TWI504637B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Description

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

The present invention relates to a diamine compound, a polyimine precursor obtained by using the diamine compound, a polymer such as polyimine, a liquid crystal alignment treatment agent containing the polymer, and a liquid crystal obtained by the liquid crystal alignment treatment agent. An alignment film and a liquid crystal display element using the liquid crystal alignment film.

The liquid crystal alignment film is a constituent member of a liquid crystal display element which has been widely used as a display device, and functions to align a liquid crystal in a predetermined direction. Nowadays, the main liquid crystal alignment film used in the industry is formed of a liquid crystal alignment treatment agent composed of a polyimide precursor, that is, a polyamic acid (also called polyamic acid) or a polyimide reaction solution. Specifically, the liquid crystal alignment treatment agent is applied to the substrate, and after heating, the alignment treatment of the liquid crystal on the substrate surface in parallel or oblique alignment is performed. The alignment treatment is, for example, a surface extension treatment by rubbing, and an alignment treatment using an anisotropic optical reaction by polarized ultraviolet irradiation or the like is also proposed.

In addition to the function of aligning the liquid crystal in a certain direction, the liquid crystal alignment film also has a function of controlling the pretilt angle of the liquid crystal. In recent years, the liquid crystal display element has been highly functionalized, and its use range has been increasing. It is required for the liquid crystal alignment film to suppress display failure of the liquid crystal display element, thereby achieving high display quality performance and reliability.

For example, the rubbing treatment is performed by wiping the surface of the liquid crystal alignment film with a cloth. However, from the viewpoint of countermeasures against foreign matter, etc., the liquid crystal alignment film is required to have a slight degree of cutting by friction treatment, in other words, high friction resistance (high mechanical strength). Patent Document 1 describes a compound containing two or more epoxy groups in a molecule in a polyimine-based liquid crystal alignment treatment agent in order to improve the friction resistance.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-146100

In the manufacturing step of the liquid crystal panel constituting the liquid crystal display element, in order to remove a small amount of chips generated by the rubbing treatment or impurities adhering to the liquid crystal alignment film during firing, there is a step of washing the liquid crystal alignment film with water or an organic solvent. . At this time, it is necessary to dissolve the liquid crystal alignment film for such a cleaning liquid, particularly an organic solvent, in other words, it is necessary to have high solvent resistance. When the liquid crystal alignment film is dissolved in the cleaning liquid, a liquid crystal alignment film having a predetermined film thickness cannot be obtained, and it is difficult to achieve high display quality of the liquid crystal display element.

Further, with the increase in the performance of liquid crystal display elements in recent years, liquid crystal display elements have been used for large-screen, high-definition liquid crystal televisions, and for use in vehicles, 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. At this time, high stability to the backlight light is required. In particular, when the voltage holding ratio of one of the electrical characteristics is lowered by the light irradiation of the backlight, image sticking failure (line burnt) which is one of display defects of the liquid crystal display element is likely to occur, and a highly reliable liquid crystal display element cannot be obtained. Therefore, in addition to the initial characteristics, the liquid crystal alignment film is required to have a characteristic that the voltage holding ratio is not easily lowered even after long-time light irradiation.

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal alignment film having the above characteristics. In other words, the object of the present invention is to provide a liquid crystal alignment film having a sufficient solvent resistance and capable of suppressing a decrease in voltage holding ratio, and a liquid crystal which can obtain the liquid crystal alignment film, by having a sufficient solvent resistance in the cleaning step of the liquid crystal panel manufacturing step. An alignment treatment agent and a liquid crystal display element having excellent display quality using the liquid crystal alignment treatment agent.

Further, an object of the present invention is to provide a polyimine precursor constituting the above liquid crystal alignment treatment agent, a polyimine, and a diamine compound for obtaining the polyimide precursor or polyimine.

As a result of intensive studies by the present inventors, the following findings have been obtained, and the present invention has been completed. In other words, by using a diamine compound of a specific configuration, it was found that a polyimine precursor having a characteristic structure can be obtained, and further, the polyimide precursor can be imidized to obtain a characteristic structure. Polyimine.

It is found that a liquid crystal alignment treatment agent comprising at least one of such a polyimide precursor and a polyimine is suitable for forming a liquid crystal alignment film, and the obtained liquid crystal alignment film is very useful for achieving the object of the present invention described above. The diamine compounds of the above specific construction include novel compounds not disclosed in the literature.

The present invention has the following essential elements.

A liquid crystal alignment treatment agent characterized by comprising: a group selected from the group consisting of a polyimide precursor having a cyclic carbonate group and a polyimide which is imidized by a ruthenium imide. At least one polymer.

2. The liquid crystal alignment treatment agent according to Item 1, wherein the cyclic carbonate group is present at the side chain end of the polyimine precursor and the polyimine.

3. The liquid crystal alignment treatment agent according to the above item 1, wherein the side chain having the cyclic carbonate group is represented by the following formula [1].

[Chemical 1]

(X ₁ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or N(CH ₃ )CO-, X ₂ is an alkylene group having 1 to 5 carbon atoms, and X ₃ is a structure represented by the following formula [1a])

[Chemical 2]

4. The liquid crystal alignment treatment agent according to any one of the above-mentioned items 1 to 3, wherein the polyimine precursor and the polyimine are a polymer having a diamine compound represented by the following formula [2] as a raw material. ,

[Chemical 3]

(X ₁ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or N(CH ₃ )CO-, X ₂ is an alkylene group having 1 to 5 carbon atoms, X ₃ is a structure represented by the following formula [1a], and n is an integer of 1 to 4)

5. The liquid crystal alignment treatment agent according to any one of items 1 to 4 above, which further comprises a base having a primary amine group and a nitrogen-containing heterocyclic ring in a molecular structure.

6. The liquid crystal alignment treatment agent according to Item 5, wherein the base is at least one compound selected from the group consisting of 3-aminopropylimidazole and 3-picolylamine.

7. The liquid crystal alignment treatment agent according to any one of the items 1 to 6 above, which contains an organic solvent which dissolves the polyimine precursor and polyimine, and the organic solvent contains 5~ in the liquid crystal alignment treatment agent. 80% by mass of a weak solvent.

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

9. The liquid crystal alignment film according to item 8, wherein the liquid crystal alignment layer is provided between the pair of electrodes, and the active energy ray and the heat are disposed between the pair of substrates. A liquid crystal display device produced by the step of polymerizing a polymerizable compound to which a polymerizable compound is polymerized, and applying a voltage between the electrodes to polymerize the polymerizable compound.

A liquid crystal display element comprising the liquid crystal alignment film according to item 9 above.

11. The liquid crystal display device of claim 10, comprising a liquid crystal layer between the electrode and the liquid crystal alignment film; and the active energy ray and the heat are disposed between the pair of substrates A liquid crystal composition of at least one of the polymerizable compounds to be polymerized is produced by applying a voltage between the electrodes to polymerize the polymerizable compound.

A diamine compound characterized by the following formula [2], (X ₁ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or N(CH ₃ )CO-, X ₂ is an alkylene group having 1 to 5 carbon atoms, X ₃ is a structure represented by the following formula [1a], and n is an integer of 1 to 4)

A polyimine precursor obtained by reacting a diamine component containing the diamine compound of the above item 12 with an acid dianhydride component.

14. The polyimine precursor according to the above item 13, wherein the diamine component further contains a diamine compound represented by the following formula [3].

(Y ₁ is a single bond, and is selected from the group consisting of -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O-, -COO-, and -OCO- An organic group, a Y ₂ -based single bond, or a divalent organic group selected from the group consisting of (CH ₂ ) _b - (b is an integer of 1 to 10), and a Y ₃ -based single bond selected from -(CH ₂ ) _c -(c a divalent organic group in the group of 1 to 10, -O-, -CH ₂ O-, -COO-, and -OCO-. Y ₄ is selected from the group consisting of a benzene ring, a cyclohexyl ring, and a heterocyclic ring. a group of cyclic groups, wherein any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms. a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a divalent organic group substituted with a fluorine atom, or a divalent organic group selected from an organic group having a carbon number of 12 to 25 having a steroid skeleton. Y ₅ is selected a cyclic group in which a free benzene ring, a cyclohexyl ring, and a heterocyclic ring are grouped, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms or 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 divalent organic group substituted with a fluorine atom, and n is an integer of 0 to 4. Y ₆ is 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, Containing from 1 to 18 carbon atoms of the fluoroalkyl group, m an integer of 1 to 4. The line). 15. The polyimine precursor according to the above item 13 or 14, wherein the acid dianhydride component is a tetracarboxylic dianhydride represented by the following formula [4], [Chem. 8]

(Z ₁ is a 4-valent organic group having 4 to 13 carbon atoms and a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms).

