TW201512158A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Provided is a liquid crystal alignment agent capable of forming a liquid crystal alignment film with which adhesive properties between a sealant and the liquid crystal alignment film can be improved, the occurrence of display unevenness in the vicinity of a frame of an element can be inhibited, even under high-temperature/high-humidity conditions, and a reduction in voltage retention rate can be inhibited. This liquid crystal alignment agent includes: (A) a component including a compound represented by formula [1] (in formula [1]: X1 represents either a divalent organic group having a C1-20 aliphatic hydrocarbon group, or a C6-24 divalent organic group having a benzene ring or a cyclohexane ring; and X2 is selected from formulae [1-1] to [1-5]) (in formula [1-3], W1 represents hydrogen or a benzene ring); and (B) a component including at least one polymer selected from the group consisting of polyimide precursors and polyimides obtained by causing a reaction between a diamine component and a tetracarboxylic acid component.

Description

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

The present invention relates to a liquid crystal alignment treatment agent used for the production of a liquid crystal display element, a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.

A film made of an organic material such as a polymer material is widely used as an interlayer insulating film, a protective film, or the like in the field of electronic devices, focusing on ease of formation, insulating properties, and the like. Among them, in the liquid crystal display device which is widely known as a display device, an organic film composed of polyimine is used as a liquid crystal alignment film.

The liquid crystal alignment film is used by the user for the purpose of controlling the alignment state of the liquid crystal. Recently, with the high definition of the liquid crystal display element, it is required to suppress the contrast reduction of the liquid crystal display element or the display failure caused by long-term use.

In the case of using a polyimine as a liquid crystal alignment film, a liquid crystal alignment film formed using a liquid crystal alignment treatment agent to which an alkoxysilane compound is added has been proposed as a liquid crystal alignment property to improve liquid crystal alignment. The display screen is not easy to display poorly in the peripheral part of the screen. (For example, refer to Patent Document 1 or 2).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 61-171762

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-119226

In recent years, liquid crystal display elements have been used for mobile applications such as smart phones and mobile phones. In such applications, in order to ensure a large number of display surfaces, it is necessary to use a sealant width between substrates which are followed by liquid crystal display elements to be narrower than in the past. Further, for the above reason, it is also required that the drawing position of the sealant is at a position in contact with the end portion of the liquid crystal alignment film which is weak in adhesion to the sealant or at the upper portion of the liquid crystal alignment film. In such a case, water is easily mixed into the liquid crystal display element between the sealant and the liquid crystal alignment film due to use under high temperature and high humidity conditions, and display unevenness occurs in the vicinity of the frame edge of the liquid crystal display element.

Further, when water is mixed into the liquid crystal display element, the voltage holding ratio, which is one of the electrical characteristics of the liquid crystal display element, is greatly lowered, and one of the display defects of the liquid crystal display element, that is, the afterimage defect (also referred to as line residual image) is likely to occur. A liquid crystal display element with high reliability cannot be obtained.

Therefore, the object of the present invention is to provide a combination of the above characteristics, which can improve the adhesion between the sealant and the liquid crystal alignment film at a high temperature. In the high-humidity condition, the liquid crystal alignment treatment agent of the liquid crystal alignment film and the liquid crystal display element having the liquid crystal alignment film which suppress the occurrence of display unevenness in the vicinity of the frame edge of the liquid crystal display element and suppress the decrease in the voltage holding ratio can be suppressed.

As a result of intensive studies, the present inventors have found that a liquid crystal alignment treatment agent containing a compound having a specific structure and at least one polymer selected from the group consisting of a polyimide and a polyimide is used. It is extremely effective in terms of purpose, and the present invention has been completed.

That is, the present invention has the following gist.

(1) A liquid crystal alignment treatment agent comprising the following components (A) and (B).

Component (A): a compound represented by the following formula [1].

Component (B): at least one polymer selected from the group consisting of a polyimide precursor obtained by reacting a diamine component with a tetracarboxylic acid component and a polyimine.

(X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent organic group having a carbon number of 6 to 24 having a benzene ring or a cyclohexane ring, and X ² represents a formula [1] -1]~ The structure selected in the formula [1-5]).

(W ¹ represents a hydrogen atom or a benzene ring).

(2) The liquid crystal alignment treatment agent according to the above (1), wherein X ^{1 of the} above formula [1] is an alkylene group having 1 to 10 carbon atoms.

(3) The liquid crystal alignment treatment agent according to (1) or (2) above, wherein X ^{2 of the} above formula [1] is a formula [1-1], a formula [1-2], and a formula [1-4] The structure selected in the middle.

(4) The liquid crystal alignment treatment agent according to any one of the above (1), wherein the diamine component in the polymer of the component (B) contains at least one of the following formulas [2] A diamine compound of the structure shown.

(Y represents a substituent of a structure selected from the following formula [2-1] to formula [2-6], and m represents an integer of 1 to 4).

(a represents an integer from 0 to 4, and b represents an integer from 0 to 4.

Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or OCO-, and Y ² represents a single bond or -(CH _{2 b} - (b is an integer from 1 to 15), Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton, and any of the above cyclic groups The hydrogen atom may also 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 Substituted with a fluorine atom, Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may also 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, n is an integer of 0 to 4, and Y ^{6 is} represented by 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 fluorine-containing alkoxy group having 1 to 18 carbon atoms, and Y ⁷ represents -O- _{, -CH 2 O -, - COO} -, - OCO -, - CONH- or -NHCO-, Y ⁸ is a C Alkyl group of 8 to 22.

Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms.

(5) The liquid crystal alignment treatment agent according to any one of the above (1), wherein the tetracarboxylic acid component in the polymer of the component (B) contains the following formula [3]. Compound.

(Z ¹ is a group of a structure selected from the following formula [3a] to formula [3j]).

(Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different, and Z ⁶ and Z ^{7 each} represent a hydrogen atom or a methyl group, and each may be the same or different).

(6) The liquid crystal alignment treatment agent according to any one of (1) to (5), wherein the polymer of the component (B) is a polyimine obtained by dehydrating a polyamic acid.

The liquid crystal alignment treatment agent according to any one of the above (1), wherein the component (A) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (B).

(8) A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of the above (1) to (7).

(9) A liquid crystal alignment film obtained by an inkjet method using the liquid crystal alignment treatment agent according to any one of the above (1) to (7).

(10) A liquid crystal display element comprising the liquid crystal alignment film of (8) or (9) above.

(11) The liquid crystal alignment film according to (8) or (9) above, wherein the liquid crystal layer is provided between the pair of substrates, and the active energy ray and the heat are disposed between the pair of substrates. A liquid crystal display device produced by polymerizing a polymerizable compound while applying a voltage between the electrodes is used for a liquid crystal display device produced by polymerizing the polymerizable compound.

(12) A liquid crystal display element comprising the liquid crystal alignment film of (11) above.

(13) The liquid crystal alignment film according to (8) or (9) above, wherein the liquid crystal layer is provided between the pair of substrates, and the active energy ray and the heat are disposed between the pair of substrates. A liquid crystal alignment element in which a polymerizable group is polymerized, and a liquid crystal display element produced by polymerizing the polymerizable group while applying a voltage between the electrodes is used.

(14) A liquid crystal display element comprising the liquid crystal alignment film of (13) above.

According to the present invention, a liquid crystal alignment treatment agent containing a compound having a specific structure and at least one polymer selected from the group consisting of a polyimide precursor and a polyimine can form a sealant and a liquid crystal alignment. In addition to the high-temperature and high-humidity conditions, it is possible to suppress the occurrence of display unevenness in the vicinity of the frame edge of the liquid crystal display element and suppress the decrease in the voltage holding ratio of the liquid crystal alignment film. In other words, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is excellent in reliability and can be suitably used for a large-screen and high-definition liquid crystal television.

The present invention relates to a liquid crystal alignment treatment agent containing the following components (A) and (B), a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.

(A) component: a compound (also referred to as a specific compound) represented by the following formula [1].

Component (B): at least one polymer (also referred to as a specific polymer) selected from the group consisting of a polyimide precursor obtained by reacting a diamine component with a tetracarboxylic acid component and a polyimine.

(X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent organic group having a carbon number of 6 to 24 having a benzene ring or a cyclohexane ring, and X ² represents a formula [1] -1]~ The structure selected in the formula [1-5]).

(W ¹ represents a hydrogen atom or a benzene ring).

In the liquid crystal alignment treatment agent of the present invention, the O=C=N- group (also referred to as an isocyanate group) in the specific compound is considered to be heated by the production of the liquid crystal alignment treatment agent or when the liquid crystal alignment film is produced. In the step, it is chemically bonded to the carboxyl group in the specific polymer. Therefore, the liquid crystal alignment agent of the present invention is considered to be efficiently bonded to a specific compound and a specific polymer in a liquid crystal alignment film obtained by a simple means of mixing only in an organic solvent.

Further, the double bond portion of the formula [1-1] to the formula [1-5] of X ² in the specific compound is known to be reacted by heat or ultraviolet irradiation. Further, these double bond sites are also those contained in the compound contained in the sealant.

Therefore, when the liquid crystal alignment agent of the present invention is used, the hardening step of the sealant when the liquid crystal display element is produced, that is, the ultraviolet irradiation step or the baking step, the double bond portion in the liquid crystal alignment film and the sealant The compound undergoes a chemical reaction, and the sealant and the liquid crystal alignment film are chemically bonded to improve the adhesion.

