TW201500463A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Provided is a liquid crystal alignment agent that contains at least one polymer chosen from among a polyimide precursor and a polyimide obtained by imidization of the polyimide precursor, the polyimide precursor being obtained by reacting a diamine component with a tetracarboxylic acid component that includes a tetracarboxylic acid dianhydride represented by formula [1] and an aliphatic tetracarboxylic acid dianhydride represented by formula [2]. (In formula [2], Z1 is at least one tetravalent group chosen from formulas [2a] through [2j].) (In formula [2a], Z2 through Z5 indicate a chlorine atom, a methyl group, a nitrogen atom, or a benzene ring, each of which can be the same or different; and in formula [2g], Z6 and Z7 indicate a hydrogen atom or a methyl group, each of which can be the same or different).

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 in the production of a liquid crystal display device, a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.

At present, a liquid crystal alignment film of a liquid crystal display element is mainly used as a so-called polyimine-based liquid crystal alignment film which is coated with a polyimine precursor such as polylysine or a soluble polyazide. A solution of an amine as a main component of a liquid crystal alignment treatment agent, which is fired.

The liquid crystal alignment film is an article used for the purpose of controlling the alignment state of the liquid crystal. However, with the high definition of the liquid crystal display element, the viewpoint of suppressing the decrease in the contrast of the liquid crystal display element or reducing the image sticking phenomenon is adopted, and the liquid crystal alignment film used has a high voltage holding ratio or a charge accumulated when a DC voltage is applied. It is becoming more and more important that characteristics such as less or faster mitigation of the charge accumulated by the DC voltage.

In a polyimine-based liquid crystal alignment film, a time period from the occurrence of a residual voltage due to a DC voltage to a disappearance is, for example, a polyaminic acid containing a polyaminic acid or a quinone imine group and a specific structure are used. 3-grade amine liquid crystal The liquid crystal alignment treatment agent (for example, refer to Patent Document 1), or a liquid crystal alignment treatment agent containing a soluble polyimine which is used as a raw material having a specific diamine such as a pyridine skeleton (for example, see Patent Document 2) Known. Further, the voltage holding ratio is high, and the time period from the occurrence of the residual image due to the DC voltage to the disappearance is, for example, a small amount is contained in addition to the polyamine or the quinone imidized polymer. A liquid crystal alignment treatment agent containing a compound having one carboxylic acid group in the molecule, a compound having one carboxylic acid anhydride group in the molecule, and a compound having one amino acid group in the molecule (for example, refer to Patent Document 3) ) is already known.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-316200

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-104633

[Patent Document 3] Japanese Patent Laid-Open No. Hei 8-076128

[Summary of the Invention]

In recent years, with the increase in the performance of liquid crystal display elements, liquid crystal display elements have been used for liquid crystal televisions having large screens and high definition, and for automotive applications such as car navigation systems or instrument panels. For such applications, in order to obtain high brightness, a backlight having a large amount of heat may be used. Therefore, liquid crystal The alignment film requires high reliability from other viewpoints, that is, high stability to light from the backlight. In particular, when the voltage holding ratio of one of the electrical characteristics of the liquid crystal display element is lowered by the light irradiation from the backlight, there is a problem of image sticking failure (also referred to as line residual image) which is one of display failures of the liquid crystal display element.

Therefore, in addition to the initial characteristics of the liquid crystal alignment film, it is required that, for example, after a long period of light irradiation, the voltage holding ratio is not easily lowered.

Therefore, the object of the present invention is to provide a liquid crystal alignment treatment agent, a liquid crystal alignment film, and a liquid crystal having the liquid crystal alignment film, which can suppress a decrease in voltage holding ratio even after long-time light irradiation, and which can provide a liquid crystal alignment film having excellent light resistance. Display component.

As a result of intensive studies, the present inventors have found that a polyimine precursor obtained by reacting a tetracarboxylic acid component containing two kinds of tetracarboxylic dianhydrides having a specific structure with a diamine component and a precursor of the polyimine The liquid crystal alignment treatment agent of at least one polymer of at least one type of polyimine obtained by ruthenium imidation can achieve the above object very effectively, and the present invention has been completed.

That is, the present invention has the following technical features.

(1) A liquid crystal alignment treatment agent characterized by containing a tetracarboxylic acid component selected from the group consisting of a tetracarboxylic dianhydride represented by the following formula [1] and a tetracarboxylic dianhydride represented by the following formula [2] A polymer obtained by reacting a polyimine component obtained by reacting a diamine component with at least one polymer obtained by subjecting the polyimine precursor to ruthenium imidization.

(In the formula [2], Z ¹ is selected from a tetravalent group of at least one of the following formulas [2a] to [2j]).

(In the formula [2a], 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 [2g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, Each can be the same or different).

(2) The liquid crystal alignment treatment agent according to the above (1), which comprises N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ -butyrolactone as a liquid crystal alignment treatment agent. Solvent.

(3) The liquid crystal alignment treatment agent according to the above (1) or (2), which contains a solvent selected from the following formula [D-1] to formula [D-3] as a solvent in the liquid crystal alignment treatment agent, (In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms).

(4) A liquid crystal alignment film which is obtained by using the liquid crystal alignment treatment agent of the above items (1) to (3).

(5) A liquid crystal alignment film characterized by using the liquid crystal alignment treatment agent of the above (1) to (3), which is obtained by an inkjet method.

(6) A liquid crystal display element characterized by having the liquid crystal alignment film of the above (4) or (5).

According to the liquid crystal alignment treatment agent of the present invention, it is possible to obtain a liquid crystal alignment film which is excellent in light resistance by suppressing a decrease in voltage holding ratio even after long-time light irradiation. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention has excellent reliability. Different, it can be applied to large-screen and high-definition LCD TVs.

[Formation of the Invention]

The liquid crystal alignment treatment agent of the present invention contains an aliphatic tetracarboxylic acid selected from the group consisting of tetracarboxylic dianhydride (also referred to as specific tetracarboxylic dianhydride) represented by the following formula [1] and the following formula [2]. a polyimine precursor obtained by reacting a tetracarboxylic acid component of an acid dianhydride (also referred to as a specific aliphatic tetracarboxylic dianhydride) with a diamine component, and a ruthenium imidization of the polyimine precursor A polymer (also referred to as a specific polymer) of at least one type of polyimine.

The diamine component refers to a diamine compound having two primary or secondary amine groups in the molecule. Polyimine precursor refers to polyamic acid or polyalkyl amide.

<Specific tetracarboxylic dianhydride>

The tetracarboxylic acid component of the specific polymer raw material contained in the liquid crystal alignment treatment agent of the present invention contains two types of tetracarboxylic dianhydride. One of the tetracarboxylic dianhydrides is a specific tetracarboxylic dianhydride represented by the following formula [1].

The specific tetracarboxylic dianhydride represented by the formula [1] may be a tetracarboxylic acid, a tetracarboxylic acid dihalide compound, a dicarboxylic acid dialkylate compound or a dicarboxylic acid dialkyl ester dihalide of a tetracarboxylic acid derivative thereof. Compounds (sometimes collectively referred to as Specific tetracarboxylic acid component).

The specific tetracarboxylic dianhydride represented by the formula [1] is preferably 20 mol% to 80 mol% in the tetracarboxylic acid component. Of these, it is preferably from 20 mol% to 60 mol%. It is particularly good for 20% by mole to 50% by mole.

<Specific aliphatic tetracarboxylic dianhydride>

The tetracarboxylic acid component of the specific polymer raw material contained in the liquid crystal alignment treatment agent of the present invention contains two types of tetracarboxylic dianhydride. Another type of tetracarboxylic dianhydride is a specific aliphatic tetracarboxylic dianhydride represented by the following formula [2].

In the formula [2], Z ¹ is a tetravalent group selected from at least one of the following formulas [2a] to [2j].

In the formula [2a], 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 [2g], 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 [2], Z ^{1 is} preferably a formula [2a], a formula [2c], a formula [2d], or a formula from the viewpoint of easiness of synthesis or easiness of polymerization reactivity in producing a polymer. [2e], the structure represented by the formula [2f] or the formula [2g]. More preferably, it is a structure represented by the formula [2a], the formula [2e], the formula [2f] or the formula [2g], and particularly preferably the formula [2e], the formula [2f] or the formula [2g].

The specific aliphatic tetracarboxylic dianhydride represented by the formula [2] may be a tetracarboxylic acid, a tetracarboxylic acid dihalide compound, a dicarboxylic acid dialkylate compound or a dicarboxylic acid dialkyl ester of the tetracarboxylic acid derivative thereof. Halide compounds (sometimes collectively referred to collectively as specific tetracarboxylic acid components).