16. The polyimine precursor according to item 15, wherein Z ₁ in the tetracarboxylic dianhydride is an organic group of any one of the following formulas [4a] to [4j], [Chem. 9]

(In the formula [4a], each of Z ₂ to Z ₅ is independently a group selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and in the formula [4g], each of the Z ₆ and Z ₇ systems is independently a hydrogen atom. , or methyl).

A polyimine which is obtained by subjecting a polyimine precursor according to any one of the above items 13 to 15 to dehydration ring closure.

The liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent of the present invention has a sufficient solvent resistance in the cleaning step in the liquid crystal panel manufacturing step, and can suppress a decrease in voltage holding ratio even when irradiated with light. A liquid crystal display element having such a liquid crystal alignment film has excellent display quality.

Further, according to the present invention, a novel diamine compound of the above liquid crystal alignment agent raw material can be provided, and a polyimine precursor produced by a diamine compound and a polyimine can be provided.

[Formation of the Invention]

The liquid crystal alignment treatment agent of the present invention contains any one of a polyimide precursor having a cyclic carbonate group and a polyimine obtained by subjecting the polyimide precursor to dehydration ring closure. The cyclic carbonate group is preferably located at the respective side chain ends of the polyimine precursor and the polyimine.

Specifically, the liquid crystal alignment treatment agent of the present invention contains at least a polyimine precursor having a side chain of the following formula [1] and at least a polyimine obtained by subjecting the polyimine precursor to dehydration ring closure. One kind.

[化10]

In the formula [1], X ₁ is selected from -O-(ether bond), -NH-(amino bond), -N(CH ₃ )-(methylated amine bond), -CONH-(guanamine) Key), -NHCO- (inverse amide bond), -CH ₂ O- (methylene ether bond), -COO- (ester bond), -OCO- (reverse ester bond), -CON(CH ₃ )- A bonding group of a group of (N-methylated decylamine bond) and N(CH ₃ )CO-(N-methylated sulfhydryl bond). From the viewpoint of easy synthesis of raw materials and easy viewpoint, X _{1 is} preferably -O-, -NH-, -CONH-, -NHCO-, -CON(CH ₃ )-, -CH ₂ O-, -COO. - or OCO-. More preferably -O-, -CONH-, -CON(CH ₃ )-, -CH ₂ O- or COO-.

In the formula [1], X ₂ is an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms.

In the formula [1], X ₃ represents a cyclic carbonate group. Specifically, X _{3 is} preferably a structure represented by the following formula [1a].

[11]

The cyclic carbonate group present at the end of the side chain in the formula [1] reacts with at least one of a carboxyl group and a hydroxyl group under heating to form a structure in which a polymer is crosslinked. Thereby, it is possible to form a liquid crystal alignment film which is excellent in solvent resistance and excellent in stability to light such as a backlight.

Further, when the cyclic carbonate group is located at the end of the side chain of the formula [1], a liquid crystal alignment film having a structure having a high crosslinking density and a high elongation or toughness can be obtained. Therefore, when rubbing, the elongation of the polymer is not easily hindered, and therefore, high frictional resistance can be achieved. Further, the cyclic carbonate group at the end of the side chain can effectively carry out the crosslinking reaction, and even when a crosslinkable compound is added, the residue of the crosslinkable compound which causes a decrease in the characteristics of the liquid crystal display element can be reduced. .

As described above, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent is excellent in solvent resistance in the production process of the liquid crystal panel, and the voltage holding ratio is not greatly affected by the light irradiation of the backlight. Further, since the friction resistance is also excellent, a liquid crystal display element excellent in display quality can be obtained by using the liquid crystal alignment film.

Hereinafter, the specific structure of the diamine compound used in the liquid crystal alignment agent of the present invention will be described in detail. The liquid crystal alignment agent of the present invention may contain other components in addition to the polyimine precursor and the polyimine, and preferably contains a basic compound or other diamine compound as a base.

<Specific diamine compound>

The liquid crystal alignment treatment agent of the present invention comprises a polyimine precursor obtained by reacting a diamine component with a tetracarboxylic dianhydride, and a polyimide obtained by subjecting the polyimine precursor to dehydration ring closure. In the specification, these are sometimes referred to collectively as specific polymers. The diamine component preferably contains a diamine compound represented by the following formula [2] (also referred to as a specific diamine compound in the present specification).

[化12]

In the formula [2], X ₁ , X ₂ and X ₃ have the same definitions as in the case of the above formula [1]. In the formula [2], n is an integer of 1 to 4, preferably an integer of n to 1 to 2, more preferably n is 1. The bonding position of the two amine groups (-NH ₂ ) in the formula [2] is not particularly limited. Specifically, with respect to the bonding group (X ₁ ) of the side chain, for example, the position of 2, 3 on the benzene ring, the position of 2, 4, the position of 2, 5, the position of 2, 6, 3, 4 Location, 3, 5 position. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, the position of 2, 4, the position of 2, 5, and the position of 3, 5 are preferable. Preferred combinations of X ₁ , X ₂ , X ₃ and n in the formula [2] are as shown in the combination numbers (2-1) to (2-15) shown in Table 1.

<Synthesis method of specific diamine compound>

The method for producing the specific diamine compound represented by the formula [2] is not particularly limited, and preferred methods are as follows, for example.

In one example, the specific diamine compound of the present invention is obtained by synthesizing a dinitro group represented by the following formula [2A], followed by reduction of a nitro group to conversion to an amine group. [Chemistry 13]

The method for reducing the dinitro group is not particularly limited, and is usually carried out using palladium-carbon, platinum oxide, nickel iridium nickel, platinum black, lanthanum-alumina, sulphurized platinum carbon or the like as a catalyst, in ethyl acetate, toluene, A method of reducing a solvent such as tetrahydrofuran, dioxane or an alcohol using hydrogen, hydrazine or hydrogen chloride. Further, X ₁ , X ₂ , X ₃ and n in the formula [2A] are the same as defined in the formula [2] in the above specific diamine compound.

Formula [. 2A] bis-nitro coupling system between X ₁ and X ₂ X _3, X ₁ bonded to the method dinitro portion interposed Thereafter, or between connecting portions so dinitro X ₁ and X ₂ are bonded portion Then, the method of bonding with X _{3 is} obtained.

These bonding groups can be appropriately selected by a known method using organic synthesis. For example, when X ₁ is an ether or a methylene ether bond, a method of forming such a bonding group, for example, a halogen derivative containing a dinitro group and a hydroxy derivative containing X ₂ and X ₃ in a base There is a method of reacting, or a method of reacting a dinitro group-containing hydroxy derivative with a halogen-substituted derivative containing X ₂ and X ₃ in the presence of a base.

When X ₁ is an amino group bond, for example, a method of reacting a corresponding halogen derivative containing a dinitro group with an amine group-substituted derivative containing X ₂ and X ₃ in the presence of a base may be mentioned.

When X ₁ is a guanamine bond, for example, there is a method of reacting a corresponding dinitro group-containing ruthenium chloride with an amine substituent containing X ₂ and X ₃ in the presence of a base. When X ₁ is a reverse guanamine bond, for example, there is a method of reacting a corresponding dinitro group-containing amine substituent with X ₂ and X ₃ -containing ruthenium chloride in the presence of a base.

When X ₁ is an ester bond, for example, there is a method of reacting a corresponding dinitro group-containing ruthenium chloride with a hydroxy group-substituted derivative containing X ₂ and X ₃ in the presence of a base.

When X ₁ is a reverse ester bond, for example, there is a method of reacting a corresponding dinitro group-containing hydroxy derivative with an acid chloride body containing X ₂ and X ₃ in the presence of a base.

Specific examples of the dinitro-containing halogen derivative and the dinitro-containing derivative are 3,5-dinitrochlorobenzene, 2,4-dinitrochlorobenzene, and 2,4-dinitrofluorobenzene. 3,5-dinitrobenzoic acid chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzylidene chloride, 2,4-dinitrobenzoic acid, 3,5-dinitro Benzyl chloride, 2,4-dinitrobenzyl chloride, 3,5-dinitrobenzyl alcohol, 2,4-dinitrobenzyl alcohol, 2,4-dinitroaniline, 3,5- Dinitroaniline, 2,6-dinitroaniline, 2,4-dinitrophenol, 2,5-dinitrophenol, 2,6-dinitrophenol or 2,4-dinitrophenyl Acetic acid, etc. One or a plurality of kinds can be selected and used in consideration of the easiness and reactivity of the method for obtaining the raw materials.

<alkaline compound>

The liquid crystal alignment agent of the present invention preferably contains a basic compound as a base in order to crosslink the cyclic carbonate group of the polyimide precursor or the polyimine. The type of the basic compound is not particularly limited as long as it has sufficient alkalinity when the cyclic carbonate group is subjected to a crosslinking reaction.