From the above viewpoints, it is understood that the liquid crystal alignment treatment agent containing the specific compound of the present invention and the specific polymer has high adhesion to the sealant, and can be formed to suppress the frame edge of the liquid crystal display element even under high temperature and high humidity conditions. A liquid crystal alignment film which exhibits unevenness in display and suppresses a decrease in voltage holding ratio.

<specific compound>

The specific compound of the present invention is a compound represented by the following formula [1].

(X ¹ and X ² have the same meanings as defined above, and X ² represents a structure selected from the following formulas [1-1] to [1-5]).

(W ¹ represents a hydrogen atom or a benzene ring).

In the formula [1], X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent organic group having a carbon number of 6 to 24 having a benzene ring or a cyclohexane ring. Among them, from the viewpoint of availability and production of the compound, an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 5 carbon atoms is more preferable.

In the formula [1], X ² is a structure selected from the formula [1-1] to the formula [1-5].

In the formula [1-3], W ₁ represents a hydrogen atom or a benzene ring. Among them, a hydrogen atom is preferred.

In the formula [1], X ^{2 is} preferably a structure represented by the formula [1-1], the formula [1-2] or the formula [1-4] from the viewpoint of reactivity by heat or ultraviolet irradiation.

More specifically, the structure represented by the following formula [1a] - formula [1d] is mentioned.

(X ³ represents an alkylene group having a carbon number of 1 to 5, a benzene ring or a cyclohexane ring, and X ⁴ represents an alkylene group having a carbon number of 1 to 5, a benzene ring or a cyclohexane ring).

(X ⁵ represents an alkylene group having a carbon number of 1 to 5, a benzene ring or a cyclohexane ring, and X ⁶ represents an alkylene group having a carbon number of 1 to 5, a benzene ring or a cyclohexane ring).

<specific polymer>

The specific polymer of the component (B) of the present invention is at least one polymer selected from the group consisting of a polyimide precursor obtained by reacting a diamine component with a tetracarboxylic acid component and a polyimine.

The polyimine precursor is a structure represented by the following formula [A].

(R ¹ is a tetravalent organic group, R ² is a divalent organic group, and A ¹ and A ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, each of which may be the same or different, and A ³ and A ⁴ represent a hydrogen atom. The alkyl group or the ethyl group having 1 to 5 carbon atoms may be the same or different, and n represents a positive integer).

The diamine component is a diamine compound having two primary or secondary amine groups in the molecule, and examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, and a dihalogenated tetracarboxylic acid compound. a dicarboxylic acid dialkyl ester compound or a dihalogenated tetracarboxylic acid dialkyl ester compound.

The specific polymer is preferably used as a raw material by using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] as a raw material. The polyaminic acid constituted by the structural formula of the repeating unit represented by the formula [D] or the polyimine obtained by imidating the polyphosphonium amide.

(R ¹ and R ² are the same meanings as defined in the formula [A]).

(R ¹ and R ² are the same meanings as defined in the formula [A]).

Further, an alkyl group having 1 to 8 carbon atoms of A ¹ and A ² represented by the formula [A] and a formula [A] can be introduced into the polymer of the formula [D] obtained above by a usual synthesis method. The alkyl groups of the A ³ and A ^{4 having} a carbon number of 1 to 5 are shown or an ethylene group.

<Diamine component>

As the diamine component for producing the specific polymer of the component (B), a well-known diamine compound can be used.

In particular, at least one or more kinds of diamine compounds (also referred to as specific diamine compounds) having a structure represented by the following formula [2] are preferably used.

(Y represents a substituent of a structure selected from the following formula [2-1] to formula [2-6], and m represents an integer of 1 to 4).

In the formula [2-1], a represents an integer of 0 to 4. Among them, in particular, from the viewpoint of availability of raw materials or ease of synthesis, it is preferably 0 or 1.

In the formula [2-2], b represents an integer of 0 to 4. Among them, in particular, from the viewpoint of availability of raw materials or ease of synthesis, an integer of 0 or 1 is preferable.

In the formula [2-3], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. In particular, from the viewpoint of availability of raw materials or ease of synthesis, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO-. More preferably, it is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or COO-.

In the formula [2-3], Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) is preferred.

In the formula [2-3], Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable from the viewpoint of easiness of synthesis. More preferably a single _{bond, - (CH 2) c -} (c is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

In the formula [2-3], Y ^{4 is a} divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may also have a carbon number of 1 to 3 The alkyl group, the alkoxy group having 1 to 3 carbon atoms, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom are substituted. Further, Y ⁴ may be a divalent organic group selected from an organic group having a carbon number of 12 to 25 having a steroid skeleton. Among them, in particular, from the viewpoint of easiness of synthesis, an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferred.

In the formula [2-3], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may also have a carbon number of 1 to 3 The alkyl group, the alkoxy group having 1 to 3 carbon atoms, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom are substituted. Among them, a benzene ring or a cyclohexane ring is preferred.

In the formula [2-3], n represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials or ease of synthesis, it is preferably from 0 to 3. More preferably 0~2.

In the formula [2-3], Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine having 1 to 18 carbon atoms. Alkoxy group. Among them, an alkyl group having 1 to 18 carbon atoms, an 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.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2-3] for constituting the substituent Y in the formula [2] are exemplified by international The same combination of (2-1) to (2-629) disclosed in Tables 6 to 47 of pages 13 to 34 of the publication WO 2011/132751 (published on 2011.10.27). Further, Y1 to Y6 in the tables of the International Publications correspond to Y ¹ to Y ^{6 of the} present invention.

In the formula [2-4], Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-. Among them, -O-, -CH ₂ O-, -COO- or -CONH- is preferred. More preferably -O-, -COO- or -CONH-.

In the formula [2-4], Y ⁸ represents an alkyl group having 8 to 22 carbon atoms.

In the formula [2-5], Y ⁹ and Y ^{10 each} independently represent a hydrocarbon group having 1 to 12 carbon atoms.

In the formula [2-6], Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms.

The method for producing the specific diamine compound represented by the formula [2] is not particularly limited, and preferred examples thereof include those shown below.

As an example, the specific diamine compound represented by the formula [2] can be obtained by synthesizing a dinitro compound represented by the following formula [2-A] and further reducing the nitro group to convert it into an amine group.

(Y represents a substituent of the structure selected from the above formula [2-1] to formula [2-6], and m represents an integer of 1 to 4).

The method for reducing the dinitro group of the dinitro compound represented by the formula [2-A] is not particularly limited, and is usually carried out in ethyl acetate or toluene. Examples of a solvent such as tetrahydrofuran, dioxane or an alcohol solvent include palladium-carbon, platinum oxide, Raney nickel, platinum black, lanthanum-alumina, and platinum sulfide carbon as catalysts in hydrogen and helium. Or a method of reacting under hydrogen chloride.

Although the specific structure of the specific diamine compound represented by the formula [2] is shown below, it is not limited to these examples.

Specific diamine compounds may, for example, be 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,4-Diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, Further, a diamine compound having the structure represented by the following formulas [2-7] to [2-47] may be mentioned.

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

(R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and R ² represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, and a fluorine-containing alkane Base or alkoxy group containing fluorine).

(R ³ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or -CH ₂ -, and R ⁴ represents an alkyl group having 1 to 22 carbon atoms , alkoxy, alkyl containing fluorine or alkoxy containing fluorine).

(R ⁵ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ - or -O-, R ⁶ is a fluorine group, cyanide Base, trifluoromethyl, nitro, azo, formyl, ethyl, ethoxy or hydroxy).

(R ⁷ represents an alkyl group having 3 to 12 carbon atoms. Further, the cis-trans isomerism of 1,4-cyclohexylene group is preferably a trans isomer).

(R ⁸ represents an alkyl group having 3 to 12 carbon atoms. Further, the cis-trans isomerism of 1,4-cyclohexylene group is preferably a trans isomer).

(B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, B ³ represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and B ² represents an oxygen atom or -COO-* (only , the bonding position with "*" is bonded to B ³ ), and B ¹ represents an oxygen atom or -COO-* (only, the bonding position with "*" is bonded to (CH ₂ )a ² Further, a ¹ represents an integer of 0 or 1, a ² represents an integer of 2 to 10, and a ³ represents an integer of 0 or 1.

In the specific diamine compound represented by the above formula [2], a liquid crystal alignment treatment agent obtained from a specific polymer is used to form a liquid crystal alignment film, and the substituent Y in the formula [2] is used as the specific polymer. [2-3] shown In the case of the diamine compound of the structure, the pretilt angle of the liquid crystal can be increased. When the pretilt angle is to be increased, in the above diamine compound, a diamine compound represented by the formula [2-25] to the formula [2-40] or the formula [2-43] to the formula [2-47] is used. Preferably. More preferably, it is a diamine compound represented by the formula [2-29] to the formula [2-40] or the formula [2-43] to the formula [2-47].

The amount of the diamine compound for increasing the pretilt angle is preferably 5 mol% or more and 80 mol% or less of the entire diamine component. From the viewpoint of the coatability of the liquid crystal alignment agent or the electrical characteristics of the liquid crystal alignment film, it is more preferably 5 mol% or more and 60 mol% of the entire diamine component.

The specific diamine compound represented by the formula [2] can be mixed according to the solubility or coating property of the specific polymer to the solvent, the alignment property of the liquid crystal when the liquid crystal alignment film is used, the voltage retention ratio, and the storage charge. Use two or more types.

As the diamine component for producing a specific polymer, a diamine compound (also referred to as another diamine compound) other than the specific diamine compound represented by the formula [2] can be used as the diamine component. Specific examples of other diamine compounds are listed below, but are not limited thereto.