The specific aliphatic tetracarboxylic dianhydride represented by the formula [2] is preferably 20 mol% to 80 mol% in the total tetracarboxylic acid component. Very good is 20% to 60% by mole.

Further, the specific aliphatic tetracarboxylic dianhydride is blended with a solvent of a specific polymer contained in the liquid crystal alignment agent of the present invention, or a coating property of a liquid crystal alignment agent, and a liquid crystal alignment property as a liquid crystal alignment film. The characteristics such as the voltage holding ratio and the accumulated electric charge can be used in one type or in a mixture of two or more types.

<Other tetracarboxylic acid compounds>

The tetracarboxylic acid component in the specific polymer contained in the liquid crystal alignment treatment agent of the present invention may be used in addition to the specific tetracarboxylic dianhydride and the specific aliphatic tetracarboxylic dianhydride insofar as the effects of the present invention are not impaired. Tetracarboxylic acid compounds (also known as other tetracarboxylic acid compounds).

Specific examples thereof include a tetracarboxylic dianhydride, a tetracarboxylic acid compound, or a dicarboxylic acid dihalide compound shown below.

Mention may be made of pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3 6,7-nonanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-linked Pyromellitic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)fluorene, double (3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-dual ( 3,4-Dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyloxane, bis(3,4-dicarboxyphenyl)diphenylnonane, 2,3,4,5 -pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10-anthracene Tetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

The tetracarboxylic acid compound, the solubility of the specific polymer contained in the liquid crystal alignment agent of the present invention, the solubility of the liquid crystal alignment treatment agent, the alignment property of the liquid crystal when the liquid crystal alignment film is used, and the voltage retention ratio The characteristics of accumulating charges and the like can be used in one type or in a mixture of two or more types.

<Diamine component>

A known diamine component can be used as the diamine component for the specific polymer contained in the liquid crystal alignment agent of the present invention.

Among them, a diamine compound having a structure represented by the following formula [3] is preferably used.

In the formula [3], Y represents a formula selected from the following formula [3-1], formula [3-2], formula [3-3], formula [3-4], [3-5] or formula [3- 6] at least one monovalent group, m represents an integer of 1 to 4, and -(Y) _m represents m substituents Y.

In the formula [3-1], a represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials or ease of synthesis, an integer of 0 or 1 is preferred.

In the formula [3-2], b represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials or ease of synthesis, an integer of 0 or 1 is preferred.

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

In the formula [3-3], 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 preferable.

In the formula [3-3], 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, from the viewpoint of easiness of synthesis, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable. 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 [3-3], Y ⁴ is 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 pass through an alkyl group having 1 to 3 carbon atoms. The group is substituted with 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. Further, Y ⁴ may also be a divalent organic group selected from an organic group having a carbon number of 12 to 25 having a steroid skeleton. Among them, from the viewpoint of easiness of synthesis, a benzene ring, a cyclohexane ring or an organic group having a carbon number of 17 to 51 having a steroid skeleton is preferred.

In the formula [3-3], 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 pass through an alkyl group having 1 to 3 carbon atoms. The group is substituted with 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. Among them, a benzene ring or a cyclohexane ring is preferred.

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

In the formula [3-3], 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 fluorine-containing alkane having 1 to 18 carbon atoms. Oxygen. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferable. 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.

A preferred combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [3-3] of the substituent Y in the formula [3], for example, is related to the international publication. The same combination of (2-1) to (2-629) disclosed in Tables 13 to 47 of 13 to 34 of WO2011/132751. Further, in the tables of the International Publications, although Y ¹ to Y ⁶ of the present invention are represented by Y1 to Y6, Y1 to Y6 can also be interpreted as Y ¹ to Y ⁶ . The organic group having a carbon number of 12 to 25 having a steroid skeleton is interpreted as an organic group having a carbon number of 17 to 51 having a steroid skeleton.

In the formula [3-4], Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-. Of these, -O-, -CH ₂ O-, -COO- or -CONH- are preferred. More preferably -O-, -COO- or -CONH-.

In the formula [3-4], Y ⁸ represents an alkyl group having 8 to 22 carbon atoms.

In the formula [3-5], Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group having 1 to 12 carbon atoms.

In the formula [3-6], Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms.

The method for producing the diamine compound represented by the above formula [3] is not particularly limited, and preferred methods are, for example, those described below. One of the examples is a diamine compound represented by the formula [3] which is obtained by synthesizing a dinitro compound represented by the following formula [3-A], followed by reduction of the nitro group and conversion into an amine group.

(In the formula [3-A], Y represents a formula selected from the above formula [3-1], formula [3-2], formula [3-3], formula [3-4], formula [3-5] or formula At least one substituent in [3-6], m represents an integer of 1 to 4).

The dinitro group of the dinitro compound represented by the formula [3-A] is further The original method is not particularly limited, and is generally used in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent, and palladium-carbon, platinum oxide, nickel nickel, platinum black, and rhodium-alumina. Or a method in which platinum sulfide carbon or the like is used as a catalyst and reacted under hydrogen, hydrazine or hydrogen chloride.

The specific structure of the diamine compound represented by the above formula [3] is as follows, but is not limited thereto.

That is, the diamine compound represented by the formula [3], except 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-di In addition to the amino resorcin, for example, there are diamine compounds having the structures shown by the following formulas [3-7] to [3-47].

(In the formula [3-7] to the formula [3-10], A ¹ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

(In the formula [3-35]~Form [3-37], R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or CH ₂ OCO-, and R ² represents a carbon number of 1 ~22 alkyl, alkoxy, fluoroalkyl or fluoroalkoxy).

(In the formula [3-38]~Form [3-40], R ³ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or - CH ₂ -, R ⁴ represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(In the formula [3-41] and the formula [3-42], R ⁵ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, - CH ₂ - or -O-, R ⁶ represents a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxy group).

(In the formula [3-43] and the formula [3-44], R ⁷ represents an alkyl group having a carbon number of 3 to 12. Further, the cis-trans isomerization of the 1,4-cyclohexylene group is each a counter Preferred isomers).

(In the formula [3-45] and the formula [3-46], R ⁸ represents an alkyl group having 3 to 12 carbon atoms. Further, the cis-trans isomerization of the 1,4-cyclohexylene group is inversely Preferred isomers).

(In the formula [3-47], 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 group. Atom or -COO-* (but with a "*" bond and B ³ bond), B ¹ represents an oxygen atom or -COO-* (but with a "*" bond and (CH ₂ )a ² Bond))). 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 diamine compound represented by the above formula [3], a liquid crystal alignment treatment agent obtained by using a specific polymer of the diamine compound having the structure represented by the formula [3-3] in the formula [3], When it is a liquid crystal alignment film, the pretilt angle of a liquid crystal can be improved. In this case, for the purpose of improving the effects, among the above diamine compounds, the formula [3-25] to the formula [3-40] or the formula [3-43] to the formula [3-47] is used. Diamine compounds are preferred. More preferably, it is a diamine compound represented by the formula [3-29] to the formula [3-40] or the formula [3-43] to the formula [3-47]. Moreover, in order to further enhance these effects, these diamine compounds are preferably 5 mol% or more and 80 mol% or less of the entire diamine component. The diamine compound is more preferably 5 mol% or more and 60 mol% or less of the entire diamine component from the viewpoints of the coating property of the composition and the liquid crystal alignment agent or the electrical properties of the liquid crystal alignment film.

The solubility of the specific polymer contained in the liquid crystal alignment agent of the present invention in the solubility of the diamine compound represented by the above formula [3], or the coating property of the liquid crystal when it is used as a liquid crystal alignment film, and the voltage retention ratio. The characteristics of accumulating charges and the like can be used in one type or in a mixture of two or more types.

A diamine compound (also referred to as another diamine compound) other than the diamine compound represented by the above formula [3] can be used as the diamine component for the specific polymer contained in the liquid crystal alignment agent of the present invention. Following Other diamine compounds are listed, but are not limited to these examples.

For example, there are 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'-diamine Biphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-di Aminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane , 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl 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, double (3- Aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3' -thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-di Aminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-Diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl (3,4'-diaminodiphenyl) Amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminodi Benzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobiphenyl Ketone, 2,3'-diaminobenzophenone, 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-aminobenzene) Ethylene, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane , 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl) Methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1 , 3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'- [1,4-phenylphenylbis(methylene)]diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4'-[1,4 -phenylphenylbis(methylene)]diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[1,4-phenylene Bis(methylene)]diphenylamine, 3,3'-[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylene bis[(4-aminophenyl) Methyl ketone], 1,4-phenylene bis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3- Phenyl bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzene) Formate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene (3-) Amino benzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl) Phthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N, N'-(1,3-phenylene) bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N '-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)m-xylyleneamine, N,N'-bis(3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxyl) Diphenyl hydrazine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl] Hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amine 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-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1, 4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1 , 5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane 1,10-(4-Aminophenoxy)decane, 1,10-(3-amine Phenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-amine Phenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl) Methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoglycol Alkane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diamine Dodecane and the like.