Specifically, for example, an alkali metal such as sodium hydroxide or potassium hydroxide or a hydroxide of an alkaline earth metal, an inorganic amine compound such as ammonia, or an organic amine compound such as pyridine or triethylamine may be mentioned. Among them, an organic amine compound is preferred from the viewpoint of electrical characteristics of the liquid crystal alignment film. Specific examples of the organic amine compound include, for example, a nitrogen-containing heterocyclic amine compound represented by the following formula [M1] to formula [M156]. These amine compounds may be directly added to a solution of a specific polymer, and it is preferred to form a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass, in a suitable solvent. The solvent is not particularly limited as long as it is an organic solvent which dissolves the specific polymer of the present invention.

[Chemistry 14]

[化15]

[Chemistry 16]

[化17]

[化18]

[Chemistry 19]

More preferred organic amine compounds are, for example, M6, M7, M16, M17, M20, M35, M36, M40, M49, M50, M60~M62, M69, M70, M76, M118~M121, M135, or M140. More preferably, it is M6, M16, M17, M35, M36, M40, M49, M50, M60, M61, M118, M120, M121, or M140. Most preferably M6, M17, M35, M40, M61, or M118. The basic compound contained in the liquid crystal alignment treatment agent of the present invention may be used in one type or in combination of two or more types.

The content of the basic compound in the liquid crystal alignment agent of the present invention is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the specific polymer, in order to promote the carboxyl group contained in the polyglycine or polyimine. Or the hydroxyl group reacts, and the alignment of the liquid crystal is prevented from decreasing, more preferably 0.1 to 50 parts by mass, particularly preferably 1 to 30 parts by mass.

<Polyimine precursor and polyimine> In the present invention, the specific polymer is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide. In the specific polymer, the diamine component represented by the following formula [A] and the tetracarboxylic dianhydride component represented by the following formula [B] are subjected to condensation polymerization, which is relatively simple, and therefore preferably has the following formula [C] The polyamine nucleic acid represented by the repeating unit and the polyimine obtained by subjecting the polyamic acid to hydrazine imidization. [Chemistry 20]

In the formula [B], R ₁ is a divalent organic group, and R ₂ is a tetravalent organic group. [Chem. 21]

In the formula [C], R ₁ and R ₂ have the same meanings as defined in the formula [A] and the formula [B], and each of R ₁ and R ₂ may be one type, or a plurality of different types may be combined, n series Indicates a positive integer.

The polyimide precursor and the polyimide of the present invention are obtained by using a diamine component and an acid dianhydride component containing the above specific diamine compound. The diamine component may contain a diamine compound represented by the following formula [3] (also referred to as a specific side chain type diamine compound in the present specification). [化22]

In the formula [3], Y ₁ is a single bond, and is selected from the group consisting of -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO-. Organic base. Among them, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or COO- is preferred because it is easy to synthesize a side chain structure. More preferably a single _{bond, - (CH 2) a -} ( integer from 1 to 10 of _a line), - O -, - CH 2 O- or COO-. In the formula [3], Y ₂ is a single bond or a divalent organic group selected from the group consisting of (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], Y ₃ is a single bond, and is selected from the group consisting of -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO- Organic base. Among them, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO- is relatively easy to synthesize, and thus is preferable. More preferably a single _{bond, - (CH 2) c -} ( c an integer of 1 to 10 lines), - O -, - CH 2 O -, - COO- or OCO-. In the formula [3], Y ₄ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be selected from an alkyl group having 1 to 3 carbon atoms. a divalent organic group substituted with a group of alkoxy groups 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, and a group in which a fluorine atom is grouped, Or a divalent organic group selected from the group consisting of an organic group having 12 to 25 carbon atoms of a steroid skeleton. Among them, a benzene ring, a cyclohexyl ring or an organic group having a carbon number of 12 to 25 having a steroid skeleton is preferred.

In the formula [3], Y ₅ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms. a divalent organic group substituted by a group of alkoxy groups 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, and a fluorine atom. Among them, a benzene ring or a cyclohexyl ring is preferred. In the formula [3], the Y ₆ is a carbon number of 1 to 18, preferably 1 to 12, more preferably 1 to 9, an alkyl group of 1 to 18, preferably 1 to 12, more preferably 1 to 1. 9 fluoroalkyl group, carbon number 1 to 18, preferably 1 to 12, more preferably 1 to 9 alkoxy group, or carbon number 1 to 18, preferably 1 to 12, more preferably 1 to 9 fluoroalkoxy. In the formula [3], n is an integer of 0 to 4. Preferably, it is an integer of 0-2. m is an integer from 1 to 4. Preferably, it is an integer of 1 to 2. Preferred combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n in the formula [3] are shown in Tables 2 to 43.

The specific side chain type diamine compound represented by the formula [3] is more specifically a structure represented by the following formula [3-1] to the formula [3-31]. [化23]

In the formula [3-1] to the formula [3-3], R ₁ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -, or -CH ₂ OCO-, R ₂ -based carbon An alkyl group having 1 to 22 alkyl groups, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

[Chem. 24]

In the formula [3-4]~form [3-6], R ₃ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or CH ₂ -, R ₄ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group. [化25]

In the formula [3-7] and the formula [3-8], 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 trifluoromethylalkyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxyl group.

[Chem. 26]

In the formula [3-9] and the formula [3-10], R ₇ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of 1,4-cyclohexene are each a trans isomer. . [化27]

In the formula [3-11] and the formula [3-12], R ₈ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of 1,4-cyclohexene are each a trans isomer. . [化28]

In the formula [3-13], A ₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A 3 is a 1,4-cyclohexylene group or a 1,4-phenyl group, and A ₂ is an oxygen group. atom or a COO - * (but attaching "*" of the link key and A ₃ are bonded), A ₁ based an oxygen atom or a COO - * (but attaching "*" the coupling linkage (CH ₂₎ a ₂₎ bonded) . Further, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1. [化29]

[化30]

[化31]

[化32]

[化33]

<Other diamine compounds>

The polyimine precursor of the present invention can be obtained by using the specific diamine compound represented by the formula [2], but the specific side chain type represented by the above formula [3] can be used in combination within a range not affecting the effects of the present invention. Amine compounds and other diamine compounds. Specific examples of such other diamine compounds are as follows.

For example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-Dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol , 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diamine Biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-di Hydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3, 3'-Trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diamine linkage Benzene, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodi Phenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-di Diphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, Dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4, 4'-Diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-Diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine , N-methyl (3,4'-diaminodiphenyl)amine, N-methyl (2,2'-diaminodiphenyl)amine, N-methyl (2,3'-di Aminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4 -diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-Diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-di Amino naphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4- Bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3 - bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4 -aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]diphenylamine, 4,4 '-[1,3-Exophenylbis(methylene)]diphenylamine, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine, 3,4'-[1 , 3-phenylphenylbis(methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3'-[1,3-stretch Phenyl bis(methylene)]diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3-aminophenyl) Methyl ketone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4- Phenyl bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoic acid) Ester), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl) pair Phthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate Formate, N,N'-(1,4-phenylene)bis(4-aminophenylguanamine), N,N'-(1,3-phenylene)bis(4-aminobenzene) Indoleamine, N,N'-(1,4-phenylene)bis(3-aminophenylguanamine), N,N'-bis(1,3-phenylene)bis(3-amino group Benzoylamine, 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-aminobenzene) ,4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 '-Bis[4-(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-amine Phenylphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2 '-Bis(3-Aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 3,5-diaminobenzoic acid, 2,5-diamine Benzoic acid, 1,3-double (4- Phenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-amino) Phenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-amine Phenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3- Aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis (4) -aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxy)decane, 1,10-(3- Aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4- Aromatic diamines such as aminophenoxy)dodecane and 1,12-(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane and bis(4-amino group) An alicyclic diamine such as -3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6- Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11- Diamine XI 1,12-dodecane diamine and the aliphatic diamine and the like. Further, the other diamine compound may, for example, be an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring in the side chain of the diamine or a large cyclic substituent having such a structure. Specifically, for example, there is a diamine represented by the following formula [DA1] to formula [DA12].

[化34]

In the formula [DA1] to the formula [DA5], A ₁ is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.

[化35]

In the formula [DA6]~[DA11], A ₂ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, and A ₃ represents An alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group. [化36]

In the formula [DA12], p is an integer of 1 to 10. Further, a diamine compound represented by the following formula [DA13] to formula [DA20] can be used within a range that does not affect the effects of the present invention. [化37]

In the formula [DA17], m is an integer of 0 to 3, and in the formula [DA20], n is an integer of 1 to 5. A diamine compound having a carboxyl group in the molecule represented by the following formula [DA21] to formula [DA25] can be used within a range that does not affect the effects of the present invention. [化38]

In the formula [DA21], m ₁ is an integer of 1 to 4, and in the formula [DA22], the A ₄ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ )-, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or N(CH ₃ )CO-. m ₂ and m ₃ each represent an integer of 0 to 4, and m ₂ + m ₃ represents an integer of 1 to 4. In the formula [DA23], m ₄ and m ₅ are each an integer of 1 to 5, and in the formula [DA24], A ₅ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m ₆ is 1 to 5; Integer. In the formula [DA25], A ₆ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ )-, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- Or N(CH ₃ )CO-, m ₇ is an integer from 1 to 4.