For example, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3 , 3'-dimethoxy-4,4'-diaminobiphenyl, 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'-diaminodiphenyl Alkane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodi Phenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether , 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-double (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'-diaminodiyl) Phenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diamine Naphthalene, 2,2'-diaminobenzophenone, 2,3'-di Benzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene , 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-double (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-aminobenzene) Oxy)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-phenylene bis(methylene) )]Diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine , 3,4'-[1,3-stretch Phenyl bis(methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3'-[1,3-phenylene bis( Methylene)]diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylphenylbis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene double (4-Aminobenzoic acid ester), 1,4-phenylphenylbis(3-aminobenzoate), 1,3-phenylphenylbis(4-aminobenzoate), 1 , 3-phenylphenyl bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, Bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4- Aminobenzylamine, N,N'-(1,3-phenylene)bis(4-aminobenzylamine), N,N'-(1,4-phenylene)bis(3- Aminobenzylamine, N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)-p-xylylene Indoleamine, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)m-xylyleneamine, N,N'- Bis(3-aminophenyl)m-xylamine 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminobenzene) Oxy)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 -aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 1,3-double (4-Aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-double ( 3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-double (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)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4- Aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-amine Phenoxy group) undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane, bis(4-amino ring Hexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1 ,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1 , 11-diaminoundecane or 1,12-diaminododecane, and the like.

Further, examples of the other diamine compound include an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring in the side chain of the diamine, and further, a macrocyclic ring having such a group Shape substitutes, etc. Specifically, a diamine compound represented by the following formula [DA1] to [DA7] can be exemplified.

(A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, and A ² represents a linear chain having a carbon number of 1 to 22 or A branched alkyl group or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(p represents an integer from 1 to 10).

As long as the effects of the present invention are not impaired, a diamine compound represented by the following formula [DA8] to formula [DA13] can be used as the other diamine compound.

(m represents an integer from 0 to 3, and n represents an integer from 1 to 5).

Further, as long as the effects of the present invention are not impaired, a diamine compound represented by the following formula [DA14] to formula [DA17] can also be used.

(A ¹ represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N ( CH ₃ )CO-, m ¹ and m ² each represent an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4, and in the formula [DA15], m ³ and m ⁴ represent an integer of 1 to 5, respectively. In the formula [DA16], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, m ⁵ represents an integer of 1 to 5, and A ³ represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO- , -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-, m ⁶ represents an integer from 1 to 4).

Further, a diamine compound represented by the following formula [DA18] and formula [DA19] can also be used as the other diamine compound.

Further, as long as the effects of the present invention are not impaired, a diamine compound represented by the following formula [DA20] can also be used.

(A ¹ represents -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )-, and -N ( CH ₃ ) CO-selected divalent organic group, A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, and A ³ is a single bond, -O- , -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, and -O(CH ₂ ) _m - (m is an integer of 1 to 5), and A ⁴ is an aromatic heterocyclic ring containing nitrogen, and n is an integer of 1 to 4).

The other diamine compound described above may also be used as a liquid crystal according to the solubility of a specific polymer to a solvent or the coating property of a liquid crystal alignment treatment agent. In the case of the alignment film, the properties of the liquid crystal alignment, the voltage holding ratio, and the storage charge are used in combination of one or two or more kinds.

<tetracarboxylic acid component>

The tetracarboxylic acid component of the specific polymer for producing the component (B) of the present invention is preferably a tetracarboxylic dianhydride represented by the following formula [3] or a tetracarboxylic acid of the tetracarboxylic acid derivative. A dihalogenated tetracarboxylic acid compound, a tetracarboxylic acid dialkyl ester compound or a dihalogenated tetracarboxylic acid dialkyl ester compound (all also collectively referred to as a specific tetracarboxylic acid component).

In the formula [3], Z ¹ is a group of a structure selected from the following formulas [3a] to [3j].

In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different.

In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and each may be the same or different.

In the structure represented by the formula [3] of the specific tetracarboxylic acid component, Z ^{1 is} preferably a formula [3a] or a formula in terms of easiness of synthesis or ease of polymerization reactivity in producing a polymer. [3c], a structure represented by the formula [3d], the formula [3e], the formula [3f] or the formula [3g]. More preferably, it is a structure represented by the formula [3a], the formula [3e], the formula [3f] or the formula [3g], and particularly preferably the formula [3e], the formula [3f] or the formula [3g].

The specific tetracarboxylic acid component is preferably at least 1 mol% of the total tetracarboxylic acid component. More preferably, it is 5 mol% or more, and particularly preferably 10 mol% or more. Among them, 15% to 100% by mole is preferred.

Further, when a specific tetracarboxylic acid component having the structure of the formula [3e], the formula [3f] or the formula [3g] is used, the amount thereof to be used is preferably 20 mol% or more of the entire tetracarboxylic acid component. More preferably 30% by mole or more. Further, all of the tetracarboxylic acid components may be a tetracarboxylic acid component of the formula [3e], the formula [3f] or the formula [3g].

In the specific polymer, other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used as long as the effects of the present invention are not impaired.

Examples of the other tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a dihalogenated tetracarboxylic acid compound, a dicarboxylic acid dialkyl ester compound, or a dihalogenated tetracarboxylic acid dialkyl ester compound.

That is, as other tetracarboxylic acid components, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8 may be mentioned. -naphthalene tetracarboxylate 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-dicarboxyl Phenyl) hydrazine, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro- 2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2 ,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4 , 9,10-nonanetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

The specific tetracarboxylic acid component and the other tetracarboxylic acid component may also have solubility in a solvent or a coating property of a liquid crystal alignment agent according to the present invention, alignment of a liquid crystal as a liquid crystal alignment film, and voltage retention. The characteristics such as the rate and the stored charge are used in combination of one type or two types.

<Method of Manufacturing Specific Polymer>

The method of synthesizing a specific polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component composed of one or more kinds of diamine compounds to obtain a polydecylamine. acid. Specifically, there are methods as follows.

(1) A method of obtaining polyphosphamic acid by polycondensing a tetracarboxylic dianhydride with a diamine compound of a first or second stage.

(2) A method in which a tetracarboxylic acid is subjected to a dehydration-polycondensation reaction with a first- or second-order diamine compound to obtain a poly-proline.

(3) A method of obtaining polyphosphoric acid by polycondensing a dihalogenated tetracarboxylic acid with a diamine compound of a first or second stage.

In order to obtain an alkyl amide, a method of polycondensing a tetracarboxylic acid obtained by esterifying a carboxylic acid dialkyl with a diamine compound of a grade 1 or a second is used to esterify a carboxylic acid dialkylate. Further, a method of polycondensing a dihalogenated tetracarboxylic acid with a diamine compound of a 1st or 2nd stage or a method of converting a carboxyl group of a polylysine into an ester.

In order to obtain a polyimine, a method of obtaining a polyimine by ring-closing the polyamic acid or polyalkyl amide is used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent containing a diamine component and a tetracarboxylic acid component. The organic solvent to be used at this time is not particularly limited as long as it dissolves the produced polyimide precursor. Although specific examples of the organic solvent used for the reaction are listed below, the examples are not limited thereto.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethyl group can be mentioned. Ethylamine, dimethyl hydrazine or 1,3-dimethyl-tetrahydroimidazolidone.

Further, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following may be used. A solvent represented by the formula [D-1] to the formula [D-3].

(D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² represents an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms).

These may be used alone or in combination. Further, even if it is a solvent which does not dissolve the polyimide precursor, it may be used in the above solvent in the range in which the produced polyimide precursor is not precipitated. Further, the water in the organic solvent hinders the polymerization reaction and further causes the produced polyimide precursor to be hydrolyzed. Therefore, the organic solvent is preferably a dehydrated dryer.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, for example, the following methods can be used, and all methods can be used.

(1) A method in which a solution obtained by dispersing or dissolving a diamine component in an organic solvent is stirred, and the tetracarboxylic acid component is directly or dispersed or dissolved in an organic solvent.

(2) Conversely, a method of adding a diamine component to a solution in which an tetracarboxylic acid component is dispersed or dissolved in an organic solvent.

(3) A method of mutually adding a diamine component and a tetracarboxylic acid component.

Further, when a plurality of kinds of diamine components or tetracarboxylic acid components are used for the reaction, respectively, the reaction can be carried out in a state of being mixed in advance, or the reaction can be carried out individually or in combination, and the low-molecular weight of the individual reaction can be mixed. As a polymer. The polymerization temperature at this time can be selected from -20 to 150 ° C. Any temperature is preferably in the range of -5 to 100 °C. Further, the reaction can be carried out at any concentration. However, when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction liquid becomes too high, and it is difficult to uniformly stir. Therefore, it is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then an organic solvent is added.

In the polymerization reaction of the polyimine precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably from 0.8 to 1.2. As with the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimine precursor.

The polyimine of the present invention is a polyimine obtained by ring-closing the polyimine precursor, and a ring closure ratio of the proline group (also referred to as a ruthenium amide ratio) in the polyimide. It does not have to be 100%, and can be adjusted arbitrarily according to the purpose or purpose.

The method for imidating the polyimine precursor ruthenium may include a hydrazine imidization in which the solution of the polyimide precursor is directly heated or a catalyst in which a catalyst is added to the solution of the polyimide precursor.醯imination.

