WO2012121257A1

WO2012121257A1 - Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: WO2012121257A1
Application number: PCT/JP2012/055709
Authority: WO
Inventors: 徳俊三木; 耕平後藤; 雅章片山; 奈穂菊池
Original assignee: 日産化学工業株式会社
Priority date: 2011-03-07
Filing date: 2012-03-06
Publication date: 2012-09-13
Also published as: CN103502312A; KR20140015441A; JP6003882B2; TW201249897A; TWI525129B; KR101842740B1; JPWO2012121257A1; CN103502312B

Abstract

Provided is a composition, particularly a liquid crystal aligning agent, that can form a high-quality polyimide film having uniform characteristics, particularly a liquid crystal alignment film, using a low thermal treatment temperature. Said composition is characterized by including: a polyimide precursor obtained by reacting a diamine component including a first diamine indicated by formula [1] and a second diamine indicated by formula [2] with a tetracarboxylic acid dianhydride component having an alicyclic structure; and/or a polyimide obtained by imidizing the polyimide precursor; and a cyclic ketone that dissolves the polyimide precursor and/or the polyimide. (R₁ and R₂ are each independently C1-12 linear or branched hydrocarbon groups, X is a C8-22 aliphatic group or a group indicated by formula [2A], and n is an integer between 1 and 4.)

Description

Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a composition used for forming a film, in particular, a liquid crystal alignment treatment agent used for forming a liquid crystal alignment film, a liquid crystal alignment film to be obtained, and a liquid crystal display element using the liquid crystal alignment film.

A film made of an organic material such as a polymer material has been widely used as an interlayer insulating film, a protective film, and the like in electronic devices because of its ease of formation and insulation performance. In a liquid crystal display element well known as a display device, an organic film made of an organic material is used as a liquid crystal alignment film.

In the liquid crystal display element, the liquid crystal alignment film is formed on the surface of the substrate that sandwiches the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction. Further, the liquid crystal alignment film has a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction.
In recent years, liquid crystal display elements have become highly functional, and the range of use of these liquid crystal display elements has expanded, and the liquid crystal alignment film has performance and reliability for achieving high display quality by suppressing display defects of the liquid crystal display elements. Is also sought.

Currently, as a main liquid crystal alignment film used industrially, a polyimide organic film which is excellent in durability and suitable for controlling the pretilt angle of liquid crystal is widely used. The liquid crystal alignment film made of this polyimide organic film is composed of a polyamic acid (also called polyamic acid) which is a polyimide precursor and / or a liquid crystal aligning agent which is a composition containing a polyimide solution imidized with polyamic acid. It is formed. That is, the polyimide-based liquid crystal alignment film is formed by applying a liquid crystal alignment treatment agent comprising a polyimide solution or a polyamic acid solution, which is a polyimide precursor, to a substrate and firing at a high temperature of about 200 ° C. to 300 ° C. (For example, refer to Patent Document 1).

Japanese Unexamined Patent Publication No. 09-278724

The baking process for forming the polyimide-based liquid crystal alignment film requires a particularly high temperature in the process of manufacturing a liquid crystal display element. Therefore, in the case where a thin and light plastic substrate having a low heat resistance is used in place of a normal glass substrate as the substrate of the liquid crystal display element, it is required to enable firing at a lower temperature. Similarly, low-temperature firing of the liquid crystal alignment film is also required in order to suppress deterioration such as a decrease in color characteristics in the color filter and to reduce energy costs in manufacturing the liquid crystal display element. Furthermore, the temperature of the baking process is also required to be lowered from the viewpoint of suppressing a decrease in reliability of the liquid crystal display element (such as a decrease in characteristics during long-term use).
Also, in the formation of films such as interlayer insulating films and protective films in other electronic devices and the like, it is required to lower the temperature of the heat treatment process. Low-temperature firing prevents the deterioration of the characteristics of the electronic device and is effective in reducing energy costs.

Therefore, the present invention provides a composition capable of forming a polyimide organic film formed by heating at a low temperature, particularly a liquid crystal alignment treatment agent capable of forming a liquid crystal alignment film by heating at a low temperature, and the liquid crystal alignment treatment agent. An object is to provide a liquid crystal alignment film and a liquid crystal display element using the liquid crystal alignment film.