When the specific side chain type diamine compound and the other diamine compound are used as a liquid crystal alignment film, the liquid crystal alignment property, the voltage holding ratio, and the charge accumulation property can be used in one type or in a mixture of two or more types.

<Tetracarboxylic dianhydride> The polyimine precursor of the present invention is obtained by a reaction of a diamine component and a tetracarboxylic acid component. Specific examples of the tetracarboxylic acid component are given below. In order to obtain a specific polymer of the present invention, a tetracarboxylic dianhydride represented by the following formula [4] (also referred to as a specific tetracarboxylic dianhydride in the present specification) is preferably used as a part of a raw material. [39]

In the formula [4], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms, and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms, preferably 4 to 6 carbon atoms. A preferred specific example of Z _{1 is represented} by the following formula [4a] to formula [4i].

[4θ]

In the formula [4a], Z ₂ to Z ₅ are a group selected from a hydrogen atom, a methyl group, a chlorine atom and a benzene ring, and each may be the same or different. In the formula [4g], Z ₆ and Z ₇ are each a hydrogen atom or a methyl group, and each may be the same or different.

In the formula [4], a particularly preferable structure of Z ₁ is a formula [4a], a formula [4c], a formula [4d], a formula [4e], a [4f] or a formula from the viewpoints of polymerization reactivity or ease of synthesis. [4g]. In the present invention, other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride may be used in combination within a range not affecting the effects of the present invention. The other tetracarboxylic dianhydride is, for example, a tetracarboxylic dianhydride of a tetracarboxylic acid shown below. Specific examples thereof are pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-decanetetracarboxylic 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 Perylene tetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxybiphenyltetracarboxylic acid, 1,2,3,4-cyclobutane Tetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2, 3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3,4-dicarboxy- 1-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo[3,3, 0] octane-2,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane -2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2,6>] eleven Alkane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3 , 4-tetrahydronaphthalene-1,2-dicarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxo Tetrahydrofuranyl-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0,2,7]t-12,5,9, 10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2: 3,5:6 dicarboxylic acid or 1,2,4,5-cyclohexanetetracarboxylic acid or the like. In the present invention, one or two or more types may be selected from the above-mentioned tetracarboxylic dianhydride in consideration of characteristics such as liquid crystal alignment property, voltage holding property, and charge accumulation. <Specific Polymer> The liquid crystal alignment treatment agent of the present invention contains at least one of a polyamidene precursor having a cyclic carbonate group and a polyimide which is imidized by the ruthenium imine precursor. The present invention sometimes refers to a polybendimimine precursor and a polybendimimine collectively as a specific polymer. The polyimine precursor is a structure represented by the following formula [A].

[化41]

(In the formula [A], R ₁ is a tetravalent organic group, R ₂ is a divalent organic group, and A ₁ and A ₂ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each may be the same or different, and the n system is Represents a positive integer).

The specific polymer of the present invention is preferably obtained by using a diamine component represented by the following formula [B] and a tetracarboxylic dianhydride represented by the following formula [C] as a raw material, and a specific polymer can be obtained relatively easily. Polylysine which is a structural formula of a repeating unit represented by the following formula [D] or a polyimine which is imidized by the hydrazide.

[化42]

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

[化43]

In the present invention, a method of synthesizing a specific polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. In general, a tetracarboxylic acid component selected from the group consisting of tetracarboxylic acid and a derivative thereof is reacted with a diamine component composed of one or more kinds of diamine compounds to obtain a polyamine. acid. Specifically, a method in which a tetracarboxylic dianhydride and a diamine component are polycondensed to obtain a polyamic acid, and a method in which a tetracarboxylic acid and a diamine component are subjected to a dehydration-polycondensation reaction to obtain a poly-proline acid can be used. A method in which a tetracarboxylic acid dihalide and a diamine component are polycondensed to obtain a polyamic acid. In order to obtain a polyalkyl amide, a method of polycondensing a tetracarboxylic acid and a diamine component obtained by dialkylating a carboxylic acid group, and a tetracarboxylic acid dialkylating a carboxylic acid group may be used. A method of polycondensing a halide with a diamine component or a method of converting a carboxyl group of a polylysine 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 more the proportion of the cyclic carbonate group in the specific polymer, the better the characteristics of the obtained liquid crystal alignment film using the liquid crystal alignment treatment agent containing the specific polymer. Specifically, the solvent resistance in the liquid crystal panel manufacturing step is excellent, and the friction resistance is also good. Further, even if the backlight is irradiated with light, the decrease in the voltage holding ratio can be suppressed.

When a cyclic carbonate group is introduced into a specific polymer using a specific diamine compound, the specific diamine compound is used in an amount of 1 mol% or more, preferably 5 mol, based on the characteristics of the solvent resistance. More than or equal to 10% of the ear, more preferably 10% by mole or more. Further, 100 mol% of the diamine component is likely to be a specific diamine compound. However, from the viewpoint of maintaining uniform coating properties when the liquid crystal alignment agent is applied, the amount of the specific diamine compound to be used is preferably 80% by mole or less, more preferably 40% by mole or less based on the diamine component. When the polyimine precursor of the present invention is obtained by the reaction of a diamine component and a tetracarboxylic acid component, a known synthesis method can be used. For example, a method of reacting a diamine component with a tetracarboxylic acid component in an organic solvent can be used. This method is preferred because it is carried out in an organic solvent at a relatively high efficiency, and the occurrence of by-products is less.

The organic solvent used for the reaction of the diamine component and the tetracarboxylic acid component is not particularly limited as long as it is a polylysine which can be produced by dissolution. Specific examples thereof are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl azine, Tetramethylurea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl fluorenyl Ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cellosolve, ethyl celecoxib, methyl sarbuta acetate, ethyl celesta Subacetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Acetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol single Acetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether , 3-methyl-3-methoxybutyl acetate, tripropyl Alcohol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl Ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, lactic acid Methyl ester, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethyl Methyl ethyl oxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxy Butyl propionate, diglyme or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination. Further, even a solvent which does not dissolve the polyimide precursor can be used in combination with the above solvent as long as it does not precipitate the polyamic acid after the formation. Further, the water in the organic solvent hinders the polymerization reaction and causes hydrolysis of the produced polyimide precursor. Therefore, it is preferred to use a dehydrated organic solvent.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, the following method may be employed: a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid component is directly added or dispersed or dissolved in an organic solvent. In the meantime, for example, there is a method in which a diamine component is added to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, or a method in which a tetracarboxylic acid component and a diamine component are alternately added. In the present invention, any of these methods can be used. When the diamine component or the tetracarboxylic acid component is composed of a plurality of compounds, the reaction may be carried out in a state of being mixed beforehand, or may be sequentially reacted, or the low molecular weight after the respective reactions may be mixed and reacted to form a high molecular weight body.

The temperature at which the diamine component and the tetracarboxylic acid component are reacted can be arbitrarily selected within the range of from -20 ° C to 150 ° C, and in view of the reaction efficiency, it 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 is difficult to obtain a high molecular weight polyimine precursor. When the concentration is too high, the viscosity of the reaction liquid is 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 thereafter an organic solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the molar number of the synthetic mole of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. As with the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polymer. Therefore, it is possible to appropriately determine the total molar ratio depending on the situation.

The polyimine of the present invention is obtained by subjecting the above-mentioned polyimine precursor to dehydration ring closure. This polyimine can be used as a polymer for obtaining a liquid crystal alignment film.

In the polyimine of the present invention, the dehydration ring closure ratio (the imidization ratio) of the polyimide precursor is not necessarily required to be 100%, and may be adjusted, for example, in the range of 45 to 85% depending on the use or purpose. A method for subjecting a polyimine precursor to ruthenium imidization, for example, a hydrazine imidization by directly heating a solution of a polyimide precursor solution, or a contact of a catalyst in a solution of a polyimide precursor solution Media imidization and the like.

The temperature at which the polyimine precursor is thermally imidized in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water formed by the ruthenium imidization reaction is excluded from the reaction system. It is preferred to carry out the reaction on the outside. The catalyst oxime imidization of the polyimide precursor is added to the polyamidene precursor solution by adding a basic catalyst and an acid anhydride, and is stirred at -20 to 250 ° C, preferably 0 to 180 ° C. Media imidization. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the acid anhydride is 1 to 50 moles of the amidate group, preferably 3 to 3 30 times Mo. 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. The acid anhydride is, for example, acetic anhydride, trimellitic anhydride, or pyromellitic anhydride. Among them, acetic anhydride is preferred because it is easy to purify after completion of the reaction. 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 polyimide precursor or polyimine is recovered from the reaction solution of the polyimide precursor or the polyimine, the reaction solution may be poured into a weak solvent to precipitate. The weak solvent used for the precipitation is, for example, methanol, acetone, hexane, butyl sarbuta, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, or water. The polymer which is added to the weak solvent and precipitated is filtered and recovered, and then dried at normal temperature or under heat at 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 this case, the weak solvent is, for example, an alcohol, a ketone or a hydrocarbon, and when three or more kinds of weak solvents selected from the above are used, the purification efficiency can be further improved, which is preferable.

