as a ruthenium catalyst was added, and pyridine (5.0 g) was added, and the reaction was carried out at 80 ° C. 4 hours. The reaction solution was poured into methanol (380 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (J). The polyimine had a hydrazine imidation ratio of 72%, a number average molecular weight of 19,300, and a weight average molecular weight of 41,300.

To the obtained polyimine powder (J) (3.0 g), NMP (22.0 g) was added, and the mixture was stirred at 70 ° C for 15 hours to be dissolved. To the solution, 3.0 g of 3AMP (1 wt% NMP solution), NMP (2.0 g), and BCS (20.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (J1).

In addition, 0.06 g of the polymerizable compound RM1 (10% by mass based on the solid content) was added to 10.0 g of the liquid crystal alignment agent (J1), and the mixture was stirred at room temperature for 3 hours to be dissolved, thereby preparing a liquid crystal alignment agent ( J2).

In addition, 0.06 g of the polymerizable compound RM2 (10% by mass based on the solid content) was added to 10.0 g of the above liquid crystal alignment agent (J1). The liquid crystal alignment agent (J3) was obtained by stirring at room temperature for 3 hours to dissolve.

(Comparative Example 4)

BODA (3.0 g, 12.0 mmol), p-PDA (0.7 g, 6.0 mmol), BABP (2.4 g, 6.0 mmol), DA-6 (3.0 g, 8.0 mmol) were dissolved in NMP (32.0 g), After reacting at 60 ° C for 4 hours, CBDA (1.5 g, 7.7 mmol) and NMP (6.0 g) were added, and the mixture was reacted at 40 ° C for 10 hours to obtain a polyaminic acid solution.

To the polyamic acid solution (30 g), NMP was added, and after diluting to 6.5% by mass, acetic anhydride (5.8 g) as a ruthenium amide catalyst and pyridine (4.4 g) were added, and the reaction was carried out at 80 ° C. 4 hours. The reaction solution was poured into methanol (360 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (K). The polyimine had a ruthenium iodide ratio of 73%, a number average molecular weight of 19,300, and a weight average molecular weight of 41,300.

To the obtained polyimine powder (K) (3.0 g), NMP (22.0 g) was added, and the mixture was stirred at 70 ° C for 15 hours to be dissolved. To the solution, 3.0 g of 3AMP (1 wt% NMP solution), NMP (2.0 g), and BCS (20.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (K1).

In addition, 0.06 g of the polymerizable compound RM1 (10% by mass based on the solid content) was added to 10.0 g of the liquid crystal alignment agent (K1), and the mixture was stirred at room temperature for 3 hours to be dissolved to obtain a liquid crystal alignment agent. (K2).

In addition, 0.06 g of the polymerizable compound RM2 (10% by mass based on the solid content) was added to 10.0 g of the liquid crystal alignment agent (K1), and the mixture was stirred at room temperature for 3 hours to be dissolved, thereby preparing a liquid crystal alignment agent ( K3).

<Manufacture of liquid crystal cell for PSA> (Example 8)

Using the liquid crystal alignment agent (A1) obtained in Example 1, the production of a liquid crystal cell was carried out in the order shown below. The liquid crystal alignment agent (A1) obtained in Example 1 was spin-coated on an ITO surface of an ITO electrode substrate having an ITO electrode pattern of a line/space of 5 μm each having a pixel size of 100 μm × 300 μm on a hot plate at 80 ° C. After drying for 90 seconds, it was sintered in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.

Further, the liquid crystal alignment agent (A1) was spin-coated on the ITO surface on which the electrode pattern was not formed, and dried using a hot plate at 80 ° C for 90 seconds, and then sintered in a hot air circulating oven at 200 ° C for 30 minutes to form a film thickness of 100 nm. Liquid crystal alignment film.

After a 4 μm particle spacer was spread on the liquid crystal alignment film of one of the two substrates, a sealant was printed thereon (solvent-type thermosetting epoxy resin, STRICTBOND XN-1500T manufactured by Mitsui Chemicals Co., Ltd.) . Next, the surface of the other substrate is formed on the side of the liquid crystal alignment film as the inner side, and is bonded to the previous substrate. Thereafter, the sealant is hardened to obtain an empty unit cell. Liquid crystal MLC-6608 (trade name, manufactured by Meike Co., Ltd.) was injected into the empty cell by a reduced pressure injection method to obtain a liquid crystal cell.