Further, other diamine compounds have, for example, a side chain in the diamine An alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring, and a macrocyclic substituent having such a composition. Specifically, for example, there are diamine compounds represented by the following formulas [DA1] to [DA7].

(In the formula [DA1]~Form [DA6], A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-; A ² It is a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(In the formula [DA7], p represents an integer from 1 to 10).

The diamine compound represented by the following formula [DA8] to formula [DA13] can be used as the other diamine compound insofar as the effect of the present invention is not impaired.

(In the formula [DA10], m represents an integer of 0 to 3, and in the formula [DA13], n represents an integer of 1 to 5).

In addition, as the other diamine compound, a diamine compound represented by the following formula [DA14] to formula [DA17] can be used as long as the effect of the present invention is not impaired.

(In the formula [DA14], 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 are each An integer representing from 1 to 5, 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 in the formula [DA17], 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).

In addition, other diamine compounds can also use the following formula [DA18] and a diamine compound represented by the formula [DA19].

The other diamine compound exemplified above, the solubility of the specific polymer contained in the liquid crystal alignment agent of the present invention, the coating property of the solvent, the alignment property of the liquid crystal when the liquid crystal alignment film is used, the voltage retention ratio, The characteristics of the accumulated charges and the like can be used in one type or in a mixture of two or more types.

<specific polymer>

The specific polymer contained in the liquid crystal alignment treatment agent of the present invention is selected from the group consisting of a specific tetracarboxylic acid component containing the specific tetracarboxylic dianhydride represented by the above formula [1] and containing the specific fat represented by the above formula [2]. a polyimine precursor obtained by reacting a specific aliphatic tetracarboxylic acid component of a tetracarboxylic dianhydride with a diamine component, and a polyimine obtained by subjecting the polyimine precursor to ruthenium imidization At least one polymer.

In addition, the polyimine precursor obtained by reacting the specific aliphatic tetracarboxylic acid component with the above-described diamine component has a structure represented by the following formula [A].

(In the formula [A], R ¹ is a tetravalent organic group derived from a specific aliphatic tetracarboxylic acid component, R ² is derived from a divalent organic group of a diamine component, and A ¹ and A ² are a hydrogen atom or a carbon number of 1 The alkyl groups of ~8 may be the same or different, and A ³ and A ⁴ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an ethyl fluorenyl group, each of which may be the same or different, and n represents a positive integer).

The specific polymer contained in the liquid crystal alignment agent of the present invention is a specific tetracarboxylic dianhydride represented by the above formula [1], a specific aliphatic tetracarboxylic dianhydride represented by the following formula [B], and the following formula. The reason why the diamine compound represented by [C] is a raw material and can be easily produced is therefore a polylysine which is composed of a structural formula of a repeating unit represented by the following formula [D] or the polyamine. The acid is subjected to a ruthenium imidized polyimine. Further, the specific tetracarboxylic dianhydride represented by the formula [B] is the same as the specific aliphatic tetracarboxylic dianhydride represented by the above formula [2]. At this time, R ¹ in the formula [B] is the same tetravalent group as Z ¹ in the formula [2].

(In the formula [B] and the formula [C], R ¹ and R ² have the same meanings as defined in the formula [A]).

(In the formula [D], R ¹ and R ² have 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 an alkane having 1 to 5 carbon atoms of A ³ and A ⁴ represented by the formula [A] can be obtained by a usual synthesis method. The group or the ethyl group is introduced into the polymer of the formula [D] obtained above.

<Method of Manufacturing Specific Polymer>

The specific polymer of the present invention reacts a tetracarboxylic acid component containing a specific tetracarboxylic dianhydride represented by the above formula [1] and a specific aliphatic tetracarboxylic dianhydride represented by the above formula [2] with a diamine component. Income. Specifically, a method of polycondensing a specific tetracarboxylic dianhydride, a specific aliphatic tetracarboxylic dianhydride, and a diamine component to obtain a polyamic acid, and dehydrating polycondensation of a tetracarboxylic acid component and a diamine component can be used. Or a method of polycondensation to obtain poly-proline.

In order to obtain polyalkyl amide, the following formula can be used. Method for polycondensing a tetracarboxylic acid and a diamine component which dialkylate a carboxylic acid group, and a method for polycondensing a dicarboxylic acid dihalide and a diamine component which dialkylate a carboxylic acid group Or a method of converting a carboxyl group of polyproline to an ester.

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

The reaction of the diamine component with the tetracarboxylic acid component usually involves the diamine component and the tetracarboxylic acid component in an organic solvent. The organic solvent to be used in this case is not particularly limited as long as it is a polyimide precursor which can be produced by dissolution. Specific examples of the organic solvent used for the reaction are listed below, but are not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl Amidoxime, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D- 1]~ Solvent represented by the formula [D-3].

(In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, in the formula [D-3] , D ³ represents an alkyl group having 1 to 4 carbon atoms).

These can be used alone or in combination. Further, even a solvent which does not dissolve the polyimide precursor can be used in the above solvent as long as it does not precipitate in the precipitated polyimide precursor. Further, since the water in the organic solvent hinders the polymerization reaction and causes hydrolysis of the produced polyimide precursor, the organic solvent is preferably dried and dried.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, for example, a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred to directly add a tetracarboxylic acid component or to disperse or dissolve a tetracarboxylic acid component. a method of adding to an organic solvent; conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent; a method of adding a tetracarboxylic acid component and a diamine component, etc. Use any of these methods. Further, when the diamine component or the tetracarboxylic acid component is reacted in a plurality of types, the reaction may be carried out in a state of being mixed beforehand, or the reaction may be carried out in sequence, or the respective reactions may be carried out. The low molecular weight body is mixed to form a polymer. The polymerization temperature at this time may be any temperature of from -20 ° C to 150 ° C, but is preferably in the range of from -5 ° C to 100 ° C. Further, the reaction can be carried out at any concentration. However, when the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. When 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 is carried out at a high concentration, and then an organic solvent can be added.

In the polymerization reaction of the polyimide 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 0.8~1.2. As with the general polycondensation reaction, as the molar ratio approaches 1.0, the molecular weight of the resulting polyimine precursor becomes larger.

The polyimine which constitutes a specific polymer contained in the liquid crystal alignment treatment agent of the present invention is a polyimine obtained by ring-closing the polyimine precursor, and a closed loop of a proline group in the polyimide. The rate (also referred to as the oxime imidization rate) does not have to be 100%, and can be arbitrarily adjusted depending on the purpose or purpose.

A method for subjecting a polyimine precursor to ruthenium imidization, for example, a hydrazine imidization in which a solution of a polyimide precursor is directly heated or a catalyst is added to a solution of a polyimide precursor The catalyst is imidized.

The temperature at which the polyimine precursor is thermally imidated in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, preferably water produced by the imidization reaction. The reaction was carried out while excluding the outside of the system.

The catalyst oxime imidization of the polyimine precursor adds a basic catalyst and an acid anhydride to the solution of the polyimide precursor, and is at -20 to 250 ° C, preferably 0 to 180 ° C. Stir under. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group; the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles. The basic catalyst is, for example, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has a moderate basicity required for carrying out the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. When acetic anhydride is used, purification after completion of the reaction becomes easy. Preferably. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When the resulting polyimine precursor or polyimine is recovered from the reaction solution of the polyimide precursor or the polyimide, the reaction solution is poured into a solvent to precipitate. The solvent used for the precipitation is, for example, methanol, ethanol, isopropanol, acetone, hexane, butyl sirolimus, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water or the like. After being introduced into a solvent and allowing the precipitated polymer to be recovered by filtration, it can be dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the precipitate-recovered polymer is redissolved in an organic solvent, and the reprecipitation recovery operation is repeated 2 to 10 times to reduce impurities in the polymer. In the solvent at the time, for example, an alcohol, a ketone, a hydrocarbon, or the like is used, and when a solvent selected from three or more types selected from the above is used, the purification efficiency can be further improved, which is preferable.

The molecular weight of the specific polymer contained in the liquid crystal alignment agent of the present invention is determined by GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained by the above, the workability at the time of film formation, and the coating property. The weight average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<Liquid alignment treatment agent>

The liquid crystal alignment treatment agent of the present invention forms a coating solution for a liquid crystal alignment film, and contains a polymer component and a solvent to form a coating solution for a polymer film.