The temperature at which the polyimide precursor is thermally imidated in the solution is 100 to 400 ° C, preferably 120 to 250 ° C, preferably to remove water formed by the imidization reaction. The outside of the system is carried out.

The ruthenium imide of the polyimide precursor can be stirred at -20 to 250 ° C, preferably 0 to 180 ° C by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor. Come on. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3, of the proline group. ~30 mole Times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has an appropriate basicity for allowing the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, in particular, when acetic anhydride is used, purification after completion of the reaction becomes easy, which is preferable. The imidization rate of the imidization of the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, the reaction solution is poured into a solvent to precipitate. Examples of the solvent used for the precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl celecoxib, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. The polymer which is charged and precipitated can be recovered by filtration, and dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the polymer recovered by precipitation is redissolved in an organic solvent, and the operation of reprecipitation recovery is repeated 2 to 10 times to reduce impurities in the polymer. In the case of the solvent, for example, an alcohol, a ketone or a hydrocarbon may be used. When three or more solvents selected in the above are used, the efficiency of purification can be further improved, which is preferable.

When the molecular weight of the specific polymer is considered in consideration of the strength of the liquid crystal alignment film obtained, the workability at the time of formation of the liquid crystal alignment film, and the coating film property, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 5,000. ~1,000,000; more preferably 10,000~150,000.

<Liquid alignment treatment agent>

The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and is used to form a coating solution of a liquid crystal alignment film containing a specific compound, a specific polymer, and a solvent.

The content of the specific compound in the liquid crystal alignment agent is 0.1 to 30 parts by mass based on 100 parts by mass of the specific polymer. Among them, 0.5 to 30 parts by mass is preferred, and particularly preferably 1 to 20 parts by mass.

All of the polymer components in the liquid crystal alignment agent may be all of the specific polymers of the present invention, or may be mixed with other polymers. In this case, the content of the polymer other than the polymer is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the specific polymer of the present invention. The polymer other than the above may be a polyimine-based polymer which does not use the diamine compound represented by the above formula [2] and a specific tetracarboxylic acid component. Further, examples of the polymer other than the polymer include a cellulose polymer, an acrylic polymer, a methacrylic polymer, polystyrene, polyamine, polyoxyalkylene, and the like.

From the viewpoint of forming a uniform liquid crystal alignment film by coating, the solvent content in the liquid crystal alignment treatment agent is preferably from 70 to 99.9% by mass, more preferably from 80 to 99, in terms of the solvent in the liquid crystal alignment treatment agent. %. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.

The solvent used for the liquid crystal alignment treatment agent is not particularly limited as long as it dissolves a specific compound and a specific polymer solvent (also referred to as a good solvent). Specific examples of the good solvent are listed below, but are not limited thereto.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl hydrazine, γ-butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, methyl ethyl Ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone is particularly preferably used. Further, when the specific compound and the specific polymer have high solubility in a solvent, it is preferred to use a solvent represented by the above formula [D-1] to formula [D-3].

The good solvent in the liquid crystal alignment treatment agent is preferably from 10 to 100% by mass based on the total amount of the solvent contained in the liquid crystal alignment treatment agent. Among them, 20 to 90% by mass is preferred. More preferably 30 to 80% by mass.

In the liquid crystal alignment treatment agent, a solvent (also referred to as a poor solvent) which improves the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used as long as the effect of the present invention is not impaired. Specific examples of the poor solvent are listed below, but are not limited thereto.

For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1 can be cited. -butanol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentyl Alcohol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol , 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butyl Glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2- Ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dibutyl ether, 2- Pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl Acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propyl carbonate, ethyl carbonate, 2-(methoxymethoxy)ethanol , ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, furan methanol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-( Butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene Alcohol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol , triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, pyruvic acid Ethyl ester, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid , 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, the above formula [D -1]~ A solvent such as the formula [D-3].

In particular, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, or the above formula [D-1]~ The solvent represented by the formula [D-3] is preferred.

The poor solvent is preferably from 1 to 70% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, 1 to 60% by mass is preferred. More preferably, it is 5 to 60% by mass.

In the liquid crystal alignment treatment agent, a compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclic carbonate group may be introduced as long as the effect of the present invention is not impaired; and it is selected from a hydroxyl group, a hydroxyalkyl group and a lower stage. A compound having at least one substituent group in a group of alkoxyalkyl groups; and a compound having a polymerizable unsaturated bond (also collectively referred to as a crosslinkable compound). These substituents or polymerizable unsaturated bonds must have two or more of the crosslinkable compounds.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl trimer isocyanate, and tetraglycidyl group. Aminodiphenylene, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl ether, triphenyl Glycidyl etherethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl- 2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl M-xylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxypropane) Oxy)phenyl)ethyl)phenyl)propane, 1,3-bis(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-(4-() 1-(4-(2,3-Epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol and the like.

The crosslinkable compound having an oxetanyl group is a crosslinkable compound having at least two oxetanyl groups represented by the following formula [4].

Specifically, a crosslinkable compound represented by the formula [4a] to the formula [4k] disclosed in pages 58 to 59 of International Publication WO2011/132751 (2011.10.27) is mentioned.

The crosslinkable compound having a cyclic carbonate group is a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [5].

Specifically, a crosslinkable compound represented by the formula [5-1] to the formula [5-42] disclosed in pages 76 to 82 of International Publication WO2012/014898 (published in 2012.2.2) is mentioned.

The crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group may, for example, be an amine-based resin having a hydroxyl group or an alkoxy group, such as a melamine resin, a urea resin, a guanamine resin, or an acetylene. Urea-formaldehyde resin, succinimide-formaldehyde resin, ethylene urea-formaldehyde resin, and the like. Specifically, a melamine derivative or a benzoguanamine derivative in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group or both may be used. Or acetylene urea. The melamine derivative or the benzoguanamine derivative may also exist as a dimer or a trimer. These are preferably those having an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups per one triazine ring.

Examples of such a melamine derivative or a benzoguanamine derivative include a triazine ring per commercially available product, and an average of 3.7 MX-750 substituted by a methoxymethyl group; each triazine ring, The methoxymethyl group is substituted on average by 5.8 MW-30 (manufactured by the above, Sanwa Chemical Co., Ltd.) or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methylated melamine; methoxymethylated butoxymethylated melamine of Cymel 235, 236, 238, 212, 253, 254, etc.; butoxymethylated melamine of Cymel 506, 508, etc.; such as Cymel 1141 a methoxymethylated isobutoxymethylated melamine containing a carboxyl group; a methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123; a methoxy group such as Cymel 1123-10 Butylated oxymethylated benzoguanamine; such as butyloxymethylated benzoguanamine of Cymel 1128; methoxymethylated ethoxylated methylated benzene containing a carboxyl group such as Cymel 1125-80 And guanamine (above, Mitsui Cyanamid company). Further, examples of the acetylene urea include butoxymethylated acetylene urea such as Cymel 1170; methylolated acetylene urea such as Cymel 1172; methoxymethylolated acetylene urea of PowderLink 1174 and the like.

Examples of the benzene having a hydroxyl group or an alkoxy group or a phenolic compound include 1,3,5-glycol (methoxymethyl)benzene and 1,2,4-para(isopropoxymethyl)benzene. 1,4-bis(sec-butoxymethyl)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and the like.

More specifically, a crosslinkable compound represented by the formula [6-1] to the formula [6-48] disclosed in pages 62 to 66 of International Publication WO2011/132751 (2011.10.27 publication) is mentioned.

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tris(A). a cross-linking compound having three polymerizable unsaturated groups in the molecule, such as propylene methoxy ethoxy trimethylolpropane, glycerol polyglycidyl ether poly(meth) acrylate, etc.; (Meth) acrylate, diethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate Ester, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate , propylene oxide bisphenol type di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, glycerol di(meth) acrylate, pentaerythritol di(meth) acrylate, ethylene Alcohol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether di(meth) acrylate, phthalic acid diglycidyl a crosslinkable compound having two polymerizable unsaturated groups in the molecule, such as oleyl ester di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate; (methyl) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, phthalic acid 2-(Methyl)propenyloxy-2-hydroxypropyl ester, 3-chloro-2-hydroxypropyl (meth)acrylate, mono (meth) acrylate, 2-(methyl) propylene phosphate Oxyethyl ester or N-hydroxymethyl (methyl) A crosslinkable compound having one polymerizable unsaturated group in the molecule, such as acrylamide.

Further, a compound represented by the following formula [7] can also be used.

(E ₁ represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring, and a phenanthrene ring, and E ₂ represents The group selected from the following formula [7a] and formula [7b], n represents an integer of 1 to 4).

The compound is an example of a crosslinkable compound, and is not limited thereto. In addition, the crosslinkable compound to be used in the liquid crystal alignment treatment agent of the present invention may be one type or two or more types.

The content of the crosslinkable compound in the liquid crystal alignment agent is preferably 0.1 to 150 parts by mass based on 100 parts by mass of the total polymer component. In order to carry out the crosslinking reaction, the effect of exhibiting the object is preferably from 0.1 to 100 parts by mass, particularly preferably from 1 to 50 parts by mass, per 100 parts by mass of the total polymer component.

The liquid crystal alignment treatment agent can improve the film of the liquid crystal alignment film by applying the liquid crystal alignment treatment agent as long as the effect of the present invention is not impaired. A compound with thick uniformity or surface smoothness.

Examples of the compound which improves the uniformity of the film thickness of the liquid crystal alignment film or the surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant.