The obtained liquid crystal cell is irradiated with a DC voltage of 15 V from the outside of the liquid crystal cell, through a 325 nm high-pass filter, or a 365 nm band-pass filter to illuminate 15 J. UV. Subsequently, the response speed was measured in the following order, and the response speed after UV irradiation was compared. Further, the pretilt angle of the pixel portion of the unit cell after the UV irradiation was measured. The results are shown in Table 1.

<Measurement method of response speed>

First, in a measuring device including a polarizing plate and a light amount detector in a group of a backlight and a crossed polarizer configuration, a liquid crystal cell is disposed between a group of polarizing plates. At this time, a pattern of line/space ITO electrodes is formed, which forms an angle of 45 with respect to the crossed polarizers. Subsequently, a rectangular wave having a voltage of ±6 V and a number of cycles of 1 kHz is applied to the liquid crystal cell described above, and the change from the luminance observed by the light amount detector to saturation is read using an oscilloscope, and the luminance when the voltage is not applied is 0. %, a voltage of ±4V is applied, and the value of the saturation brightness is 100%, and the time taken for the change of brightness from 10% to 90% is used as the response speed.

<Measurement of pretilt angle>

LCD ANALYZER LCA-LUV42A manufactured by Mingling Technology Co., Ltd. was used.

(Examples 9 to 14, Comparative Examples 5 and 6)

The same operation as in Example 8 was carried out except that the liquid crystal alignment agent shown in Table 1 was used instead of the liquid crystal alignment agent (A1), and the response speed before and after the UV irradiation and the pretilt angle were measured. The results are summarized in Table 1.

<Manufacture of liquid crystal cell for SC-VA> (Example 15)

Using the liquid crystal alignment agent (B2) obtained in Example 2, the production of the liquid crystal cell was carried out in the order shown below. The liquid crystal alignment agent (B2) obtained in Example 1 was spin-coated on an ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line width of 5 μm was formed at 80 ° C. After drying on a hot plate for 90 seconds, it was sintered in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.

Further, the liquid crystal alignment agent (A2) was spin-coated on the ITO surface on which the electrode pattern was not formed, and dried on a hot plate at 80 ° C for 90 seconds, and then sintered in a hot air circulating oven at 200 ° C for 30 minutes to form a film thickness of 100 nm. Liquid crystal alignment film.

After a 4 μm particle spacer was spread on the liquid crystal alignment film of one of the two substrates, a sealant was printed thereon (solvent-type thermosetting epoxy resin, STRICTBOND XN-1500T manufactured by Mitsui Chemicals Co., Ltd.) . Next, the surface of the other substrate on which the liquid crystal alignment film side is formed is used as an inner side, and after bonding to the previous substrate, the sealing agent is cured to obtain an empty cell. Liquid crystal MLC-6608 (trade name, manufactured by Meike Co., Ltd.) was injected into the empty cell by a reduced pressure injection method to obtain a liquid crystal cell.

A state in which a DC voltage of 20 V is applied to the obtained liquid crystal cell is irradiated by a 325 nm high-pass filter or a 365 nm band-pass filter from the outside of the liquid crystal cell. UV of 15J. Subsequently, the response speed was measured in the same manner as in Example 8, and the response speed after UV irradiation was compared. Further, the pretilt angle of the pixel portion of the unit cell after the UV irradiation was measured. The results are shown in Table 2.

(Examples 15 to 18, Comparative Examples 7 to 11)

The same operation as in Example 8 was carried out except that the liquid crystal alignment agent shown in Table 1 was used instead of the liquid crystal alignment agent (B2), and the response speed before and after the UV irradiation and the pretilt angle were measured. Result collection As shown in table 2.

As shown in Table 1 and Table 2, it was confirmed that any of the PSA containing RM in the liquid crystal and the SC-VA containing RM in the alignment film, in the examples, not only the wavelength of 325 nm but also the ultraviolet irradiation of 365 nm Underneath, a tilt angle can also occur. On the other hand, in the comparative example, a sufficient tilt angle did not occur.