As described above, the liquid crystal alignment treatment agent of the present invention contains The specific polymer is selected from the group consisting of a tetracarboxylic acid component containing a specific tetracarboxylic dianhydride represented by the above formula [1] and a specific aliphatic tetracarboxylic dianhydride represented by the above formula [2]. a polyimine precursor obtained by reacting a specific tetracarboxylic acid component and a specific aliphatic tetracarboxylic acid component with a diamine component, and at least a polyimine obtained by subjecting the polyimine precursor to ruthenium imidization 1 kind of polymer. By using a liquid crystal alignment treatment agent containing such a specific polymer, a liquid crystal alignment film excellent in light resistance and excellent in voltage retention characteristics (voltage holding ratio) can be obtained. The reason for this is as follows.

The specific tetracarboxylic dianhydride has a structure in which two dicarboxylic dianhydrides are bonded by a methylene group. Since the methylene group is flexible (soft), the polytetraimide precursor or polycondensation obtained by reacting the specific tetracarboxylic dianhydride having such a methylene group with a specific aliphatic tetracarboxylic dianhydride and a diamine component The quinone imine is a cross-linker in the molecule and in the molecule by the softness of the methylene group. As a result, the specific polymer is polymerized and the density is high. The liquid crystal alignment film having a specific polymer having a high density becomes a dense film, and as shown in the examples below, even after strong ultraviolet irradiation, the voltage holding ratio can be suppressed from being lowered, and the light resistance is excellent.

In general, the aromatic acid anhydride is weak in light resistance, but the specific tetracarboxylic dianhydride has a soft methylene group as described above, so that the light resistance of the liquid crystal alignment film having a specific polymer does not decrease and can be maintained high. Voltage retention rate.

Such excellent voltage holding characteristics are obtained by using a specific tetracarboxylic dianhydride having a methylene group and a non-aromatic specific aliphatic tetracarboxylic dianhydride as a raw material of a specific polymer, so that the effect can be further increased.

As a result of the above, by using two kinds of tetracarboxylic dianhydrides of a specific tetracarboxylic dianhydride and a specific aliphatic tetracarboxylic dianhydride, it can be used as a raw material of the specific polymer contained in the liquid crystal alignment treatment agent of the present invention. A liquid crystal alignment film which is excellent in light resistance and excellent in voltage retention characteristics is obtained.

All of the polymer components in the liquid crystal alignment treatment agent of the present invention may be all specific polymers, or may be mixed with other polymers other than the polymer. In this case, the content of the polymer other than the polymer is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass based on the specific polymer. Other polymers other than the polymer include, for example, a polyimine precursor which does not use the specific tetracarboxylic dianhydride represented by the above formula [1] and the specific aliphatic tetracarboxylic dianhydride represented by the above formula [2]. Or polyimine. Further, there are, for example, an acrylic polymer, a methacrylic polymer, polystyrene or polyoxyalkylene.

The solid content concentration in the liquid crystal alignment agent of the present invention can be appropriately changed by setting the thickness of the liquid crystal alignment film to be formed, and is preferably 0.5 to 10% by mass, and more preferably 1 to 8% by mass. When the solid content concentration is less than 0.5% by mass, it may become difficult to form a uniform and non-defective coating film, and when it is more than 10% by mass, the storage stability of the solution may be deteriorated. Here, the solid component refers to a component obtained by removing a solvent from a liquid crystal alignment treatment agent, and refers to the specific polymer described above, a polymer other than the polymer, and various additives described below.

The solvent in the liquid crystal alignment treatment agent of the present invention is preferably from 70 to 99.9% by mass in terms of the solvent in the liquid crystal alignment treatment agent from the viewpoint of coating to form a uniform liquid crystal alignment film. This content can be based on the purpose of the liquid The thickness of the crystal alignment film is appropriately changed.

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

For example, there are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl hydrazine, γ- Butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. Among them, preferred are, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ -butyrolactone or a solvent represented by the above formula [D-1] to formula [D-3]. These can be used alone or in combination.

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ -butyrolactone are preferably used. Further, when the solubility of the specific polymer in the solvent is high, 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 of the present invention is preferably from 10 to 100% by mass based on the total amount of the solvent contained in the liquid crystal alignment treatment agent. It is preferably 20 to 90% by mass. More preferably 30 to 80% by mass.

The liquid crystal alignment treatment agent of the present invention can use a solvent (also referred to as a weak solvent) for improving the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied, within a range that does not impair the effects of the present invention. . Specific examples of the weak solvent are listed below, but are not limited to these examples.

For example, there are ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butene Alcohol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 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-butanediol , 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-butyl Oxyethane, 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, Propylene carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol Butyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, decyl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy Propyl alcohol, 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 glycol 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, lactate B Ester, methyl acetate, ethyl acetate, n-butyl acetate, acrylic acid Alcohol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Propionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate An ester, isoamyl lactate or a solvent represented by the above formula [D-1] to formula [D-3].

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether, or the above formula [D-1]~ is preferably used. A solvent or the like represented by the formula [D-3].

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

The liquid crystal alignment treatment agent of the present invention may contain crosslinkability having an epoxy group, an isocyanate group, an oxetane group or a cyclic carbonate group, within a range not impairing the effects of the present invention. a compound; a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxy alkyl group; or a crosslinkable compound having a polymerizable unsaturated bond. These substituents or polymerizable unsaturated bonds must have two or more of the crosslinkable compounds.

A crosslinkable compound having an epoxy group or an isocyanate group, for example, bisphenol acetone glycidyl ether, novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylamino group Diphenylene, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl Glycidyl ether ethane, bisphenol hexafluoroacetamidine dihydrate Oleic ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis (2) , 3-glycidoxy) Octafluorobiphenyl, triglycidyl-p-aminophenol, meta-xylenediamine, 2-(4-(2) ,3-glycidoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane or 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, for example, there is a crosslinkable compound represented by the formula [4a] to the formula [4k] disclosed in 58-59 of International Publication WO01/132751.

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

Specifically, for example, there is a crosslinkable compound represented by the formula [5-1] to the formula [5-42] disclosed in 76-82 of International Publication WO01/132751.

a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group, for example, an amine-based resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, or a guanamine resin , Glycoluril-formaldehyde resin, Succinylamide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group or both may be used. The melamine derivative or the benzoguanamine derivative may be present in the form of a dimer or a trimer. Among these, one triazine ring is preferred to have an average of three or more and six or less hydroxymethyl groups or alkoxymethyl groups.

Examples of such a melamine derivative or a benzoguanamine derivative, for example, a triazine ring of a commercial product, MX-750 substituted by an average of 3.7 methoxymethyl groups, and a triazine ring, an average of 5.8. Methoxymethylated melamine substituted by methoxymethyl substituted MW-30 (above manufactured by Sanwa-Chemical Co., Ltd.) or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. , methoxymethylated butoxymethylated melamine of Cymel 235, 236, 238, 212, 253, 254, etc., butoxymethylated melamine of Cymel 506, 508, etc., such as carboxyl group of Cymel 1141 Methoxymethylated isobutoxymethylated melamine, such as methoxymethylated ethoxymethylbenzamide of Cymel 1123, methoxymethylated butoxy of Cymel 1123-10 Methylated benzoquinone An amine such as butoxymethyl benzoguanamine of Cymel 1128, a carboxyl group-containing methoxymethylated ethoxymethyl benzoguanamine such as Cymel 1125-80 (manufactured by Mitsui Cyanamid Co., Ltd.). Further, examples of the glycoluril include, for example, butoxymethylated glycoluril of Cymel 1170, methylolated glycoluril of Cymel 1172, and methoxymethylolated glycoluril of Powderlink 1174.

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

More specifically, for example, the crosslinkable compound represented by the formula [6-1] to the formula [6-48] disclosed in pages 62 to 66 of International Publication WO2011/132751.

A crosslinkable compound having a polymerizable unsaturated bond, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, tris(methyl) a propylene methoxy ethoxy trimethylolpropane or a glycerol polyglycidyl ether poly(meth) acrylate equivalent to a crosslinkable compound having three polymerizable unsaturated groups in the molecule; further, for example, ethylene glycol (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 II Acrylate, propylene oxide bisphenol type di(meth) acrylate, 1,6-hexanediol di(A) Acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(methyl) Acrylate, bis-glycidyl phthalate di(meth) acrylate or hydroxytrimethyl acetic acid neopentyl glycol di(meth) acrylate is equal to crosslinkability of two polymerizable unsaturated groups in the molecule a compound; further, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2- Hydroxypropyl (meth) acrylate, 2-(methyl) propylene oxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono The acrylate, 2-(meth) propylene methoxyethyl phosphate or N- hydroxymethyl (meth) acrylamide is equivalent to a crosslinkable compound having one polymerizable unsaturated group in the molecule.