More specifically, Eftop EF301, EF303, EF352 (above, Tokem products company); Megafac F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.); Fluorad FC430, FC431 (above, Sumitomo 3M) Company system); Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.

Further, in the liquid crystal alignment treatment agent, a nitrogen-containing heterocyclic ring represented by the formula [M1] to the formula [M156] disclosed in pages 69 to 73 of International Publication WO2011/132751 (2011.10.27 publication) may be added. An amine compound is a compound that promotes charge removal in a liquid crystal alignment film to promote charge removal of an element. The amine compound may be added directly to the liquid crystal alignment treatment agent, and is preferably added in a suitable solvent to a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent to be used is not particularly limited as long as it is an organic solvent which dissolves the above specific polymer.

In the liquid crystal alignment treatment agent, in addition to the above-mentioned poor solvent, a crosslinkable compound, a compound which improves the film thickness uniformity or surface smoothness of the resin film or the liquid crystal alignment film, and a compound which promotes charge removal, A dielectric or a conductive material for the purpose of changing the dielectric properties such as the dielectric constant or the conductivity of the liquid crystal alignment film may be added as long as it does not impair the effects of the present invention.

<Liquid alignment film. Liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film by coating and baking on a substrate, followed by rubbing treatment or alignment treatment such as light irradiation. Further, in the case of vertical alignment use or the like, it can be used as a liquid crystal alignment film without alignment treatment. The substrate to be used in this case is not particularly limited as long as it is a substrate having high transparency, and a glass substrate can be used, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. From the viewpoint of process simplification, it is preferred to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed. Further, in the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as long as it is only a single-sided substrate, and a material such as aluminum that reflects light can be used as the electrode.

The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, generally, screen printing, lithography, flexographic printing, and inkjet printing are used. Other coating methods include a dipping method, a roll coating method, a slit coating method, a spinning method, a spray method, and the like, and these can be used according to the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, it can be heated at 30 to 300 ° C by a heating means such as a hot plate, a heat cycle type oven, or an IR (infrared) type oven in response to the solvent used for the liquid crystal alignment treatment agent. The solvent is evaporated at a temperature of 30 to 250 ° C to become a liquid crystal alignment film. When the thickness of the liquid crystal alignment film after firing is too thick, the power consumption of the liquid crystal display element If the force is unfavorable and the thickness is too thin, the reliability of the liquid crystal display element may be lowered, so that it is preferably 5 to 300 nm, more preferably 10 to 100 nm. When the liquid crystal is aligned horizontally or obliquely, the liquid crystal alignment film after firing is treated by rubbing, polarized ultraviolet irradiation or the like.

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention, and a liquid crystal cell is produced by a known method to obtain a liquid crystal display element.

In the method for producing a liquid crystal cell, for example, a pair of substrates on which a liquid crystal alignment film is formed may be prepared, and a spacer may be disposed on a liquid crystal alignment film of one of the substrates, so that the liquid crystal alignment film surface is inside, and the other is bonded to the other side. The substrate is a method of injecting and sealing a liquid crystal under reduced pressure, or a method of sealing a substrate by dropping a liquid crystal on a liquid crystal alignment film surface on which a spacer is spread, and the like.

Further, the liquid crystal alignment agent of the present invention is preferably used in a liquid crystal display device in which a liquid crystal layer is provided between one of the electrodes and the substrate is disposed between the pair of substrates. A liquid crystal composition of a polymerizable compound polymerized by at least one of an active energy ray and a heat is produced by polymerizing a polymerizable compound by applying a voltage between the electrodes while irradiating and heating the active energy ray. Here, as the active energy ray, ultraviolet rays are suitable. The ultraviolet light has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, ultraviolet rays and heating can be simultaneously performed.

The above liquid crystal display element is represented by PSA (Polymer) Sustained Alignment) to control the pretilt angle of liquid crystal molecules. In the PSA system, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is added to the liquid crystal material, and after the liquid crystal cell is assembled, a photopolymerizable compound is irradiated with ultraviolet rays or the like while a specific voltage is applied to the liquid crystal layer. The pretilt angle of the liquid crystal molecules is controlled by the generated polymer. That is, since the alignment state of the liquid crystal molecules at the time of polymer formation is also stored after the voltage is removed, the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer or the like. Further, in the PSA method, since the rubbing treatment is not required, it is suitable for the formation of a vertical alignment type liquid crystal layer which is difficult to control the pretilt angle by the rubbing treatment.

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from a liquid crystal alignment treatment agent, and a liquid crystal cell is produced, and the polymerizable compound is polymerized by at least one of ultraviolet irradiation and heating. It can control the alignment of liquid crystal molecules.

An example of the production of a liquid crystal cell of the PSA method is to prepare a substrate on which a liquid crystal alignment film is formed, and a spacer is disposed on the liquid crystal alignment film of one of the substrates, so that the liquid crystal alignment film surface is inside, and the other is bonded to the liquid crystal alignment film. One of the substrates, a method of injecting and sealing a liquid crystal under reduced pressure, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface on which a spacer is dispersed, and a substrate is bonded and sealed.

A polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays is mixed in the liquid crystal. The polymerizable compound is a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. At this time, the polymerizable compound is qualitatively related to the liquid crystal component 100. The amount of the component is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize, and the alignment of the liquid crystal cannot be controlled. When the amount is more than 10 parts by mass, the unreacted polymerizable compound increases, and the afterimage characteristics of the liquid crystal display element are lowered.

After the liquid crystal cell is produced, an alternating current or a direct current voltage is applied to the liquid crystal cell, and heat or ultraviolet rays are irradiated to polymerize the polymerizable compound. Thereby, the alignment of the liquid crystal molecules can be controlled.

Further, the liquid crystal alignment agent of the present invention is preferably used in a liquid crystal display device which is formed by providing a liquid crystal layer between one of the electrodes and the pair of substrates. A liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat is produced by applying a voltage between electrodes. Here, as the active energy ray, ultraviolet rays are suitable. As the ultraviolet light, the wavelength is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, ultraviolet rays and heating can be simultaneously performed.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat, a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, or a polymerization property is used. A method based on a polymer component.

Since the liquid crystal alignment treatment agent of the present invention contains a specific compound having a double bond site which is reacted by heat or ultraviolet irradiation, the alignment of the liquid crystal molecules can be controlled by at least one of irradiation and heating of ultraviolet rays.

The production of the liquid crystal cell having the liquid crystal alignment film containing the polymerizable group and the alignment control of the liquid crystal molecules after the production of the liquid crystal cell can be carried out in the same manner as the liquid crystal cell of the PSA method.

A liquid crystal display element having a liquid crystal alignment film produced by using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like.

[Examples]

The following examples are given to illustrate the invention in further detail, but should not be construed as limiting.

"Slightly remembered compounds used in synthesis, examples and comparative examples"

<specific compound>

P1: a compound represented by the following formula [P1]

P2: a compound represented by the following formula [P2]

P3: a compound represented by the following formula [P3]

<Monomer for producing a polyimide-based polymer (specific polymer)>

(specific diamine compound)

A1: 3,5-diamino benzoic acid

A2: a diamine compound represented by the following formula [A2]

A3: 1,3-diamino-4-octadecyloxybenzene

A4: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene

A5: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxymethyl]benzene

A6: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene

A7: a diamine compound represented by the following formula [A7]

(other diamine compounds)

B1: p-phenylenediamine

B2: m-phenylenediamine

(specific tetracarboxylic acid component)

C1:1,2,3,4-cyclobutanetetracarboxylic dianhydride

C2: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

C3: tetracarboxylic dianhydride represented by the following formula [C3]

C4: tetracarboxylic dianhydride represented by the following formula [C4]

<solvent>

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

ECS: ethylene glycol monoethyl ether

EC: diethylene glycol monoethyl ether

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

"Method for Measuring the Molecular Weight of Polyimine Polymers"

The molecular weight of the polyimine precursor and the polyimine is a normal temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Co., Ltd.) and a column (KD-803, KD-805). Shodex Co., Ltd.) was measured in the following manner.

Column temperature: 50 ° C

Solvent: N,N'-dimethylformamide (lithium bromide-hydrate (LiBr.H ₂ O) 30 mmol/L (liter), phosphoric acid. Anhydrous crystal (o-phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) 10ml/L as an additive)

Flow rate: 1.0ml/min

The calibration curve was prepared using standard samples: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (Polymer) Laboratories company).

"Method for Measuring the Amination Rate of Polyimine Imine"

20 mg of polyimine powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR standard sampling tube, 5 (manufactured by Kusano Scientific Co., Ltd.), adding dimethylated dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane) mixed product) (0.53 ml), and ultrasonically applied to completely dissolve it. This solution was measured for proton NMR at 500 MHz by an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Ltd.). Determine the protons from the structure that has not changed before and after the imidization, and use the peak integral value of the proton and the proton peak integral value of the NH group derived from proline from 9.5 to 10.0 ppm as the reference proton. The formula determines the yield of ruthenium.

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

In the above formula, x is the proton peak integrated value derived from the NH group of valine acid, the peak integrated value of the y-based reference proton, and the proline is based on the proline acid when the α-poly-proline (0%) For one of the NH protons, the ratio of the number of reference protons.

<Synthesis Example 1>

C1 (3.45 g, 17.6 mmol), A2 (0.73 g, 3.57 mmol) and B1 (1.54 g, 14.3 mmol) were mixed in NMP (17.2 g), and reacted at 40 ° C In the hour, a polyamic acid solution (1) having a resin solid content concentration of 25% by mass was obtained. The polyamine has a number average molecular weight of 26,600 and a weight average molecular weight of 85,200.