It is presumed that in the liquid crystal alignment agent of the comparative example, since the polymerizable compound itself hardly absorbs ultraviolet rays of 365 nm, it does not have a liquid crystal alignment film at a site where radicals are generated, and it is not required to initiate polymerization of RM. The sufficient radicals, in addition, have a radically generated radical, and the effect is extremely small, so that the polymerization reaction of RM cannot be initiated in the same manner. On the other hand, in the liquid crystal alignment agent of the example, it is estimated that sufficient radicals can be generated even when irradiated with ultraviolet rays on the long wavelength side, and the polymerizable compound is polymerized at the interface of the liquid crystal alignment film to form a tilt angle.

<Evaluation of Voltage Retention Rate> (Embodiment 19)

Using the liquid crystal alignment agent (A1) obtained in Example 1, a liquid crystal cell was externally irradiated with a 365 nm band-pass filter on the obtained liquid crystal cell by the method shown above. After UV irradiation for 30 minutes using a UV lamp, the RM remaining in the liquid crystal cell is sufficiently reacted, and a voltage of 1 V is applied for 60 μs at a temperature of 60 ° C to measure the voltage after 1667 ms, and the voltage can be calculated. To what extent is the voltage retention rate. The results are shown in Table 3.

(Examples 20 and 21, Comparative Examples 12 to 14)

The voltage holding ratio was measured by performing the same operation as in Example 19 except that the liquid crystal alignment agent shown in Table 3 was used instead of the liquid crystal alignment agent (A1). The results are summarized in Table 3.

As shown in Table 3, in either of the PSA containing RM in the liquid crystal and the SC-VA containing RM in the alignment film, it was confirmed in the comparative example whether or not it was irradiated with UV of 365 nm of a longer wavelength. Out The voltage holding rate is reduced. On the other hand, in the embodiment, the high voltage holding ratio is exhibited. From these results, it is known that the liquid crystal alignment agent of the present invention can produce a sufficiently high tilt angle and a voltage holding ratio even when a long wavelength UV is used, so that it is highly suitable for producing a highly reliable PSA or SC-VA liquid crystal display. element.

Claims (19)