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

(In the formula [7], 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 or a phenanthrene ring. The group, E ₂ represents a group selected from the following formula [7a] or formula [7b], and n represents an integer of 1 to 4).

The above compound is an example of a crosslinkable compound, but is not limited thereto. Moreover, the crosslinkable compound used for the liquid crystal alignment treatment agent of the present invention may be one type or a combination of two or more types.

The content of the crosslinkable compound in the liquid crystal alignment agent of the present invention 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 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.

When the liquid crystal alignment treatment agent of the composition of the present invention is used as a liquid crystal alignment film, the charge movement in the liquid crystal alignment film is promoted, and the compound which releases the charge of the liquid crystal cell using the liquid crystal alignment film is promoted, preferably added. The nitrogen-containing heterocyclic amine compound represented by the formula [M1] to the formula [M156] disclosed in pages 69 to 73 of International Publication No. WO2011/132751. The amine compound may be directly added to the composition, but it is preferably added in a suitable solvent to a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass. The solvent is not particularly limited as long as it is an organic solvent capable of dissolving the above specific polyamidene-based polymer.

In the liquid crystal alignment treatment agent of the present invention, a compound which improves the film thickness uniformity or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used within the range which does not impair the effects of the present invention. Further, a compound or the like which enhances the adhesion between the liquid crystal alignment film and the substrate can also be used.

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

More specifically, for example, EFTOP EF301, EF303, EF352 (above, TOHKEM PRODUCTS), MEGAFAC F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), FLUORAD FC430, FC431 (above Sumitomo 3M) ASAHI GUARD AG710, SURFLONS-382, SC101, SC102, SC103, SC104, SC105, SC106 (above is manufactured by Asahi Glass Co., Ltd.). The use ratio of the surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include, for example, a functional decane-containing compound or an epoxy group-containing compound described below.

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-( 2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethyl Oxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1,4,7 - triazadecane, 10-triethoxydecyl-1,4,7-triazole Heteroane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl 3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl 3-aminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N-bis(oxyethylene)-3-aminopropyltri Ethoxy decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4 -hexanediol, N,N,N',N',-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane Or N, N, N', N', -tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

When the compound to be adhered to the substrate is used, it is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent. When the amount is less than 0.1 part by mass, the effect of improving the adhesion property cannot be expected, and when it is more than 30 parts by mass, the storage stability of the liquid crystal alignment treatment agent may be deteriorated.

In the liquid crystal alignment treatment agent of the present invention, in addition to the above-mentioned weak solvent, a crosslinkable compound, a compound which promotes charge release of a liquid crystal cell, and a compound which improves film thickness uniformity or surface smoothness of the liquid crystal alignment film, A dielectric substance for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film may be added without impairing the effect of the present invention. Or conductive material.

<Liquid alignment film ‧ Liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention is applied to a substrate, and after firing, it is subjected to alignment treatment by rubbing treatment or light irradiation, and can be used as a liquid crystal alignment film. Moreover, in the case of a vertical alignment use or the like, it can be used as a liquid crystal alignment film even 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 plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to the glass substrate. From the viewpoint of process simplification, it is preferred to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed. Further, when the reflective liquid crystal display element is only a single-sided substrate, an opaque substrate such as a germanium wafer may be used. In this case, a material such as aluminum that reflects light may be used as the electrode.

The coating method of the liquid crystal alignment treatment agent is not particularly limited, but is generally carried out industrially by screen printing, lithography, letterpress printing, or inkjet method. Other coating methods include, for example, a dipping method, a roll coating method, a slit coating method, a spin coating method, or a spray method, and the like can be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, the solvent used in the liquid crystal alignment treatment agent is blended 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. Preferably, the temperature is 30 to 250 ° C, and the solvent is evaporated to become a liquid crystal alignment film. When the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the liquid crystal display element The reliability is sometimes lowered, so 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 or 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 by the above-described method, and a liquid crystal cell is produced by a known method to obtain a liquid crystal display element. For example, a liquid crystal display device having a liquid crystal cell having two substrates disposed opposite to each other, a liquid crystal layer disposed between the substrates, and a liquid crystal layer disposed between the substrate and the liquid crystal layer The liquid crystal alignment film formed by the alignment treatment agent. Such a liquid crystal display element of the present invention has, for example, a vertical alignment (VA: Vertical Alignment) method or an IPS (In-Plane Switching) method, a twisted nematic (TN: Twisted Nematic) method, and an OCB alignment (OCB: Optically). Compensated Bend) and the like may also be a PSA (Polymer Sustained Alignment) method or the like. Further, the liquid crystal alignment film may be provided on at least one of the two substrates.

In the method for producing a liquid crystal cell, for example, a pair of substrates on which a liquid crystal alignment film is to be formed is formed, and a spacer is spread on a liquid crystal alignment film of a single-sided substrate, so that the liquid crystal alignment film surface is inside, and the other single side is bonded. A method of sealing a substrate by injecting a liquid crystal into a reduced pressure, or a method of sealing a liquid crystal onto a liquid crystal alignment film surface on which a spacer is dispersed, and bonding the substrate to perform sealing.

As described above, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention can be used even after long-time light irradiation. Since the liquid crystal alignment film having a reduced voltage holding ratio is suppressed, it is excellent in reliability, and can be applied to a liquid crystal television having a large screen and a high definition.

Hereinafter, embodiments of the present invention will be described in more detail.

[Examples]

Hereinafter, the present invention will be described in more detail with reference to examples but the present invention is not limited thereto.

The abbreviations used in the synthesis examples and examples are as follows.

<tetracarboxylic dianhydride> (specific tetracarboxylic dianhydride)

A1: tetracarboxylic dianhydride represented by the following formula [A1]

(specific aliphatic tetracarboxylic dianhydride)

A2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [A2])

A3: Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [A3])

A4: tetracarboxylic dianhydride represented by the following formula [A4]

A5: tetracarboxylic dianhydride represented by the following formula [A5]

(other tetracarboxylic dianhydride)

A6: pyromellitic dianhydride (tetracarboxylic dianhydride represented by the following formula [A6])

<Diamine component>

B1: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene (diamine compound represented by the following formula [B1])

B2: 1,3-diamino-5-[4-(trans-4-n-heptylcyclohexyl)phenoxymethyl]benzene (diamine compound represented by the following formula [B2])

B3: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene (hereinafter, the formula [B3] Diamine compound

B4: 1,3-diamino-5-{4-[4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxymethyl}benzene (shown by the following formula [B4] Diamine compound)

B5: a specific side chain type diamine compound represented by the following formula [B5]

B6: 1,3-diamino-4-octadecyloxybenzene (diamine compound represented by the following formula [B6])

B7: m-phenylenediamine (diamine compound represented by the following formula [B7])

B8: p-phenylenediamine (diamine compound represented by the following formula [B8])

B9: 3,5-diaminobenzoic acid (diamine compound represented by the following formula [B9])

B10: a diamine compound represented by the following formula [B10]

<organic solvent> (polar solvent)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

G-BL: γ-butyrolactone

(other organic solvents)

BCS: 2-butoxyethanol

PB: propylene glycol monobutyl ether

<Measurement of molecular weight of polyimine precursor and polyimine]

The molecular weight of the polyimine precursor and the polyimine in the synthesis example is a room temperature gel permeation chromatography (GPC) device (GPC-101). The column (KD-803, KD-805) (manufactured by Shodex Co., Ltd.) was measured as follows.

Column temperature: 50 ° C

Solvent: N,N'-dimethylformamide (additive is lithium bromide-hydrate (LiBr‧H ₂ O) is 30 mmol / L (liter), phosphoric acid ‧ anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) is 10ml/L)

Flow rate: 1.0ml/min

Standard sample for the production of calibration lines: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by TOSOH) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratories).

(Determination of the imidization rate of polyfluorene imine)

The ruthenium imidization ratio of the polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, 5 (manufactured by Kusano Scientific Co., Ltd.) was added with hydrogenated dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane) mixed product) (0.53 ml), and ultrasonic waves were applied to completely dissolve. This solution was measured for proton NMR at 500 MHz by an NMR measuring machine (JNW-ECA500) (manufactured by JEOL DATUM Co., Ltd.). The sulfhydrylation rate is determined by using protons from a structure that does not change before and after imidization as a reference proton, and the peak value of the proton is used and the NH group derived from proline which is present in the vicinity of 9.5 ppm to 10.0 ppm. The cumulative value of the proton peak is obtained by the following formula.