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

<Liquid Crystal Alignment Treatment Agent> The liquid crystal alignment treatment agent of the present invention is a solution for forming a liquid crystal alignment film, and is a solution obtained by dissolving a resin component for forming a resin film of a liquid crystal alignment film in an organic solvent. The resin component contains a polymer selected from at least one of the above-mentioned fixed polymers. The content of the resin component in the liquid crystal alignment agent is preferably from 1 to 20% by mass, more preferably from 3 to 15% by mass, particularly preferably from 3 to 10% by mass. In the present invention, all of the resin components contained in the liquid crystal alignment treatment agent may be a specific polymer. Further, in addition to the specific polymer, other polyimine precursors or polyimines having no cyclic carbonate group may be used. Further, examples of the polymer other than the polyimine precursor and the polyimine are, for example, an acrylic polymer, a methacrylic polymer, polystyrene or polyamine. The content of the other specific polymer may be from 0.5 to 15% by mass, preferably from 1 to 10% by mass.

When the organic solvent is contained in the liquid crystal alignment treatment agent of the present invention, the content of the organic solvent is preferably from 70 to 99% by mass, more preferably from 80 to 99% by mass, from the viewpoint of forming a uniform film by coating. This content can be appropriately changed depending on the film thickness of the liquid crystal alignment film. The organic solvent at this time is not particularly limited as long as it is an organic solvent in which the specific polymer is dissolved. More specifically, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl indoleamine, 2-pyrrolidone , N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, 1,3- Dimethyl-imidazolidinone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate Ester, diglyme or 4-hydroxy-4-methyl-2-pentanone. These can be used alone or in combination.

In the liquid crystal alignment treatment agent of the present invention, a crosslinkable compound having an epoxy group, an isocyanate group or an oxetanyl group may be introduced in a range which does not affect the effects of the present invention, and has a group selected from a hydroxyl group and an alkoxy group. A crosslinkable compound having at least one substituent in a group and a crosslinkable compound having a polymerizable unsaturated bond.

A crosslinkable compound having an epoxy group or an isocyanate group, for example, bisphenol acetone glycidyl ether, novolak epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidyl group Aminobiphenyl, tetraglycidyl-m-toluenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidol Ethyl ether, bisphenol hexafluoroacetamido diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2- Trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl-m-xylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-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 [5]. [化44]

Specifically, for example, there is a crosslinkable compound represented by the following formula [5-1] to formula [5-11].

[化45]

[Chem. 46]

[化47]

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, an anthracene resin, a glycol urea-formaldehyde Resin, amber amide-formaldehyde resin or ethylene urea-formaldehyde resin. As the crosslinkable compound, for example, a melamine derivative, a benzoquinone derivative or a glycol urea or the like in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group or both may be used. At this time, the melamine derivative and the benzoquinone derivative may also exist in the form of a dimer or a trimer. These are preferably those having an average of 3 or more and 6 or less methylol groups or alkoxymethyl groups per one triazine ring.

Examples of such melamine derivatives or benzoquinone derivatives, for example, MX-750, which is substituted by an average of 3.7 methoxymethyl groups per one triazine ring, and one triazine ring per one, are averaged. 5.8 methoxymethyl-substituted MW-30 (above manufactured by Sanwa Chemical), or methoxymethylation of CYMEL 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methoxymethylated butoxymethylated melamine of melamine, 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 ethoxymethylated phenylhydrazine of CYMEL 1123, methoxymethylated butoxy of CYMEL 1123-10 Methylated benzoquinone, such as butoxymethylated phenylhydrazine of CYMEL 1128, methoxymethylated ethoxylated phenylhydrazine containing a carboxyl group such as CYMEL 1125-80 (manufactured by Mitsui Chemicals Co., Ltd.). Further, examples of the glycol urea are, for example, butoxymethylated glycol urea of CYMEL 1170, hydroxylated glycol urea of CYMEL 1172, and the like, such as methoxymethylolated glycol urea of POWERLINK 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(second butoxymethyl)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and the like. More specifically, for example, there is a crosslinkable compound represented by the following formula [6-1] to formula [6-48]. [48]

[化49]

[化50]

[化51]

[化52]

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 crosslinkable compound having three polymerizable unsaturated groups in the molecule of propylene methoxy ethoxy trimethylolpropane, glycerol polyglycidyl ether poly(meth) acrylate, and the like Acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate, ring Oxypropane bisphenol type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol II Glycidyl ether di(meth)acrylate, diethylene glycol glycidyl ether di(meth)acrylate, diglycidyl phthalate a crosslinkable compound having two polymerizable unsaturated groups in a molecule such as (meth) acrylate or hydroxypivalic acid neopentyl glycol di(meth)acrylate, and further, (meth)acrylic acid 2- Hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(methyl)propene Nonyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth)acrylate, mono (meth) acrylate, 2-(methyl) propylene oxy ethoxylate A crosslinkable compound having one polymerizable unsaturated group in a molecule such as a phosphatidyl ester or an N-methylol (meth) acrylamide. Further, a compound represented by the following formula [7] can also be used. [化53]

In the formula [7], A ₁ is a group selected from a cyclohexyl ring, a bicyclohexyl ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring or a phenanthrene ring, and A _{2 is} selected from the group consisting of The group of the following formula [7a] or formula [7b], n is an integer of 1 to 4. [54]

The above compound is an example of a crosslinkable compound, but is not limited thereto. Further, the crosslinkable compound contained in the liquid crystal alignment agent of the present invention may be one type or two or more types. The content of the cross-linking compound is preferably 0.1 to 150 parts by mass based on 100 parts by mass of the resin component of the liquid crystal alignment agent, and the effect of the purpose is exhibited for the crosslinking reaction, and the alignment of the liquid crystal is prevented from being lowered. It is 0.1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass. A nitrogen-containing heterocyclic amine compound represented by the following formula [M1] to the formula [M156] can be added as a compound which promotes charge transfer in the liquid crystal alignment film and promotes charge elimination using a liquid crystal cell of the liquid crystal alignment film. The amine compound may be directly added to the solution of the polymer, but it is preferably added in a suitable solvent to form a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent is not particularly limited as long as it is an organic solvent in which the above polymer is dissolved.

[化55]

[化56]

[化57]

[化58]

[化59]

[60]

The liquid crystal alignment treatment agent of the present invention can be used in an organic solvent (also referred to as a weak solvent) or a compound which improves the film thickness uniformity or surface smoothness when the liquid crystal alignment treatment agent is applied, within a range that does not impair the effects of the present invention. A compound in which a liquid crystal alignment film and a substrate are adhered to each other.

Specific examples of the weak solvent for increasing the film thickness uniformity or the surface smoothness include, for example, isopropanol, methoxymethylpentanol, methyl stilbene, ethyl stilbene, and butyl 赛苏苏. , Methyl sulphate acetate, ethyl sirolimus acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetic acid Ester, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol Alcohol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetic acid Ester monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl -3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, Propyl ether, two Hexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, acetone Ester, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methyl Oxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butyl Oxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1- Monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate A solvent or the like having a low surface tension such as an ester. These weak solvents can be used one kind or a mixture of plural kinds. When the weak solvent is used, the amount thereof is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.

Examples of the compound which improves the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a rhodium-based surfactant, and a nonionic surfactant. More specifically, for example, EF TOP EF301, EF303, EF352 (manufactured by TOHKEM PRODUCTS), MAGAFAC F171, F173, R-30 (made by Dainippon Ink), FLORARD FC430, FC431 (manufactured by Sumitomo 3M), Asahigard AG710, SURFLON S -382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The ratio of use of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include, for example, those having a functional decane compound or an epoxy group-containing compound as described below. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxy decane, 3-ureidopropyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyltrimethoxy decane, N-ethoxycarbonyl-3-aminopropyl three Ethoxy decane, N-triethoxydecyl propyl triethylidene triamine, N-trimethoxydecyl propyl triethylidene triamine, 10-trimethoxydecyl-1,4, 7-triazanonane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltri Ethoxy decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethyl)-3- Aminopropyltrimethoxydecane, N-bis (oxyethyl) )-3-Aminopropyltriethoxydecane, 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-diglycidyl) Aminomethyl)cyclohexane or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

When a compound which improves the adhesion to the substrate is used, the amount of the compound added is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment agent. . When it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and when it is more than 30 parts by mass, the liquid crystal alignment may be deteriorated.