A liquid crystal alignment agent characterized by containing a polymer having a side chain structure represented by the following formula (I); In the formula (I), a point indicates a bond to a polymer main chain, and Sp is a single bond, or an unsubstituted or alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom. The alkylene group may have an unsaturated bond, or a branched chain, or a cyclic structure; X represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, - CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-; Cy represents at least one or more of a carbonyl carbon bond necessarily having a quinone imine group The unsaturated hydrocarbon group having a carbon number of 5 to 14 which is unsaturatedly bonded, a part of a carbon atom constituting the cyclic hydrocarbon may be substituted by a hetero atom, and a hydrogen atom of the cyclic hydrocarbon may be a fluorine atom or a molecular weight of 14 to 100. Replaced by the organic base of one price. The liquid crystal alignment agent of claim 1, wherein the polymer having the side chain structure represented by the above formula (I) is a polyimine precursor having a side chain structure represented by the above formula (I) and At least one polymer selected from the group consisting of polyimine obtained by imidization of hydrazine. The liquid crystal alignment agent of claim 1, wherein the side chain structure described in the above formula (I) is represented by the following formula (II); In formula (II), the dots represent the bonds with the polymer backbone, n is an integer selected from 1 to 12, and X represents a single bond, -O-, -COO-, -OCO-, -NHCO-, - CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-; Cy represents a carbonyl group having a certain quinone imine group At least one or more unsaturated carbon-bonded cyclic hydrocarbon groups having 5 to 14 carbon atoms may be substituted by a hetero atom. The liquid crystal alignment agent of claim 3, wherein n in the above formula (II) is an integer of from 1 to 6, and Cy is a cyclic hydrocarbon group shown below, wherein two points respectively represent a bond with a quinone imine carbonyl carbon Knot The liquid crystal alignment agent of claim 3, wherein n in the above formula (II) is an integer of 1 to 6, X represents -O-, and Cy is cyclohexene, benzene, naphthalene or biphenyl. The liquid crystal alignment agent of claim 1, wherein the polymer further has a side chain which vertically aligns the liquid crystal. The liquid crystal alignment agent of claim 6, wherein the side chain in which the liquid crystal is vertically aligned is at least one selected from the following formulas (III-1) and (III-2); (X ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; X ² represents a single bond or (CH) ₂ ) _b - (b is an integer from 1 to 15); X ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- Or -OCO-; X ⁴ represents a bivalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom of the cyclic group may be a C 1 to 3 alkane a group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and further, X ⁴ may have a cholesterol skeleton a divalent organic group selected from the organic group having 17 to 51 carbon atoms; X ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, and any of the cyclic groups The hydrogen atom may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Substituted; n represents an integer from 0 to 4; X ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a carbon number of 1 to 18 Fluoroalkoxy) -X ⁷ -X ⁸ [III-2] (X ⁷ represents a single bond, -O-, -CH ₂ O-, - CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO-; X ⁸ represents an alkyl group having 8 to 22 carbon atoms or a carbon number of 6 to 18 Fluorinated alkyl). The liquid crystal alignment agent of claim 1, wherein the polymer is still It has a side chain containing a photoreactive group in the structure. The liquid crystal alignment agent of claim 8, wherein the side chain containing a photoreactive group in the structure is represented by the following (IV) or (V); -R ⁸ -R ⁹ -R ¹⁰ [IV ] (R ⁸ represents a single _{bond, -CH 2 -, - O -} , - COO -, - OCO -, - NHCO -, - CONH -, - NH -, - CH 2 O -, - N (CH 3) - , -CON(CH ₃ )-, or -N(CH ₃ )CO-; R ⁹ represents a single bond, a C 1~20 alkyl group which may be substituted by a fluorine atom, and an alkyl group -CH ₂ - It may be optionally substituted by -CF ₂ - or -CH=CH-. When any of the following groups is not adjacent, it may be substituted by these groups; -O-, -COO-, -OCO- , -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring or a heterocyclic ring; R ¹⁰ represents a photoreactive group selected by the following formula) _{-Y 1 -Y 2 -Y 3 -Y 4} -Y 5 -Y 6 [V] (Y 1 represents _{-CH 2 -, - O -,} - CONH -, - NHCO -, - COO -, - OCO-, -NH-, or -CO-; Y ₂ is an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring, and 1 or a plurality of alkylene groups, divalent carbocyclic rings or heterocyclic rings. a hydrogen atom, which may be substituted by a fluorine atom or an organic group; Y ₂ , when the following groups are not adjacent, -CH ₂ - may be substituted by the groups; -O-, -NHCO- , -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-; Y ₃ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, - OCO-, -NH-, -CO-, or a single bond; Y ₄ represents cinnamoyl; Y ₅ is a single bond, a C 1~30 alkyl group, a divalent carbocyclic ring or a heterocyclic ring, One or more hydrogen atoms of the alkylene group, the divalent carbocyclic ring or the heterocyclic ring may be substituted by a fluorine atom or an organic group; and Y ₅ , when the following groups are not adjacent, - CH ₂ - may be substituted by such groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-; Y ₆ represents an acrylic group or a photopolymerizable group based on methacrylic acid). The liquid crystal alignment agent of claim 1, wherein the