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

In the above formula, x is derived from the proton peak cumulative value of the NH group of the proline, the peak cumulative value of the y-based reference proton, and α is the poly-proline (the imidization ratio is 0%). The ratio of the number of reference protons of the NH proton of the amine acid.

<Synthesis Example 1>

A1 (3.82 g, 18.0 mmol), B1 (4.11 g, 10.8 mmol), B7 (2.75 g, 25.2 mmol) were mixed in NMP (22.8 g), and reacted at 40 ° C for 5 hours, then A2 (3.53 g, 18.0 mmol) and NMP (18.7 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (A) having a solid content concentration of 20.0% by mass. The polyamine had a number average molecular weight of 11,500 and a weight average molecular weight of 38,600.

<Synthesis Example 2>

A1 (3.81 g, 18.0 mmol), B2 (4.25 g, 10.8 mmol), B8 (2.72 g, 25.1 mmol) were mixed in NMP (23.1 g), and reacted at 40 ° C for 5 hours, then A2 (3.52 g, 18.0 mmol) and NMP (18.9 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid content concentration of 20.0% by mass.

After adding NMP to the obtained polyamic acid solution (15.0 g), and diluting it to 6% by mass, acetic anhydride (2.01 g) and pyridine (1.02 g) as a ruthenium amide catalyst were added at 40 ° C. Reaction for 4 hours. Do this The reaction solution was poured into methanol (350 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (B). The polyimine had a hydrazine imidation ratio of 50%, a number average molecular weight of 12,500, and a weight average molecular weight of 38,200.

<Synthesis Example 3>

A1 (2.83 g, 13.3 mmol), B6 (3.76 g, 10.0 mmol), B10 (2.72 g, 23.3 mmol) were mixed in NMP (16.9 g), and reacted at 40 ° C for 5 hours, then A2 (3.92 g, 20.0 mmol) and NMP (13.8 g) were reacted at 40 ° C for 6 hours to obtain a polyglycine solution having a solid content concentration of 20.0% by mass.

After adding NMP to the obtained polyamic acid solution (15.1 g), and diluting it to 6 mass%, acetic anhydride (2.28g) and pyridine (1.18g) which are a ruthenium-imidation catalyst were added, and it was 40 degreeC. Reaction for 3 hours. This reaction solution was poured into methanol (350 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (C). The polyimine had a hydrazine imidation ratio of 70%, a number average molecular weight of 11,500, and a weight average molecular weight of 31,400.

<Synthesis Example 4>

A1 (4.50 g, 21.2 mmol) and B7 (4.59 g, 42.4 mmol) were mixed in NMP (21.8 g), and reacted at 40 ° C for 5 hours, then A3 (5.31 g, 21.2 mmol) and NMP (17.8 g) were added. The reaction was carried out at 50 ° C for 6 hours to obtain a polyamic acid having a solid content concentration of 20.0% by mass. Solution.

After adding NMP to the obtained polyamic acid solution (15.0 g), and diluting it to 6% by mass, acetic anhydride (2.73 g) and pyridine (1.60 g) as a ruthenium amide catalyst were added at 40 ° C. Reaction for 3.5 hours. This reaction solution was poured into methanol (350 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (D). The polyimine had a ruthenium iodide ratio of 53%, a number average molecular weight of 13,100, and a weight average molecular weight of 35,000.

<Synthesis Example 5>

A1 (1.10 g, 5.19 mmol), B1 (3.95 g, 10.4 mmol), B9 (2.37 g, 15.6 mmol) were mixed in NMP (22.9 g), and reacted at 40 ° C for 5 hours, then A2 (4.07 g, 20.8 mmol) and NMP (18.7 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid content concentration of 20.0% by mass.

After adding NMP to the obtained polyamic acid solution (15.0 g), and diluting it to 6% by mass, acetic anhydride (2.12 g) and pyridine (1.15 g) as a ruthenium amide catalyst were added at 40 ° C. Reaction for 3 hours. This reaction solution was poured into methanol (350 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (E). The polyimine had a hydrazine imidation ratio of 52%, a number average molecular weight of 12,600, and a weight average molecular weight of 36,200.

<Synthesis Example 6>

A1 (7.80 g, 36.7 mmol) and B8 (6.11 g, 56.5 mmol) were mixed in NMP (22.0 g), and reacted at 40 ° C for 5 hours, then A2 (3.88 g, 19.8 mmol) and NMP (18.0 g) were added. The reaction was carried out at 40 ° C for 6 hours to obtain a polyamic acid solution (F) having a solid content concentration of 20.0% by mass. The polyamine had a number average molecular weight of 11,200 and a weight average molecular weight of 38,500.

<Synthesis Example 7>

A1 (1.41 g, 6.65 mmol), B5 (2.62 g, 5.32 mmol), B9 (3.24 g, 21.3 mmol) were mixed in NMP (23.9 g), and reacted at 40 ° C for 5 hours, then A3 (4.99 g, 19.9 mmol) and NMP (19.5 g) were reacted at 50 ° C for 6 hours to obtain a polyamic acid solution (G) having a solid content concentration of 20.0% by mass. The polyamine had a number average molecular weight of 13,500 and a weight average molecular weight of 35,600.

<Synthesis Example 8>

A1 (3.06 g, 14.4 mmol), B3 (3.74 g, 8.65 mmol), B10 (2.47 g, 20.2 mmol) were mixed in NMP (1.53 g), and reacted at 40 ° C for 5 hours, then A4 (3.23 g, 14.4 mmol) and NMP (12.6 g) were reacted at 50 ° C for 6 hours to obtain a polyamic acid solution having a solid content concentration of 20.0% by mass.

After adding NMP to the obtained polyamic acid solution (15.0 g) and diluting it to 6 mass%, acetic anhydride (1.89 g) and pyridine (0.90 g) as a ruthenium amide catalyst were added at 50 ° C. Reaction for 3 hours. Do this The reaction solution was poured into methanol (350 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (H). The polyimine had a hydrazine imidation ratio of 70%, a number average molecular weight of 11,800, and a weight average molecular weight of 30,400.

<Synthesis Example 9>

A1 (2.25 g, 10.6 mmol), B4 (2.71 g, 6.06 mmol), B7 (1.64 g, 15.2 mmol), B9 (1.38 g, 9.09 mmol) were mixed in NMP (2.23 g), and reacted at 40 ° C. After the hour, A4 (4.42 g, 19.7 mmol) and NMP (18.3 g) were added, and the mixture was reacted at 50 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.

After adding NMP to the obtained polyamic acid solution (15.0 g), and diluting it to 6 mass%, acetic anhydride (2.20g) and pyridine (1.12g) which are a ruthenium-imidation catalyst were added, and 50 degreeC was 50 degreeC. Reaction for 3 hours. This reaction solution was poured into methanol (350 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (I). The polyimine had a hydrazine imidation ratio of 51%, a number average molecular weight of 11,000, and a weight average molecular weight of 30,100.

<Synthesis Example 10>

A1 (2.02 g, 9.52 mmol) and B8 (3.43 g, 31.7 mmol) were mixed in NMP (22.2 g), and reacted at 40 ° C for 5 hours, then A5 (6.67 g, 22.2 mmol) and NMP (18.2 g) were added. To make 25 The reaction was carried out at ° C for 12 hours to obtain a polyamic acid solution (J) having a solid content concentration of 20.0% by mass. The polyamine had a number average molecular weight of 11,800 and a weight average molecular weight of 36,300.

<Synthesis Example 11>

A1 (11.2 g, 52.9 mmol), B1 (6.04 g, 15.9 mmol), B7 (4.01 g, 37.1 mmol) were mixed in NMP (40.2 g), and reacted at 40 ° C for 24 hours to obtain a solid concentration of 20.0. Mass % polyaminic acid solution (K). The polyamine had a number average molecular weight of 7,100 and a weight average molecular weight of 29,800.

<Synthesis Example 12>

A2 (5.10 g, 26.0 mmol), B6 (2.94 g, 7.80 mmol), B10 (2.22 g, 18.2 mmol) were mixed in NMP (32.2 g), and reacted at 40 ° C for 8 hours to obtain a solid concentration of 20.0. Mass% polyamine solution.

After adding NMP to the obtained polyamic acid solution (15.0 g), and diluting it to 6 mass %, acetic anhydride (2.00g) and pyridine (1.01g) which are a ruthenium-imidation catalyst were added, and it was 40 degreeC. Reaction for 3 hours. This reaction solution was poured into methanol (350 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (L). The polyimine had a hydrazine imidation ratio of 70%, a number average molecular weight of 13,800, and a weight average molecular weight of 35,600.