In addition to the above, the liquid crystal alignment agent of the present invention may be added with a dielectric or a conductive material for changing the dielectric properties such as the dielectric constant or the conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired.

<Liquid alignment film ‧ Liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention is applied onto a substrate, and after firing, it can be used as a liquid crystal alignment film by an alignment treatment by rubbing treatment or light irradiation. Further, in the case of 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 at this time 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 can 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, in the case of a reflective liquid crystal display device, when only a single-sided substrate is used, an opaque substrate such as a germanium wafer may be used. In this case, a material that reflects light such as aluminum may be used as the electrode.

The coating method of the liquid crystal alignment agent is not particularly limited, but industrially, it is generally applied by screen printing, lithography, soft printing, inkjet printing or the like. Other coating methods include, for example, dipping, roll coating, slit coating, spin coating, etc., and may be used depending on the purpose.

After the liquid crystal alignment agent is applied onto the substrate, the solvent is evaporated at 50 to 300 ° C, preferably 80 to 250 ° C by a heating means such as a hot plate to form a coating film. When the thickness of the coating film after firing is too thick, the power consumption of the liquid crystal display element is unfavorable. When the film thickness is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 10. 100nm. When the liquid crystal is aligned horizontally or obliquely, the fired coating film is treated by rubbing or polarized ultraviolet light irradiation or the like.

In the liquid crystal display device of the present invention, the liquid crystal cell is produced by a conventional method from the liquid crystal alignment treatment agent of the present invention, and a liquid crystal cell is produced by the above-described method.

In the method for fabricating a liquid crystal cell, for example, a pair of substrates of a liquid crystal alignment film are prepared, and a spacer is spread on a liquid crystal alignment film of one of the substrates, so that the liquid crystal alignment film surface is inside, and the other substrate is bonded, and the liquid crystal is injected under reduced pressure. A method of encapsulating, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface on which a separator is dispersed, and a substrate is bonded and packaged.

The liquid crystal alignment film of the present invention can also be applied to a liquid crystal display device which is produced by a step of providing a liquid crystal layer between a pair of electrodes and a substrate. a liquid crystal composition of a polymerizable compound which is polymerized by at least one of an active energy ray and heat, and a step of applying a voltage between the electrodes, and irradiating the polymerizable compound by at least one of irradiation and heating of the active energy ray . its The medium active energy ray is preferably ultraviolet light.

The above liquid crystal display element controls the pretilt angle of the liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed in a liquid crystal material, and a liquid crystal cell is assembled, and a predetermined voltage is applied to the liquid crystal layer, and the photopolymerizable compound is irradiated with ultraviolet rays or the like. The polymer controls the pretilt angle of the liquid crystal molecules. The alignment state of the liquid crystal molecules at the time of polymer formation is such that even after the voltage is removed, the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. Further, since the PSA method does not require rubbing treatment, it is suitable for formation of a vertical alignment type liquid crystal layer which is difficult to control the pretilt angle by rubbing treatment.

In the liquid crystal display device of the present invention, the liquid crystal cell is produced by obtaining the liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention, and the polymerizable compound is polymerized by ultraviolet irradiation and heating. Control the alignment of liquid crystal molecules.

When an example of liquid crystal cell formation is used, for example, a pair of substrates of a liquid crystal alignment film are prepared, and a spacer is spread on a liquid crystal alignment film of one of the substrates, and the liquid crystal alignment film surface is formed inside, and the other substrate is bonded to the substrate. A method of injecting a liquid crystal and encapsulating, or a method of laminating a liquid crystal on a liquid crystal alignment film surface on which a spacer is dispersed, bonding the substrate, and encapsulating the substrate.

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

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

The liquid crystal display element of the present invention can be obtained by the steps exemplified above. Since these liquid crystal display elements are used as the liquid crystal alignment film by using the alignment film of the present invention, they are excellent in reliability, and can be applied to a large-screen, high-definition liquid crystal television or the like.

[Examples]

The invention is illustrated in more detail in the following examples. However, the invention is not limited to the embodiments.

The short sentences used in the examples and comparative examples are as follows.

<tetracarboxylic dianhydride>

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

A-2: Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride

[化61]

<Specific diamine compound>

B-1: a diamine compound synthesized in the same manner as in Example 1.

[化62]

<Other amine compounds>

B-2: 3,5-diaminobenzoic acid

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

[化63]

<alkali>

C-1: 3-aminopropyl imidazole

C-2: 3-aminopyridine

<organic solvent>

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cyrus

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

IPA: isopropanol

DMSO: dimethyl hydrazine

In the examples, the physical properties such as the molecular weight of the polyamic acid and the polyimine, or the ruthenium iodide ratio were evaluated in the following manner.

<Measurement of molecular weight of poly-proline and polyimine

The molecular weight of polyglycine and polyimine was a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Showa Denko Co., Ltd., and a pipe column (KD-803, KD-805) manufactured by Shodex Co., Ltd. The measurement conditions are as follows.

Column temperature: 50 ° C

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

Flow rate: 1.0ml/min

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by TOSOH Co., Ltd. and polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Libertry Co., Ltd.

<Measurement of sulfhydrylation rate>

20 mg of polyimine powder was placed in an NMR sample tube (manufactured by Kusano Scientific Co., Ltd., NMR sampling tube standard Φ 5), and dimethylated dimethyl hydrazine (DMSO-d6, 0.05% TMS (tetramethyl decane) mixture was added. ) 0.53ml, completely dissolved by ultrasound. This solution was measured for proton NMR at 500 MHz using a NMR measuring instrument (JNW-ECA500) manufactured by JEOL Ltd. The ruthenium imidization ratio is determined by using protons derived from unaltered structures before and after imidization as a reference proton, and the peak value of the proton is used and the NH group derived from proline is present in the vicinity of 9.5 to 10.0 ppm. The proton accumulation value is obtained by the following formula (1).

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

In the above formula (1), x is the cumulative value of the proton peak derived from the NH group of the proline, y is the cumulative value of the peak of the reference proton, and α is the reference proton relative to the polyamine (the imidization ratio) The ratio of the number of NH protons of the proline to be 0%).

Next, a synthesis example of the specific diamine compound of the present invention is shown. In the synthesis example, ¹ H-NMR refers to a nuclear magnetic resonance spectrum of a hydrogen atom in a molecule, and shows spectral data of the obtained compound.

Example 1. (Synthesis of diamine compounds)

[化64]

The synthesis of the diamine compound (B-1) is carried out according to the above synthesis scheme (Scheme), specifically, the compound (302) (21.51 g, 182.2 mmol), and triethylamine (18.44 g, 182.2 mmol) of tetrahydrofuran. (400 g) After cooling the solution to 10 ° C or lower, a solution of the compound (301) (40.00 g, 173.5 mmol) in tetrahydrofuran (200 g) was added dropwise to the mixture while taking care of heat. After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. After confirming the completion of the reaction by HPLC (high-speed liquid chromatography), the reaction solution was poured into distilled water (4.8 L), and the precipitated solid was filtered and washed with water, and then washed with methanol (324 g) to obtain a compound (303). 48.65 g, yield: 90%).

^{1 H-NMR (400MHz, DMSO} -d6, δppm): 9.03 (1H, t), 8.87 (2H, d), 5.24-5.19 (1H, m), 4.67-4.57 (3H, m), 4.47 (1H, Dd).

A mixture of compound (303) (40.00 g, 128.1 mmol), 5% palladium on carbon (aqueous form, 4.0 g, 10 wt%), and 1,4-dioxane (600 g) in the presence of hydrogen at 23 ° C Stir. After the completion of the reaction, the catalyst was filtered using diatomaceous earth, and the solvent was distilled off from the evaporator to obtain a crude oily product. Ethyl acetate (200 g) was added to the obtained crude product, and the mixture was heated and stirred, and then crystallization was carried out, followed by filtration and drying to obtain a white solid diamine compound (B-1) (yield: 17.45 g, yield: 54%).

^{1 H-NMR (400MHz, DMSO} -d6, δppm): 6.42 (2H, d), 6.04 (1H, t), 5.14-5.09 (1H, m), 5.03 (4H, br s), 4.62 (1H, t ), 4.50 (1H, dd), 4.39-4.32 (2H, m).

Example 2. <Synthesis of polyglycine 1>

A-2 (7.86 g, 31.4 mmol), B-3 (5.62 g, 12.9 mmol), B-2 (1.96 g, 12.9 mmol), and B-1 (2.79 g, 11.0 mmol) in NMP (57.1 g) The mixture was mixed and reacted at 80 ° C for 5 hours. Then, A-1 (1.05 g, 5.51 mmol) and NMP (20.1 g) were added, and reacted at 55 ° C for 6 hours to obtain a solution of polyglycine (A) (concentration 20.0). quality%). The polyamine acid (A) had a number average molecular weight of 25,528 and a weight average molecular weight of 97,025.