<Synthesis Example 2>

C2 (3.83 g, 15.3 mmol), A2 (0.93 g, 4.59 mmol) and B2 (2.81 g, 26.0 mmol) were mixed in NEP (21.0 g) and reacted at 50 ° C for 2 hours. Thereafter, C1 (2.91 g, 14.8 mmol) and NEP (10.5 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25% by mass. The polyamine has a number average molecular weight of 24,500 and a weight average molecular weight of 71,100.

<Synthesis Example 3>

In the polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 2, NEP was added, and after diluting to 6 mass%, acetic anhydride (3.95 g) and pyridine (2.45 g) were added as a ruthenium iridide. The medium was reacted at 70 ° C for 3 hours. The reaction solution was poured into methanol (460 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 (3). The polyimine has a hydrazine imidation ratio of 70%, a number average molecular weight of 22,100, and a weight average molecular weight of 60,100.

<Synthesis Example 4>

C2 (4.47 g, 17.9 mmol), A1 (1.95 g, 12.8 mmol) and A4 (4.85 g, 12.8 mmol) were mixed in NEP (25.4 g) and reacted at 80 ° C 5 hours. Thereafter, C1 (1.43 g, 7.30 mmol) and NEP (12.7 g) were added, and the mixture was reacted at 40 ° C for 8 hours to obtain a polyamic acid solution (4) having a resin solid concentration of 25% by mass. The polyamine has a number average molecular weight of 23,500 and a weight average molecular weight of 68,600.

<Synthesis Example 5>

In the polyamic acid solution (4) (30.2 g) obtained in Synthesis Example 4, NEP was added, and after diluting to 6 mass%, acetic anhydride (3.80 g) and pyridine (2.40 g) were added as a ruthenium iridide. The medium was reacted at 70 ° C for 2 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (5). The polyimide imidization ratio of this polyimine was 61%, the number average molecular weight was 19,900, and the weight average molecular weight was 57,100.

<Synthesis Example 6>

C2 (5.10 g, 20.4 mmol), A1 (1.94 g, 12.8 mmol), A2 (0.52 g, 2.55 mmol), and A5 (4.02 g, 10.2 mmol) were mixed in NMP (25.0 g), and reacted at 80 ° C hour. Thereafter, C1 (0.93 g, 4.80 mmol) and NMP (12.5 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After adding NMP to the obtained poly-proline solution (30.0 g) and diluting to 6 mass%, acetic anhydride (4.54 g) and pyridine (3.33 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 80 ° C. 3.5 hours. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. Wash this sink with methanol The precipitate was dried under reduced pressure at 100 ° C to obtain a polyimine powder (6). The polyimide imidization ratio of this polyimine was 85%, the number average molecular weight was 16,800, and the weight average molecular weight was 50,100.

<Synthesis Example 7>

C2 (2.42 g, 9.69 mmol), A1 (2.58 g, 17.0 mmol) and A6 (3.14 g, 7.27 mmol) were mixed in NEP (21.9 g), and reacted at 80 ° C for 5 hours, then added C1 (2.79 g, 14.2 mmol) and NEP (10.9 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

To the obtained polyamic acid solution (30.0 g), NEP was added, and after diluting to 6 mass%, acetic anhydride (4.40 g) and pyridine (3.25 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 80 ° C. hour. The reaction solution was poured into methanol (460 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 (7). The polyimide imidization ratio of this polyimine was 81%, the number average molecular weight was 17,400, and the weight average molecular weight was 52,800.

<Synthesis Example 8>

C2 (4.32 g, 17.3 mmol), A1 (3.00 g, 19.7 mmol) and A7 (2.43 g, 4.93 mmol) were mixed in NMP (22.2 g), and reacted at 80 ° C for 5 hours. Thereafter, C1 (1.37 g, 7.00 mmol) and NMP (11.1 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After adding NMP to the obtained poly-proline solution (30.5 g) and diluting it to 6 mass%, acetic anhydride (3.90 g) and pyridine (2.55 g) were added as a ruthenium catalyzed catalyst, and it reacted at 60 degreeC. hour. The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (8). The polyamidimide had a ruthenium iodide ratio of 53%, a number average molecular weight of 16,500, and a weight average molecular weight of 51,800.

<Synthesis Example 9>

C3 (5.40 g, 24.1 mmol), A1 (2.43 g, 15.9 mmol), A2 (0.50 g, 2.45 mmol) and A7 (3.02 g, 6.13 mmol) were mixed in NMP (34.1 g), and reacted at 40 ° C In an hour, a polyamic acid solution having a resin solid content concentration of 25% by mass was obtained.

NMP was added to the obtained polyamic acid solution (30.0 g), and after diluting to 6% by mass, acetic anhydride (4.05 g) and pyridine (2.50 g) were added as a ruthenium catalyzed catalyst, and reacted at 60 ° C for 2 hours. . The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (9). The polyamidimide had a ruthenium iodide ratio of 55%, a number average molecular weight of 16,100, and a weight average molecular weight of 48,100.

<Synthesis Example 10>

C3 (5.38 g, 24.0 mmol), A1 (2.22 g, 14.6 mmol) and A5 (3.84 g, 9.72 mmol) were mixed in NMP (34.3 g) and reacted at 40 ° C After 8 hours, a polyamic acid solution having a resin solid content concentration of 25% by mass was obtained.

NMP was added to the obtained polyamic acid solution (30.0 g), and after diluting to 6 mass%, acetic anhydride (4.00 g) and pyridine (2.50 g) were added as a ruthenium catalyzed catalyst, and it reacted at 70 degreeC for 2 hours. . The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (9). The polyimide imineization rate of this polyimine was 61%, the number average molecular weight was 17,300, and the weight average molecular weight was 51,100.

<Synthesis Example 11>

C4 (3.48 g, 11.6 mmol), A1 (1.06 g, 6.95 mmol), A2 (0.94 g, 4.63 mmol) and A3 (4.36 g, 11.6 mmol) were mixed in NEP (24.1 g) and reacted at 40 ° C hour. Thereafter, C1 (2.20 g, 11.2 mmol) and NEP (12.0 g) were added, and the mixture was reacted at 25 ° C for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass%, acetic anhydride (7.20 g) and pyridine (2.30 g) were added as a ruthenium catalyzed catalyst, and reacted at 40 ° C for 1.5 hours. . The reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (11). The polyimine has a hydrazine imidation ratio of 70%, a number average molecular weight of 17,500, and a weight average molecular weight of 40,100.

The polyamidene-based polymers are summarized and shown in Table 1.

"Evaluation of inkjet coating properties of liquid crystal alignment agents"

The liquid crystal alignment treatment agent was pressure-filtered through a membrane filter having a pore diameter of 1 μm to evaluate inkjet coating properties. The inkjet coater used HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.). ITO (Indium Tin Oxide) vapor-deposited substrate washed with pure water and IPA (isopropyl alcohol), with a coating area of 70×70 mm, a nozzle pitch of 0.423 mm, a scanning pitch of 0.5 mm, and a coating speed. 40 mm/sec, the time from the application to the temporary drying for 60 seconds, and the temporary drying was carried out on a hot plate at 70 ° C for 5 minutes.

The coating property of the obtained substrate with the liquid crystal alignment film was confirmed. Specifically, it is carried out by visually observing the coating film under a sodium lamp, and confirming the pinhole There is no. As a result, in the liquid crystal alignment film obtained in all the examples, pinholes were not observed on the coating film, and a liquid crystal alignment film excellent in coating property was obtained.

"Evaluation of display unevenness characteristics near the frame edge of liquid crystal cell after high temperature and high humidity storage (general unit cell)"

The liquid crystal alignment agent was filtered under pressure with a membrane filter having a pore diameter of 1 μm to prepare a liquid crystal cell (general unit cell). This solution was spin-coated on an ITO surface of a 100×100 mm ITO-attached substrate (100 mm in length × 100 mm in width, 0.7 mm in thickness) which was washed with pure water and IPA, and heat-treated at 100 ° C for 5 minutes on a hot plate. The film was heat-treated at 230 ° C for 30 minutes in a heat cycle type clean oven to obtain an ITO substrate having a polytheneimine liquid crystal alignment film having a film thickness of 100 nm. The coating surface of the ITO substrate was subjected to a rubbing treatment using a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation number of 1000 rpm, a roll speed of 50 mm/sec, and a pressing depth of 0.1 mm.

Two of the obtained ITO substrates with a liquid crystal alignment film were prepared, and one of them was attached with a liquid crystal alignment film surface of a substrate of a liquid crystal alignment film, and a spacer of 6 μm was spread. Thereafter, an ultraviolet curable sealant was drawn around the substrate, and liquid crystal was injected by an ODF (One Drop Filling) method to obtain a liquid crystal cell. Then, in order to cure the ultraviolet curable sealant, the liquid crystal cell was irradiated with a wavelength of 310 nm or less using a metal halide lamp having an illuminance of 60 mW, and irradiated with ultraviolet rays of 5 J/cm ² in terms of 365 nm. Thereafter, heat treatment was carried out in a heat cycle type clean oven at 120 ° C for 60 minutes to obtain a liquid crystal cell (general unit cell).

Further, in the liquid crystal cell of the liquid crystal alignment treatment agents (1) to (3) obtained in Examples 1 to 3 and the liquid crystal alignment treatment agents (21) to (22) obtained in Comparative Examples 1 and 2, A nematic liquid crystal (MLC-2003) (manufactured by Merck Japan Co., Ltd.) was used as the liquid crystal.