<Synthesis Example 13>

A3 (3.80 g, 15.2 mmol) and B7 (3.29 g, 30.4 mmol) were mixed in NMP (22.2 g), and reacted at 50 ° C for 3 hours, then A2 (2.98 g, 15.2 mmol) and NMP (18.1 g) were added. The reaction was carried out at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid content concentration of 20.0% by mass.

After adding NMP to the obtained polyamic acid solution (15.0 g), and diluting it to 6% by mass, acetic anhydride (3.10 g) and pyridine (1.52 g) as a ruthenium amide catalyst were added at 50 ° C. Reaction for 3.5 hours. This reaction solution was poured into methanol (350 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (M). The polyimine had a hydrazine imidation ratio of 50%, a number average molecular weight of 14,700, and a weight average molecular weight of 37,100.

<Synthesis Example 14>

A1 (1.03 g, 4.85 mmol), B1 (3.70 g, 9.71 mmol), B9 (2.22 g, 14.6 mmol) were mixed in NMP (22.3 g), and reacted at 40 ° C for 5 hours, then A6 (4.24 g, 19.4 mmol) and NMP (18.3 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid content concentration of 20.0% by mass.

After adding NMP to the obtained polyamic acid solution (15.0 g), and diluting it to 6 mass%, acetic anhydride (1.86g) and pyridine (0.98g) which are a ruthenium-imidation catalyst were added, and it was 40 degreeC. Reaction for 3 hours. The reaction solution was poured into methanol (350 ml), and the resulting precipitate was filtered. Got it. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (N). The polyimine had a hydrazine imidation ratio of 52%, a number average molecular weight of 13,800, and a weight average molecular weight of 34,700.

<Synthesis Example 15>

A6 (4.52 g, 20.7 mmol) and B8 (3.45 g, 31.9 mmol) were mixed in NMP (22.4 g), and reacted at 40 ° C for 5 hours, then A2 (2.19 g, 11.2 mmol) and NMP (18.3 g) were added. The reaction was carried out at 40 ° C for 6 hours to obtain a polyamic acid solution (O) having a solid content concentration of 20.0% by mass. The polyamine had a number average molecular weight of 16,100 and a weight average molecular weight of 42,000.

Table 1 shows the polyamic acid and polyimine obtained in Synthesis Examples 1 to 15.

<Example 1>

The polyamidic acid solution (A) (9.03 g), NMP (8.90 g), and BCS (12.0 g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 1 were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent. (1). It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (1), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Example 2>

The polyimine powder (B) (1.80 g) obtained in Synthesis Example 2, NMP (9.02 g), NEP (7.51 g), and BCS (13.5 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent ( 2). It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (2), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Example 3>

The polyimine powder (B) (1.50 g) obtained in Synthesis Example 2, NMP (12.4 g), NEP (10.3 g), and BCS (18.6 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (3). ). It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (3), "evaluation of inkjet coating property of liquid crystal alignment treatment agent" was carried out under the above conditions.

<Example 4>

The polyimine powder (C) (1.80 g) obtained in Synthesis Example 3, NMP (9.01 g), G-BL (9.02 g), and BCS (12.0 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent. (4). It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (4), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Example 5>

The polyimine powder (D) (1.80 g) obtained in Synthesis Example 4, NMP (7.53 g), NEP (12.1 g), G-BL (1.53 g), and PB (9.11 g) were mixed at 25 ° C for 8 hours. A liquid crystal alignment treatment agent (5) was obtained. It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (5), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Example 6>

The polyimine powder (E) (1.79 g) obtained in Synthesis Example 5, NMP (9.00 g), NEP (14.5 g), BCS (3.02 g), and PB (3.00 g) were mixed at 25 ° C for 8 hours to obtain Liquid crystal alignment treatment agent (6). It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (6), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Example 7>

The polyimine powder (E) (1.50 g) obtained in Synthesis Example 5, NMP (8.27 g), NEP (16.5 g), and PB (16.5 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (7). ). It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (7), "evaluation of inkjet coating property of liquid crystal alignment treatment agent" was carried out under the above conditions.

<Example 8>

Polylysine solution (F) (9.00 g), NMP (3.00 g), G-BL (9.06 g), and BCS (9.01 g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 6 were mixed at 25 ° C. The liquid crystal alignment treatment agent (8) was obtained in an hour. It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (8), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Example 9>

Polylysine solution (G) (9.01 g), NEP (9.02 g), G-BL (9.02 g), BCS (6.01 g), and PB (6.00 g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 7. The mixture was mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (9). It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (9), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Example 10>

The polyimine powder (H) (1.80 g), NMP (6.00 g), NEP (6.05 g), BCS (6.04 g) and PB (3.01 g) obtained in Synthesis Example 8 were mixed at 25 ° C for 8 hours to obtain Liquid crystal alignment treatment agent (10). It was confirmed that no turbidity and precipitation were observed in the liquid crystal alignment agent. Often, it is a homogeneous solution.

Using the obtained liquid crystal alignment treatment agent (10), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Example 11>

The polyimine powder (I) (1.80 g) obtained in Synthesis Example 9, NMP (12.0 g), NEP (9.00 g), and BCS (9.05 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (11). ). It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (11), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Example 12>

Polylysine solution (J) (9.04 g), NMP (16.5 g), NEP (9.02 g), and PB (4.50 g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 10 were mixed at 25 ° C for 8 hours. A liquid crystal alignment treatment agent (12) was obtained. It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (12), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Comparative Example 1>

Polylysine solution (K) (9.03 g), NMP (9.31 g), and BCS (12.2 g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 11. The mixture was mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (13). It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (13), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Comparative Example 2>

The polyimine powder (L) (1.80 g) obtained in Synthesis Example 12, NMP (9.00 g), G-BL (9.02 g), and BCS (12.0 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent. (14). It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (14), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Comparative Example 3>

The polyimine powder (M) (1.80 g) obtained in Synthesis Example 13, NMP (7.50 g), NEP (12.0 g), G-BL (1.50 g), and PB (9.00 g) were mixed at 25 ° C for 8 hours. A liquid crystal alignment treatment agent (15) was obtained. It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (15), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Comparative Example 4>

The polyimine powder (N) (1.80 g) obtained in Synthesis Example 14, NMP (9.00 g), NEP (15.0 g), BCS (3.06 g), and PB (3.03 g) were mixed at 25 ° C for 8 hours to obtain Liquid crystal alignment treatment agent (16). It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (16), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

<Comparative Example 5>

Polylysine solution (O) (9.05 g), NMP (3.00 g), G-BL (9.02 g), and BCS (9.00 g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 15 were mixed at 25 ° C. The liquid crystal alignment treatment agent (17) was obtained in an hour. It was confirmed that this liquid crystal alignment treatment agent was found to have no abnormality such as turbidity and precipitation, and was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (17), "production of liquid crystal cell and evaluation of electrical characteristics" were carried out under the above conditions.

Using the liquid obtained in each of the examples and comparative examples of the present invention In the crystal alignment treatment, "production of liquid crystal cell", "evaluation of electrical characteristics (voltage holding ratio)", and "evaluation of inkjet coating property of liquid crystal alignment treatment agent" were performed. The conditions are as follows.

Tables 1 and 2 show Examples 1 to 12 and Comparative Examples 1 to 5 The raw material (tetracarboxylic dianhydride and diamine component) of the specific polymer contained in the obtained liquid crystal alignment treatment agent.

<Production of liquid crystal cell and evaluation of electrical characteristics>

The liquid crystal alignment treatment agents obtained in Examples 1, 2, 4 to 6, 8 to 12 and Comparative Examples 1 to 5 were subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm to prepare a liquid crystal cell. This solution was spin-coated on an ITO surface of a 30×40 mm substrate (length 40 mm × width 30 mm, thickness 0.7 mm) of ITO electrode washed with pure water and IPA (isopropyl alcohol) on a heating plate. The film was heat-treated at 80 ° C for 5 minutes, and heat-treated at 230 ° C for 30 minutes in a heat cycle type dust-free oven to obtain an ITO substrate of an agglomerated iridium imine liquid crystal alignment film having a thickness of 100 nm. The coating film surface of this ITO substrate was rubbed by a rubbing apparatus having a roll diameter of 120 mm, and the rubbing was performed under the conditions of a roll rotation number of 1000 rpm, a roll travel speed of 50 mm/sec, and a press-in amount of 0.1 mm.