polymer is a polyimine precursor having a diamine component represented by the following formula (VI) as a structural unit and is obtained by imidization At least one polymer of the polyimine; The definition of the symbol in the formula is the same as the above formula (I). The liquid crystal alignment agent of claim 10, wherein the polymer further contains a polyimine precursor having a diamine component having a diamine represented by the following formula (VII) as a structural unit, and a ruthenium imine At least one polymer of the obtained polyimine; (X represents a structure of the following formula [III-1] or formula [III-2], and n represents an integer of 1 to 4); (X ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; X ² represents a single bond or (CH) ₂ ) _b - (b is an integer from 1 to 15); X ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- Or -OCO-; X ⁴ represents a bivalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom of the cyclic group may be a C 1 to 3 alkane a group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and further, X ⁴ may have a cholesterol skeleton a divalent organic group selected from the organic group having 17 to 51 carbon atoms; X ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a hetero ring, and any of the cyclic groups The hydrogen atom may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Substituted; n represents an integer from 0 to 4; X ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a carbon number of 1 to 18 the fluorine-containing ^{group); -X 7 -X 8 [III} -2] (X 7 represents a single bond, -O -, - CH ₂ O- -CONH -, - NHCO -, - CON (CH 3) -, - N (CH 3) CO -, - COO- or -OCO-; X ⁸ represents alkyl having 8 to 22 carbon atoms or 6 to 18 of Fluoroalkyl group). The liquid crystal alignment agent of claim 10, wherein the polymer further contains a polyimine precursor having a diamine component having a diamine represented by the following formula (VIII) or (IX) as a structural unit and At least one polymer of the polyimine obtained by imidization of hydrazine; (R ⁸ represents a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-; R ⁹ represents a single bond, a C 1~20 alkyl group which may be substituted by a fluorine atom, and an alkyl group -CH ₂ - Any substitution of -CF ₂ - or -CH=CH-, if any of the following groups are not adjacent, may also be substituted by the groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring or a heterocyclic ring; R ¹⁰ represents a photoreactive group selected by the following formula ); (Y ₁ represents _{-CH 2 -, - O -,} - CONH -, - NHCO -, - COO -, - OCO -, - NH-, or -CO-; Y ₂ is an alkylene group having a carbon number of 1 to 30 a divalent carbocyclic ring or a heterocyclic ring, wherein one or more hydrogen atoms of the alkylene group, the divalent carbocyclic ring or the heterocyclic ring may be substituted by a fluorine atom or an organic group; Y ₂ , in the following group -CH ₂ - may be substituted by these groups when not adjacent; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-; Y ₃ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, or a single bond; Y ₄ represents cinnamyl thiol (cinnamoyl); Y ₅ is a single bond, a C 1~30 alkyl group, a divalent carbocyclic ring or a heterocyclic ring, and 1 or a plurality of hydrogens of an alkyl group, a divalent carbocyclic ring or a heterocyclic ring. An atom, which may be substituted by a fluorine atom or an organic group; Y ₅ , where the following group is not adjacent, -CH ₂ - may be substituted by the group; -O-, -NHCO-, - CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-; Y ₆ represents a photopolymerizable group of an acryl group or a methacryl group. The liquid crystal alignment agent of claim 10, wherein the diamine represented by the formula (IV) is 10 mol% to 80 mol% of the total diamine component; -R ⁸ -R ⁹ -R ¹⁰ [IV] (R ⁸ represents a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-; R ⁹ represents a single bond, a C 1~20 alkyl group which may be substituted by a fluorine atom, and an alkyl group -CH ₂ - Any substitution of -CF ₂ - or -CH=CH-, if any of the following groups are not adjacent, may also be substituted by the groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring or a heterocyclic ring; R ¹⁰ represents a photoreactive group selected by the following formula) The liquid crystal alignment agent according to any one of Claims 1 to 13, which is used in a liquid crystal and/or a liquid crystal alignment film containing a polymerizable compound The material is obtained by reacting the polymerizable compound with ultraviolet rays at an applied voltage to obtain a liquid crystal display element. A liquid crystal alignment film characterized by being obtained from the liquid crystal alignment agent of any one of claim 1 to claim 14. A liquid crystal display element comprising the liquid crystal alignment film of claim 15. The liquid crystal display element of claim 16, wherein the liquid crystal display element is obtained by reacting the polymerizable compound by ultraviolet irradiation under an applied voltage. a polymer characterized by comprising at least one of a polyimine precursor having a side chain structure represented by the following formula (II) and a polyimine obtained by hydrazine imidization; The dots represent the bonds with the polymer backbone, n is an integer selected from 1 to 12, and X represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH- , -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-; Cy represents at least 1 having a carbonyl carbon bond necessarily bound to a quinone imine group More than one unsaturated bond of a cyclic hydrocarbon group having 5 to 14 carbon atoms, a part of a carbon atom constituting the cyclic hydrocarbon may be substituted by a hetero atom. a diamine characterized by being represented by the following formula;