Further, the liquid crystal alignment treatment agents (4) to (6) obtained in Examples 4 to 6, the liquid crystal alignment treatment agent (8) obtained in Example 8, and the liquid crystal alignment treatment agent (9) obtained in Example 9 were used. The liquid crystal alignment treatment agents (11) to (15) obtained in Examples 11 to 15, and the liquid crystal alignment treatment agents (17) to (20) obtained in Examples 17 to 20, and Comparative Examples 3 to 4 were obtained. In the liquid crystal cell of the liquid crystal alignment agents (23) to (24), nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Co., Ltd.) was used as the liquid crystal.

The obtained liquid crystal cell (general unit cell) was evaluated by visual observation of the liquid crystal alignment property in the vicinity of the sealant using a polarizing plate and a backlight, and all of the liquid crystal cells obtained in the examples and the comparative examples were uniformly displayed. Liquid crystal alignment.

Thereafter, the liquid crystal cell was stored in a high-temperature and high-humidity bath at a temperature of 80 ° C and a humidity of 90% RH for 36 hours, and the liquid crystal alignment property in the vicinity of the sealant was evaluated under the same conditions as above. Specifically, the more the liquid crystal alignment disorder is not observed in the vicinity of the sealant, the better in this evaluation.

In Tables 5 to 7, the case where the disorder of the liquid crystal alignment is not observed is "○", and the person who sees the alignment of the liquid crystal is "X".

"Evaluation of Voltage Retention Rate after High Temperature and High Humidity Storage (General Cell)"

The liquid crystal alignment treatment agent is pressurized with a membrane filter having a pore diameter of 1 μm. Filtration is carried out to produce a liquid crystal cell (generally a unit cell). The solution was spin-coated on an ITO surface of a substrate of 30×40 mm ITO electrode (length 40 mm×length 30 mm, thickness 0.7 mm) which was washed with pure water and IPA, and heat-treated at 100° C. for 5 minutes on a hot plate. The film was heat-treated at 230 ° C for 30 minutes in a heat cycle type clean oven to obtain an ITO substrate having a polytheneimine liquid crystal alignment film having a film thickness of 100 nm. The coating surface of the ITO substrate was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a crepe cloth at a roller rotation speed of 1000 rpm, a roll speed of 50 mm/sec, and a press distance of 0.1 mm.

Two ITO substrates with a liquid crystal alignment film were prepared, and a liquid crystal alignment film surface was placed inside, and a 6 μm spacer was sandwiched and combined to print an ultraviolet curing type sealing agent. Thereafter, the substrate of the other substrate is bonded to each other with the liquid crystal alignment film faces facing each other, and then the ultraviolet curing type sealing agent is cured to obtain an empty cell. Specifically, a metal halide lamp having an illuminance of 60 mW was used to filter out a wavelength of 310 nm or less, and irradiated with ultraviolet rays of 5 J/cm ² in terms of 365 nm, followed by heat treatment at 120 ° C for 60 minutes in a heat cycle type clean oven. Empty cell. The liquid crystal is injected into the empty cell by a vacuum injection method, and the injection port is sealed to obtain a liquid crystal cell (generally a unit cell).

In addition, the liquid crystal used for the production of the liquid crystal cell of each of the examples and the comparative examples is the same as the above-mentioned "Evaluation of display unevenness characteristics (general cell) in the vicinity of the cell edge of the liquid crystal cell after high-temperature and high-humidity storage".

For the obtained liquid crystal cell, a voltage of 1 V was applied at a temperature of 80 ° C for 60 μs, and the voltage after 50 ms was measured to obtain a voltage holding ratio (also referred to as VHR) to calculate how much voltage can be maintained. In addition, the measurement system was carried out using a voltage retention ratio measuring device (VHR-1) (manufactured by Toyo Technica Co., Ltd.) with a setting of Voltage: ±1 V, Pulse Width: 60 μs, and Flame Period: 50 ms.

Further, the liquid crystal cell in which the measurement of the voltage holding ratio was completed was stored in a high-temperature and high-humidity bath at a temperature of 80 ° C and a humidity of 90% RH for 48 hours, and the voltage holding ratio was measured again under the same conditions as above.

The evaluation is based on the value of the voltage holding ratio immediately after the liquid crystal cell is formed, and the smaller the decrease in the voltage holding ratio value after storage in the high-temperature and high-humidity bath, the better (Tables 5 to 7).

"Production of Liquid Crystal Cell and Evaluation of Liquid Crystal Alignment (PSA Cell)"

The liquid crystal alignment agent was filtered under pressure with a membrane filter having a pore diameter of 1 μm to prepare a liquid crystal cell and evaluate the liquid crystal alignment (PSA unit cell). This solution was spin-coated on a substrate (length 40 mm × width 30 mm, thickness 0.7 mm) with an ITO electrode of 10 × 10 mm pattern spacing of 20 μm in the center of pure water and IPA washing, and an ITO electrode with a center of 10×40 mm. The ITO surface of the substrate (40 mm in length × 30 mm in width and 0.7 mm in thickness) was heat-treated at 100 ° C for 5 minutes on a hot plate, and heat-treated at 230 ° C for 30 minutes in a heat cycle type clean oven to obtain a polyimide having a film thickness of 100 nm. Coating film.

The substrate on which the liquid crystal alignment film was attached was placed on the inner side of the liquid crystal alignment film surface, and a spacer of 6 μm was sandwiched and combined, and the periphery was adhered with a sealant to prepare an empty cell. The empty cell was injected with respect to 100% by mass of nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Co., Ltd.) by a vacuum injection method. In other words, 0.3% by mass of a liquid crystal mixture of the polymerizable compound (1) represented by the following formula was mixed, and the injection port was sealed to obtain a liquid crystal cell.

While applying a voltage of 5 V to the obtained liquid crystal cell, a metal halide lamp having an illuminance of 60 mW was used, and a wavelength of 350 nm or less was filtered out, and ultraviolet irradiation of 20 J/cm ^{2 in a} conversion of 365 nm was performed, and the alignment direction of the liquid crystal was controlled. Liquid crystal cell (PSA unit cell). The temperature in the irradiation device when the liquid crystal cell was irradiated with ultraviolet rays was 50 °C.

The response speed of the liquid crystal cell before the ultraviolet irradiation and the liquid crystal after the ultraviolet irradiation was measured. The response speed was measured from T90 to T10 from a transmittance of 90% to a transmittance of 10%.

In the PSA unit cell obtained in the examples, the liquid crystal cell after the ultraviolet irradiation had a faster response speed than the liquid crystal cell before the ultraviolet irradiation, and thus it was confirmed that the alignment direction of the liquid crystal was controlled. In addition, it was confirmed by the polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Co., Ltd.) that the liquid crystal cell was uniformly aligned.

<Example 1>

The resin solid content concentration obtained in Synthesis Example 1 was 25% by mass. NMP (19.9 g) and BCS (11.8 g) were added to the polyamic acid solution (1) (10.0 g), and the mixture was stirred at 25 ° C for 2 hours. Thereafter, P2 (0.25 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (1). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (1), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Example 2>

To a polyamic acid solution (2) (10.5 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2, NEP (18.9 g) and PB (14.4 g) were added, and the mixture was stirred at 25 ° C for 2 hours. Thereafter, P2 (0.18 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (2). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (2), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Example 3>

In the polyimine powder (3) (1.55 g) obtained in Synthesis Example 3, NEP (17.0 g) and PB (7.30 g) were added, and the mixture was stirred at 70 ° C for 24 hours to dissolve. Thereafter, P2 (0.11 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (3). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (3), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Example 4>

To a polyamic acid solution (4) (11.0 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 4, NEP (19.8 g) and PB (15.1 g) were added, and the mixture was stirred at 25 ° C for 2 hours. Thereafter, P2 (0.19 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (4). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (4), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Example 5>

NEP (17.6 g) and EC (4.30 g) were added to a polyamic acid solution (4) (11.0 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 4. PB (12.9 g) was stirred at 25 ° C for 2 hours. Thereafter, P1 (0.41 g) was added, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (5). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (5), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Example 6>

NEP (15.3 g) and PB (8.20 g) were added to the polyimine powder (5) (1.50 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, P2 (0.11 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (6). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (6), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell) and "Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)".

<Example 7>

NEP (23.1 g) and PB (12.4 g) were added to the polyimine powder (5) (1.10 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to dissolve. solution. Thereafter, P2 (0.077 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (7). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

The evaluation of the inkjet coating property of the liquid crystal alignment treatment agent was carried out using the obtained liquid crystal alignment treatment agent (7).

<Example 8>

NMP (13.4 g), EC (2.40 g), and BCS (8.50 g) were added to the polyimine powder (5) (1.55 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, P3 (0.23 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (8). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (8), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Example 9>

NEP (15.5 g) and PB (8.30 g) were added to the polyimine powder (6) (1.52 g) obtained in Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, P1 (0.26 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (9). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (9), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell) and "Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)".

<Example 10>

NEP (22.1 g) and PB (11.9 g) were added to the polyimine powder (6) (1.05 g) obtained in Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, P1 (0.18 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (10). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

The evaluation of the inkjet coating property of the liquid crystal alignment treatment agent was carried out using the obtained liquid crystal alignment treatment agent (10).