Example 3. <Synthesis of Polyimine 1>

NMP was added to a solution (25.0 g) of the polyamic acid (A) obtained in Example 2, and after diluting to 6 mass%, acetic anhydride (4.88 g) and pyridine (1.51) as a ruthenium catalyst were added. g), react at 100 ° C for 2 hours. This reaction solution was poured into methanol (314 g), and the resulting precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a powder of polyimine (B). The polyimine (B) had a ruthenium imidation ratio of 77%, a number average molecular weight of 18,898, and a weight average molecular weight of 102,005.

To 3.85 g of the powder of the polyimine (B), 18.8 g of NMP was added, and the mixture was stirred at 70 ° C for 30 hours to dissolve to obtain a solution of the polyimine (B).

Example 4. <Modulation of Liquid Crystal Alignment Treatment Agent 1>

NMP, C-1 NMP solution and BCS were added to the polyimine (B) solution obtained in Example 3, and the mixture was stirred at 50 ° C for 20 hours to prepare a polyamidene of 6 mass%, and C-1 was 0.3% by mass, NMP was 48.7% by mass, and BCS was 45% by mass. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

Example 5. <Synthesis of polyglycine 2>

A-2 (8.29 g, 33.0 mmol), B-3 (5.93 g, 13.6 mmol), B-2 (2.96 g, 19.4 mmol), and B-1 (1.47 g, 5.84 mmol) in NMP (58.8 g) The mixture was mixed and reacted at 80 ° C for 5 hours. Then, A-1 (1.14 g, 5.81 mmol) and NMP (20.3 g) were added, and reacted at 55 ° C for 6 hours to obtain a solution of polyglycine (C) (concentration 20.0). quality%). The polyamine acid (C) had a number average molecular weight of 24,325 and a weight average molecular weight of 82,359.

Example 6. <Synthesis of Polyimine 2>

In the same manner as in Example 3, NMP was added to a solution (25.0 g) of the polyamic acid (C) obtained in Example 5 to a concentration of 6 mass%, and then acetic anhydride (5.02 g) as a ruthenium catalyst was added. And pyridine (1.55 g) were reacted at 100 ° C for 2 hours. This reaction solution was poured into methanol (314 g), and the resulting precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a powder of polyimine (D). The polyimine (D) had an imidization ratio of 77%, a number average molecular weight of 20,405, and a weight average molecular weight of 82,988.

To 3.82 g of a powder of polyimine (D), 18.6 g of NMP was added, and the mixture was stirred at 70 ° C for 30 hours to dissolve to obtain a solution of polyimine (D).

Example 7. <Modulation of Liquid Crystal Alignment Treatment Agent 2>

In the same manner as in Example 4, NMP and C-1 NMP solution and BCS were added to the polyimine (D) solution obtained in Example 6, and the mixture was stirred at 50 ° C for 20 hours to prepare a polyimine of 6 mass%. C-1 was 0.3% by mass, NMP was 48.7% by mass, and BCS was 45% by mass. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

Example 8. <Modulation of Liquid Crystal Alignment Treatment Agent 3>

NMP, C-2 NMP solution and BCS were added to the polyimine (B) solution obtained in Example 3, and stirred at 50 ° C for 15 hours to prepare a polyamidimide of 6 mass% and a C-1 of 0.3. The mass% and NMP were 48.7% by mass, and the BCS was 45 mass%. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

Example 9. <Modulation of Liquid Crystal Alignment Treatment Agent 4>

NMP, C-2 NMP solution and BCS were added to the polyimine (D) solution obtained in Example 6, and stirred at 50 ° C for 20 hours to prepare a polyamidimide of 6 mass% and a C-1 of 0.3. The mass% and NMP were 48.7% by mass, and the BCS was 45 mass%. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

Example 10. <Modulation of Liquid Crystal Alignment Treatment Agent 5>

NMP and BCS were added to the solution of the polyimine solution (B) obtained in Example 3, followed by stirring to prepare a polyamidene of 6 mass%, NMP of 48.7% by mass, and BCS of 45 mass%. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

Example 11. <Modulation of Liquid Crystal Alignment Treatment Agent 6>

NMP, C-2 NMP solution and BCS were added to the polyamine acid (A) solution obtained in Example 2, and stirred to prepare a polyamidimide of 6 mass%, C-2 of 0.3 mass%, and NMP as 48.7 mass% and BCS were 45 mass%. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

Example 12. <Modulation of Liquid Crystal Alignment Treatment Agent 7>

NMP, C-2 NMP solution and BCS were added to the polyamine acid (C) solution obtained in Example 5, and stirred to prepare polyglycine (C) to be 6 mass% and C-2 to be 0.3 mass%. NMP was 48.7 mass%, and BCS was 45 mass%. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

Example 13. <Modulation of Liquid Crystal Alignment Treatment Agent 8>

NMP and BCS were added to the polyphthalic acid (A) solution obtained in Example 2, and the mixture was stirred to prepare a polyamidimide of 6 mass%, an NMP of 48.7% by mass, and a BCS of 45 mass%. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

The following are comparative examples of polylysine, polyimine, and liquid crystal alignment treatment agents.

Comparative Example 1.

A-2 (41.7 g, 166 mmol), B-3 (29.7 g, 68.3 mmol) and B-2 (19.4 g, 12.7 mmol) were mixed in NMP (290 g), and reacted at 80 ° C for 5 hours, and then added. A-1 (5.57 g, 28.4 mmol) and NMP (93.0 g) were reacted at 55 ° C for 6 hours to obtain a polyamine acid (E) solution (concentration: 20.0% by mass). The polyamine acid (E) had a number average molecular weight of 24,513 and a weight average molecular weight of 79,705.

Comparative Example 2.

In the same manner as in Example 3, NMP was added to the polyamine acid (E) solution (75.0 g) obtained in Comparative Example 1, and after diluting to 6 mass%, acetic anhydride (15.55 g) as a ruthenium catalyst was added. And pyridine (4.82 g), reacted at 100 ° C for 2 hours. This reaction solution was poured into methanol (946 g), and the resulting precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a powder of polyimine (F). The polyimine (F) had an imidization ratio of 77%, a number average molecular weight of 19,377, and a weight average molecular weight of 53,171.

To 16.6 g of the powder of the polyimine (F), 56.6 g of NMP was added, and the mixture was stirred at 70 ° C for 30 hours to dissolve to obtain a polyimine (F) solution.

Comparative Example 3.

In the same manner as in Example 4, NMP and C-1 NMP solution and BCS were added to the polyimine (F) solution obtained in Comparative Example 2, and the mixture was stirred at 50 ° C for 20 hours to prepare a polyimine of 6 mass%. C-1 was 0.3% by mass, NMP was 48.7% by mass, and BCS was 45% by mass. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

Comparative Example 4.

NMP, C-2 NMP solution and BCS were added to the polyimine (F) solution obtained in Comparative Example 2, and stirred at 50 ° C for 20 hours to prepare a polyamidimide of 6 mass% and a C-2 of 0.3. The mass% and NMP were 48.7% by mass, and the BCS was 45 mass%. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

Comparative Example 5.

NMP and BCS were added to the polyimine (F) solution obtained in Comparative Example 2, and the mixture was stirred to prepare a polyamidimide of 6 mass%, an NMP of 48.7% by mass, and a BCS of 45 mass%. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

Comparative Example 6.

NMP and C-2 NMP solution and BCS were added to the polyamine acid (E) solution obtained in Comparative Example 1, and stirred to prepare a polyamidimide of 6 mass%, C-2 of 0.3 mass%, and NMP as 48.7 mass% and BCS were 45 mass%. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

Comparative Example 7.

NMP and BCS were added to the polyamine acid (E) solution obtained in Comparative Example 1, and stirred to prepare a polyamine acid (E) of 6 mass%, NMP of 48.7% by mass, and BCS of 45 mass%. The liquid crystal alignment treatment agent was obtained by pressure filtration using a membrane filter having a pore size of 1 μm.

Table 44 shows the liquid crystal alignment treatment agents of the examples and the liquid crystal alignment treatment agents of the comparative examples.

Next, the liquid crystal alignment treatment agent of the above examples was evaluated simultaneously with the comparison of the comparative examples. First, the method of evaluation will be explained.

<Evaluation of Solvent Resistance>

The solvent resistance was evaluated by investigating the residual film ratio after solvent impregnation. Specifically, the liquid crystal alignment treatment agent was spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating oven at 230 ° C for 30 minutes to form a film thickness. 100 nm coating film. The substrate with the liquid crystal alignment film was immersed in NMP at 23 ° C for 1 minute, and the residual film ratio was determined according to the following formula. In the formula (2), a is a film thickness after immersion, and a film thickness before b-dipping.