Two sheets of the ITO substrate with the liquid crystal alignment film obtained were prepared, and the liquid crystal alignment film surface was placed inside, and a 6 μm spacer was sandwiched and combined, and then a sealant (XN-1500T) (manufactured by Mitsui Chemicals, Inc.) was printed. Next, after the other substrate and the liquid crystal alignment film surface were bonded to each other, the sealing agent was heat-treated at 150 ° C for 90 minutes in a heat cycle type dust-free oven, and was hardened to prepare an empty cell. In this empty cell, a liquid crystal cell is obtained by injecting a liquid crystal and sealing the injection port by a vacuum injection method.

Further, the liquid crystal alignment treatment agent (1) obtained in Example 1, the liquid crystal alignment treatment agent (2) obtained in Example 2, the liquid crystal alignment treatment agent (4) obtained in Example 4, and the liquid crystal alignment obtained in Example 6 were used. Liquid crystal alignment treatment agent (9) obtained by treating agent (6), and Example 9 to Example 11, liquid crystal alignment treatment agent (11), and liquid crystal obtained in Comparative Example 1. In the liquid crystal cell of the alignment treatment agent (13), the liquid crystal alignment treatment agent (14) obtained in Comparative Example 2, and the liquid crystal alignment treatment agent (16) obtained in Comparative Example 4, the liquid crystal was a nematic liquid crystal (MLC-6608) ( Merck‧Japan company).

Further, the liquid crystal alignment treatment agent (5) obtained in Example 5, the liquid crystal alignment treatment agent (8) obtained in Example 8, the liquid crystal alignment treatment agent (12) obtained in Example 12, and the liquid crystal alignment treatment obtained in Comparative Example 3 were used. In the liquid crystal cell of the liquid crystal alignment agent (17) obtained in the agent (15) and the comparative example 5, nematic liquid crystal (MLC-2041) (manufactured by Merck Japan Co., Ltd.) was used for the liquid crystal.

The liquid crystal alignment obtained by the above was used to evaluate the liquid crystal alignment. In the liquid crystal alignment, a liquid crystal cell was observed using a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Co., Ltd.), and it was confirmed whether or not there was an alignment defect. As a result, no alignment defects were observed in the liquid crystal cell obtained in each of the examples and the comparative examples, and uniform alignment was exhibited.

With respect to the liquid crystal cell fabricated as described above, a voltage of 1 V was applied for 60 μs at a temperature of 80 ° C, and the voltage after 16.67 ms and after 50 ms was measured, and how much the voltage can be maintained is calculated by the voltage holding ratio (VHR). The measurement was performed using a VHR-1 voltage retention ratio measuring device (manufactured by Toyo Corporation) with a setting of Voltage: ±1 V, Pulse Width: 60 μs, Flame Period: 16.67 ms, or 50 ms. The liquid crystal cell after the measurement of the voltage holding ratio was irradiated with ultraviolet rays of 50 J/cm ² in terms of 365 nm, and the voltage holding ratio was measured under the same conditions as above. Further, ultraviolet irradiation was carried out using a desktop type UV curing device (HCT3B28HEX-1) (manufactured by SEN LIGHT CORPORATION).

Table 3 shows the measurement results of the voltage holding ratio. Further, since the voltage holding ratio depends on the type of the diamine component, those who use the same diamine component must be compared with each other.

The liquid crystal alignment film obtained from the liquid crystal alignment treatment agents of the respective examples has a lower voltage holding ratio even when exposed to ultraviolet light irradiation, compared to the liquid crystal alignment film obtained from the liquid crystal alignment treatment agents of the respective comparative examples. .

Specifically, Example 1 uses two kinds of tetracarboxylic dianhydrides of a specific tetracarboxylic dianhydride and a specific aliphatic tetracarboxylic dianhydride, but Comparative Example 1 uses only one of the specific tetracarboxylic dianhydrides. . Further, the diamine components (B1 and B7) are the same. As a result, the voltage holding ratio of Comparative Example 1 was greatly lowered by ultraviolet irradiation.

Similarly, in Example 4, two types of tetracarboxylic dianhydride were used, but Comparative Example 2 used only another specific aliphatic tetracarboxylic dianhydride. Further, the diamine components (B6 and B10) are the same. As a result, the voltage holding ratio of Comparative Example 2 was further lowered by ultraviolet irradiation.

The same results were obtained for the comparison of Example 5 with Comparative Example 3.

Further, in the comparison of Example 6 with Comparative Example 4, Example 8 and Comparative Example 5, either of the two types of tetracarboxylic dianhydrides and other tetracarboxylic dianhydrides were used for Comparative Examples 4 and 5, but The voltage holding ratios of Comparative Examples 4 and 5 were greatly reduced by ultraviolet irradiation.

As a result, it is understood that the tetracarboxylic dianhydride of the specific type of the tetracarboxylic dianhydride and the specific aliphatic tetracarboxylic dianhydride can be used as a raw material of the specific polymer contained in the liquid crystal alignment treatment agent of the present invention. A liquid crystal alignment film having excellent light resistance is suppressed in which the reduction in voltage holding ratio is suppressed. A liquid crystal display element having such a liquid crystal alignment film does not deteriorate in voltage holding ratio even when irradiated with light for a long period of time, and has light resistance and is excellent in reliability.

<Evaluation of inkjet coating property of liquid crystal alignment treatment agent>

The liquid crystal alignment treatment agent (3) obtained in Example 3 of the present invention and the liquid crystal alignment treatment agent (7) obtained in Example 7 were subjected to pressure filtration using 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.). The coating was applied to an ITO (Indium Tin Oxide) vapor-deposited substrate washed with pure water and IPA (isopropyl alcohol), and the coated area was 70×70 mm, the nozzle pitch was 0.423 mm, and the scanning pitch was 0.5 mm. The cloth speed was 40 mm/sec, the time from application to temporary drying was 60 seconds, and the temporary drying was performed on a hot plate at 70 ° C for 5 minutes.

In each of the examples, a liquid crystal alignment film which was uniformly coated was not found on the obtained liquid crystal alignment film, and no repulsion or pinhole was observed.

The liquid crystal alignment treatment agent (3) obtained in Example 3 and the liquid crystal alignment treatment agent (7) obtained in Example 7 contain two types of tetracarboxylic acid which are specific tetracarboxylic dianhydrides and specific aliphatic tetracarboxylic dianhydrides. A specific polymer obtained by reacting an acid dianhydride with a diamine component. Specifically, implementation The liquid crystal alignment treatment agent (3) of Example 3 has the same configuration as that of the liquid crystal alignment treatment agent (2) of Example 2, and the liquid crystal alignment treatment agent (7) of Example 7 and the liquid crystal alignment treatment agent of Example 6 (6). The same composition.

Therefore, the liquid crystal alignment treatment agent (3) of Example 3 and the liquid crystal alignment treatment agent (7) of Example 7 were used, and the liquid crystal alignment film obtained by the inkjet method was observed, and the measurement results of the voltage holding ratio were observed (Examples 2 and 6). In the case of the above, it is presumed that the decrease in the voltage holding ratio is suppressed and the light resistance is excellent. Therefore, in the liquid crystal display element having the liquid crystal alignment film obtained by the inkjet method, in the same manner, even if it is irradiated with light for a long period of time, the voltage holding ratio is not lowered, and the light resistance is excellent, and the reliability is excellent.

Claims (6)

A liquid crystal alignment treatment agent characterized by containing a tetracarboxylic acid component selected from the group consisting of a tetracarboxylic dianhydride represented by the following formula [1] and an aliphatic tetracarboxylic dianhydride represented by the following formula [2] a polyimine precursor obtained by reacting an amine component and at least one polymer of the polyimine obtained by subjecting the polyimine precursor to ruthenium imidization, (In the formula [2], Z ¹ is selected from at least one tetravalent group of the following formula [2a] to formula [2j]) (In the formula [2a], 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 [2g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, Each can be the same or different). The liquid crystal alignment treatment agent of claim 1, which comprises N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ -butyrolactone as a solvent in a liquid crystal alignment treatment agent. . The liquid crystal alignment treatment agent according to the first aspect of the invention, which comprises a solvent selected from the group consisting of the solvents represented by the following formula [D-1] to the formula [D-3] as a solvent in the liquid crystal alignment treatment agent, (In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms). A liquid crystal alignment film characterized by using a liquid crystal alignment treatment agent according to claim 1 of the patent application. A liquid crystal alignment film characterized by using a liquid crystal alignment treatment agent according to claim 1 of the patent application, which is obtained by an inkjet method. A liquid crystal display element characterized by having a liquid crystal alignment film of item 4 or 5 of the patent application.