<Example 11>

NEP (9.40 g), γ-BL (4.70 g), and BCS (9.40 g) were added to the polyimine powder (7) (1.50 g) obtained in Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours. Dissolved. Thereafter, P2 (0.075 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (11). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (11), evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general crystal Cell") and "Evaluation of voltage retention rate after high temperature and high humidity storage (general unit cell)".

<Example 12>

NMP (14.1 g), ECS (2.40 g), and BCS (7.10 g) were added to the polyimine powder (7) (1.50 g) obtained in Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, P1 (0.075 g) and P2 (0.15 g) were added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (12). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (12), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Example 13>

NEP (15.5 g) and PB (8.30 g) were added to the polyimine powder (8) (1.52 g) obtained in Synthesis Example 8, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, P2 (0.15 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (13). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (13), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (general crystal Cell") and "Production of Liquid Crystal Cell and Evaluation of Liquid Crystal Alignment (PSA Cell)".

<Example 14>

NEP (15.3 g) and PB (8.20 g) were added to the polyimine powder (8) (1.50 g) obtained in Synthesis Example 8, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, P1 (0.045 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (14). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (14), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Example 15>

NEP (11.8 g), γ-BL (2.40 g) and PB (9.40 g) were added to the polyimine powder (9) (1.50 g) obtained in Synthesis Example 9, and stirred at 70 ° C for 24 hours. Dissolved. Thereafter, P3 (0.15 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (15). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (15), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (general crystal Cell)).

<Example 16>

NEP (16.2 g), γ-BL (3.20 g), and PB (12.9 g) were added to the polyimine powder (9) (1.00 g) obtained in Synthesis Example 9, and stirred at 70 ° C for 24 hours. Dissolved. Thereafter, P3 (0.10 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (16). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

The evaluation of the inkjet coating property of the liquid crystal alignment treatment agent was carried out using the obtained liquid crystal alignment treatment agent (16).

<Example 17>

NMP (15.8 g) and PB (8.50 g) were added to the polyimine powder (10) (1.55 g) obtained in Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, P1 (0.23 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (17). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (17), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Example 18>

NEP (15.8 g) and PB (8.50 g) were added to the polyimine powder (10) (1.55 g) obtained in Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Thereafter, P1 (0.11 g) and P2 (0.11 g) were added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (18). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (18), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell) and "Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)".

<Example 19>

γ-BL (12.9 g), EC (2.40 g), and BCS (8.20 g) were added to the polyimine powder (11) (1.50 g) obtained in Synthesis Example 11 and stirred at 70 ° C for 24 hours. Dissolved. Thereafter, P3 (0.15 g) was added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (19). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (19), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Example 20>

NMP (14.1 g), ECS (2.40 g), and BCS (7.10 g) were added to the polyimine powder (11) (1.50 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, P1 (0.075 g) and P2 (0.075 g) were added to the solution, and the mixture was stirred at 60 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (20). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (20), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Comparative Example 1>

NEP (18.9 g) and PB (14.4 g) were added to a polyamic acid solution (2) (10.5 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2, and the mixture was stirred at 25 ° C for 2 hours to obtain Liquid crystal alignment treatment agent (21). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (21), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Comparative Example 2>

NEP (17.0 g) and PB (7.30 g) were added to the polyimine powder (3) (1.55 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved to obtain a liquid crystal alignment treatment agent ( twenty two). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (22), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Comparative Example 3>

NEP (19.8 g) and PB (15.1 g) were added to a polyamic acid solution (4) (11.0 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 4, and stirred at 25 ° C for 2 hours to obtain Liquid crystal alignment treatment agent (23). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and a uniform solution was confirmed.

Using the obtained liquid crystal alignment treatment agent (23), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

<Comparative Example 4>

NEP (15.3 g) and PB (8.20 g) were added to the polyimine powder (5) (1.50 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved to obtain a liquid crystal alignment treatment agent ( twenty four). In the liquid crystal alignment treatment agent, not When an abnormality such as turbidity or precipitation was observed, it was confirmed that the solution was uniform.

Using the obtained liquid crystal alignment treatment agent (24), "Evaluation of display unevenness characteristics near the frame edge of the liquid crystal cell after high temperature and high humidity storage (general unit cell)" and "Evaluation of voltage retention rate after high temperature and high humidity storage" (General cell)".

From the above results, it is understood that the liquid crystal alignment treatment agent of the example can obtain a liquid crystal cell sealant even when the liquid crystal cell is stored in a high temperature and high humidity bath for a long period of time compared to the liquid crystal alignment treatment agent of the comparative example. The liquid crystal alignment film is not disordered by the nearby liquid crystal alignment. Further, even when the liquid crystal cell is stored for a long period of time in the high-temperature and high-humidity bath, a liquid crystal alignment film capable of suppressing a decrease in the voltage holding ratio can be obtained. In other words, the liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment film capable of suppressing occurrence of display unevenness and voltage retention in the vicinity of the frame edge of the liquid crystal display element under high temperature and high humidity conditions.

Specifically, it is a comparison between Example 2 and Comparative Example 1, Example 3 and Comparative Example 2, Example 4 and Comparative Example 3, and Example 6 and Comparative Example 4, and the embodiment is the same as the use (B). Comparison of comparative examples of specific polymers of the components but not specific compounds of component (A). When the liquid crystal alignment agent of the comparative example is used, when the liquid crystal cell is stored for a long period of time in the high-temperature and high-humidity bath, liquid crystal alignment is disturbed in the vicinity of the sealing agent of the liquid crystal cell, and the voltage holding ratio is largely lowered.

[Industrial availability]

Formed by using the liquid crystal alignment treatment agent of the present invention The liquid crystal display element of the liquid crystal alignment film is excellent in reliability, and can be suitably used for a large-screen and high-definition liquid crystal television, and is used as a TN element, an STN element, a TFT liquid crystal element, and particularly a vertical alignment type liquid crystal display element.

In addition, the entire contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2013-96470, filed on May 1, 2013, are hereby incorporated by reference.

Claims (14)

A liquid crystal alignment treatment agent comprising the following components (A) and (B), (A) a compound represented by the following formula [1], and (B) a component selected from the group consisting of a diamine component and a polymer obtained by reacting a tetracarboxylic acid component with at least one polymer of the group consisting of a polyimide precursor and a polyimine; (X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent organic group having a carbon number of 6 to 24 having a benzene ring or a cyclohexane ring, and X ² represents a formula [1] -1]~ the structure selected in [1-5]), (W ¹ represents a hydrogen atom or a benzene ring). The liquid crystal alignment treatment agent of claim 1, wherein X ^{1 of the} above formula [1] is an alkylene group having 1 to 10 carbon atoms. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein X ^{2 of the} above formula [1] is a structure selected from the formula [1-1], the formula [1-2], and the formula [1-4]. The liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein the diamine component in the polymer of the component (B) contains at least one diamine having a structure represented by the following formula [2] Compound, (Y represents a substituent of a structure selected from the following formula [2-1] to formula [2-6], and m represents an integer of 1 to 4); (a represents an integer from 0 to 4, b represents an integer from 0 to 4; Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or OCO-, Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ³ represents a single bond, -(CH ₂ ) _c - (c is 1 to 15 Integer), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring; or a carbon having a steroid skeleton a 12-valent organic group having 12 to 25, and any hydrogen atom on the above-mentioned cyclic group may also have an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and fluorine having 1 to 3 carbon atoms. An alkyl group, a fluorine-containing alkoxy group or a fluorine atom substituted with 1 to 3 carbon atoms, and Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring. Any hydrogen atom may also pass through an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. Substituted with a fluorine atom, n represents an integer from 0 to 4, Y 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. 1 to 18 of a fluorine-containing alkoxy group, Y ⁷ represents -O-, -CH ₂ O-, -C OO-, -OCO-, -CONH- or -NHCO-, Y ⁸ represents an alkyl group having 8 to 22 carbon atoms; Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and Y ¹¹ represents a carbon number. 1~5 alkyl). The liquid crystal alignment treatment agent according to any one of claims 1 to 4, wherein the tetracarboxylic acid component in the polymer of the component (B) contains a compound represented by the following formula [3]. (Z ¹ is a group of a structure selected from the following formula [3a] to formula [3j]); (Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different, and Z ⁶ and Z ^{7 each} represent a hydrogen atom or a methyl group, and each may be the same or different). The liquid crystal alignment treatment agent according to any one of claims 1 to 5, wherein the polymer of the component (B) is a polyimine obtained by dehydrating a polyamic acid. The liquid crystal alignment treatment agent according to any one of claims 1 to 6, wherein the component (A) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (B). A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of claims 1 to 7. A liquid crystal alignment film obtained by an inkjet method using the liquid crystal alignment treatment agent according to any one of claims 1 to 7. A liquid crystal display element having the liquid crystal alignment film of claim 8 or 9. The liquid crystal alignment film of claim 8 or 9, which is used for a liquid crystal display element, which is provided with one of the electrodes A liquid crystal layer is disposed between the pair of substrates, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a voltage is applied between the electrodes to polymerize the polymerizable compound. And manufacturing. A liquid crystal display element having the liquid crystal alignment film of claim 11. The liquid crystal alignment element according to claim 8 or 9, which is used for a liquid crystal display element, wherein the liquid crystal display element has a liquid crystal layer between the one of the electrodes, and the active energy is disposed between the pair of substrates A liquid crystal alignment film of a polymerizable group which is polymerized by at least one of a line and a heat is produced by applying a voltage between the electrodes and polymerizing the polymerizable group. A liquid crystal display element having the liquid crystal alignment film of claim 13.