Residual film rate (%) = (a / b) × 100 ‧ ‧ (2)

<Evaluation of Electrical Characteristics and UV Resistance>

The liquid crystal alignment treatment agent was spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating oven at 230 ° C for 30 minutes to form a coating film having a film thickness of 100 nm. A substrate with a liquid crystal alignment film was obtained. Two sheets of the substrate with the liquid crystal alignment film were prepared, and one of the liquid crystal alignment film faces was spread with a separator of 6 μm, and then the sealant was printed from above. Next, the liquid crystal alignment film faces the state, and after bonding to the other substrate, the sealant is cured to form an empty cell. Thus, liquid crystal MLC-6608 (manufactured by Merck‧ Japan Co., Ltd.) was injected into the empty cell by a pressure reduction injection method, and the injection port was closed to obtain a liquid crystal cell which was vertically aligned.

The liquid crystal cell was applied with a voltage of 1 V for 60 μs at a temperature of 80 ° C, and the voltage after 50 ms was measured, and the voltage was maintained as a voltage holding ratio. The liquid crystal cell after the voltage holding ratio was measured was irradiated with UV light (ultraviolet light), and the voltage holding ratio was measured again in the same manner as above. The irradiation energy was calculated based on the irradiation intensity in 350 nm. The evaluation results are shown in Table 45.

As shown in the evaluation results of Table 45, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example showed a high residual film ratio in the evaluation of the residual film ratio, and was found to be excellent in solvent resistance. On the other hand, the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of the comparative examples all showed a low residual film ratio, and the solvent resistance was remarkably inferior to those in the examples.

The solvent resistance was evaluated using a solvent other than NMP. The solvent was subjected to the same evaluation as the above-mentioned residual film rate evaluation using NMP, and the same evaluation as the above-mentioned evaluation of the residual film rate using NMP was carried out using the IPA, and the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example was used. The residual film rate was 100%. On the other hand, the residual film ratio of the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the comparative example was also 100%.

When the same evaluation as the above-described evaluation of the residual film ratio using NMP was carried out using PGME, the residual film ratio of the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example was 100%. Further, the residual film ratio of the liquid crystal alignment film obtained from the liquid crystal alignment treatment agents of Comparative Examples 3 to 5 was 100%. However, the residual film ratio of the liquid crystal alignment film of Comparative Example 6 was 30%, and the residual film ratio of the liquid crystal alignment film of Comparative Example 7 was 5%.

Comparative Examples 6 and 7 are liquid crystal alignment treatment agents containing polyglycine, and Examples 11 to 13 also contain a liquid crystal alignment treatment agent of polyglycine. When the liquid crystal alignment film obtained from the liquid crystal alignment treatment agents of Examples 11 to 13 was evaluated by the same evaluation as the above-mentioned residual film rate evaluation using NMP using PGME, the residual film ratio was 100%, and the value was high. Therefore, it was found that the examples exhibited high solvent resistance even when they contained polyphthalic acid and constituted a liquid crystal alignment treatment agent.

As a result of the above evaluation, it is understood that the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example has extremely excellent solvent resistance, and in particular, the solvent having high solubility can clearly exhibit the superiority with respect to the prior art.

Next, the electrical characteristics will be explained. The liquid crystal cell of the liquid crystal alignment treatment agent of the example was used to exhibit a voltage holding ratio of more than 90%, and it was found that the motor characteristics were excellent.

Regarding the UV resistance, the liquid crystal alignment treatment agents of Examples 11 to 13 were used to know the voltage holding ratio of the liquid crystal cell, and after UV irradiation, the value was also higher than 79%, and other examples were also shown to exceed 90%. Very high voltage retention.

As described above, the liquid crystal cell system having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example has excellent electrical characteristics and UV resistance.

In the case of the liquid crystal alignment treatment agent of the comparative example, in Comparative Example 6, the voltage retention rate of the liquid crystal cell after UV irradiation was 70.8%, and Comparative Example 7 was a low value of 74.6%. In any of the comparative examples, when 50 G of UV light was irradiated, it was found that the voltage holding ratio was not higher than 90%.

From the above evaluation results, it is found that the liquid crystal alignment film obtained by using the liquid crystal alignment agent obtained from the polyamine and the polyimine obtained by using the diamine compound of the present invention is excellent in solvent resistance and can be inhibited by light irradiation. The voltage holding rate is reduced.

[Industrial availability]

The liquid crystal alignment film of the present invention has a sufficient solvent resistance in the cleaning step in the liquid crystal panel manufacturing step, and can suppress a decrease in the voltage holding ratio even when irradiated with light. The liquid crystal display element having the liquid crystal alignment film has Excellent display quality, suitable for large screens, high-definition LCD TVs, etc.

The entire contents of the specification, the scope of the application, the drawings and the abstract of Japanese Patent Application No. 2010-133337, filed on June 10, 2010, are hereby incorporated by reference.

Claims (15)

A liquid crystal alignment treatment agent characterized by comprising: a polyimine precursor selected from the group consisting of a diamine compound having a cyclic carbonate group represented by the following formula [1] as a raw material, and the polyimine precursor At least one polymer of a group of polyimines which have been imidized by hydrazine, [Chem. 1]-X ₁ -X ₂ -X ₃ [1] (X ₁ -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or N(CH ₃ )CO-, X ₂ -based carbon a number 1 to 5 alkylene group, and X ₃ is a structure represented by the following formula [1a]) The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the diamine compound is a diamine compound represented by the following formula [2], (X ₁ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or N(CH ₃ )CO-, X ₂ is an alkylene group having 1 to 5 carbon atoms, X ₃ is a structure represented by the following formula [1a], and n is an integer of 1 to 4) The liquid crystal alignment treatment agent according to claim 1 or 2, which further comprises a base having a primary amine group and a nitrogen-containing heterocyclic ring in a molecular structure. The liquid crystal alignment treatment agent according to claim 3, wherein the base is at least one compound selected from the group consisting of 3-aminopropylimidazole and 3-pyridinemethylamine. The liquid crystal alignment treatment agent according to claim 1 or 2, which contains an organic solvent which dissolves the polyimine precursor and the polyimine, and the organic solvent contains 5 to 80% by mass in the liquid crystal alignment treatment agent. a weak solvent. A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of claims 1 to 5. The liquid crystal alignment film of claim 6, which is formed by having a liquid crystal layer between one of the electrodes and the substrate, and is disposed between the pair of substrates by active energy rays and heat A liquid crystal display device produced by the step of polymerizing the polymerizable compound by applying a voltage to the liquid crystal composition of the polymerizable compound at least one of the electrodes. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 7 of the patent application. The liquid crystal display device of claim 8 is characterized in that the liquid crystal layer is provided between the substrate having one of the electrodes and the liquid crystal alignment film. And a liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat between the pair of substrates, and a step of applying a voltage between the electrodes to polymerize the polymerizable compound . A diamine compound characterized by the following formula [2], (X ₁ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or N(CH ₃ )CO-, X ₂ is an alkylene group having 1 to 5 carbon atoms, X ₃ is a structure represented by the following formula [1a], and n is an integer of 1 to 4) A polyimine precursor which is obtained by reacting a diamine component containing an amine compound as in claim 10 of the patent application with an acid dianhydride component. The polyimine precursor according to claim 11, wherein the diamine component further contains a diamine compound represented by the following formula [3]. (Y ₁ is a single bond, and is selected from the group consisting of -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O-, -COO-, and -OCO- An organic group, a Y ₂ -based single bond, or a divalent organic group selected from (CH ₂ ) _b - (b is an integer of 1 to 10), a Y ₃ -based single bond selected from -(CH ₂ ) _c -(c a divalent organic group in the group of 1 to 10, -O-, -CH ₂ O-, -COO-, and -OCO-, and Y ₄ is selected from the group consisting of a benzene ring, a cyclohexyl ring, and a heterocyclic ring. a group of cyclic groups, wherein any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms. a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a divalent organic group substituted by a fluorine atom, or a divalent organic group selected from an organic group having a carbon number of 12 to 25 having a steroid skeleton, and Y ₅ is selected from a benzene ring a cyclic group in which a cyclohexyl ring and a heterocyclic ring are grouped, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a carbon number of 1 a fluorine-containing alkyl group of ~3, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a divalent organic group substituted by a fluorine atom, n is an integer of 0 to 4, and Y ₆ is 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 carbon The number of fluoroalkoxy groups of 1 to 18, m is an integer of 1 to 4). The polyamidiamine precursor according to claim 11 or 12, wherein the acid dianhydride component is a tetracarboxylic dianhydride represented by the following formula [4], (Z ₁ is a 4-valent organic group having 4 to 13 carbon atoms and a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms). The polyamidiamine precursor according to claim 13, wherein Z ₁ in the tetracarboxylic dianhydride is an organic group of any one of the following formulas [4a] to [4j], (In the formula [4a], each of Z ₂ to Z ₅ is independently a group selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and in the formula [4g], each of the Z ₆ and Z ₇ systems is independently a hydrogen atom. , or methyl). A polyimine which is obtained by subjecting a polybendimimine precursor according to any one of claims 11 to 14 to dehydration ring closure.