As a result of intensive studies to achieve the above object, the present inventor obtained new knowledge through the following process.
That is, in general, a polyimide-based film, for example, a liquid crystal alignment film is formed using a polyimide solution obtained by dissolving polyimide or a polyimide precursor in a solvent, or a polyimide precursor solution, as described above. The solution is applied to the substrate and is usually heat-treated at a high temperature of about 200 ° C. to 300 ° C.

When a solution of a polyimide precursor is used for film formation by this heat treatment, for example, a film is formed by performing a dehydration ring-closing reaction (thermal imidization) of polyamic acid and simultaneously removing the solvent.
When a polyimide solution is used for film formation, the main purpose of the heat treatment is to remove the solvent. For this reason, the heat treatment temperature in the case of using the polyimide solution is usually lower than that in the case of using polyamic acid, although it is affected by the boiling point of the solvent used. For example, as disclosed in Japanese Patent Laid-Open No. 9-194725, a film can be formed at a heat treatment temperature of about 200 ° C. Therefore, it is more preferable to use a polyimide solution at a low heat treatment temperature.

On the other hand, when preparing a polyimide solution, the selection of a solvent is important because it usually dissolves a polyimide that is difficult to dissolve. As a solvent for this purpose, a highly polar solvent such as N-methyl-2-pyrrolidone (hereinafter also referred to as NMP) has been used. The boiling point of the highly polar solvent is high such that, for example, the boiling point of NMP is 200 ° C. or higher. When a film is formed from a polyimide solution using NMP as a solvent, a high heat treatment temperature of about 200 ° C. near the boiling point of NMP is required. At lower temperatures, the solvent (NMP) remains in the resulting film. As a result, in the case of a liquid crystal alignment film or the like, the characteristics are degraded, and the characteristics of the liquid crystal display element are degraded.

In addition, since NMP, which is a highly polar solvent, has a relatively high surface tension characteristic, when a film is formed using a polyimide solution using NMP as a solvent, the wetting and spreading characteristics on the substrate are not good. . If the surface tension of the solvent used can be made lower, the coating property to the substrate becomes better. As a result, it is possible to form a high-quality polyimide film having more uniform characteristics without defects during printing application such as repellency and pinholes.
As mentioned above, lowering the heat treatment and improving the coatability during film formation are important in the formation of polyimide films for the purpose of insulating films and protective films for electronic devices, especially liquid crystal alignment films. Become.

The present inventor conducted research to reduce the heat treatment temperature and improve the coating property in the formation of polyimide-based films, particularly polyimide-based liquid crystal alignment films, and found that a diamine component having a specific structure and tetracarboxylic dianhydride. A polyimide precursor obtained from a raw material and / or a polyimide obtained by imidizing the polyimide precursor, dissolves well in a solvent containing a cyclic ketone having a low boiling point and a low surface tension characteristic, and as a result The inventors have found that such an object can be sufficiently achieved.

The present invention is based on the above findings and has the following gist.
(1) A diamine component containing a first diamine represented by the following formula [1] and a second diamine represented by the following formula [2] is reacted with a tetracarboxylic dianhydride component having an alicyclic structure. A composition comprising: a polyimide precursor to be obtained and / or a polyimide obtained by imidizing the polyimide precursor; and a cyclic ketone solvent for dissolving the polyimide precursor and / or the polyimide.

(In the formula [1], R ₁ and R ₂ are each independently a linear or branched hydrocarbon group having 1 to 12 carbon atoms.)

(In the formula [2], X represents a substituent, which is a hydrocarbon group having 8 to 22 carbon atoms or a group represented by the following formula [2A], and n is an integer of 1 to 4.)

(In the formula [2A], Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—. , Y ² is a single bond or (CH ₂ ) _b — (b is an integer of 1 to 15), Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15) ), —O—, —CH ₂ O—, —COO— or OCO—.
Y ⁴ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl having 1 to 3 carbon atoms) Or a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, or an organic group having 12 to 25 carbon atoms having a steroid skeleton. Y ⁵ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring (any hydrogen atom on these cyclic groups has 1 to 3 carbon atoms). And an alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. ⁶ carbon Alkyl group of 1 to 18, fluorine-containing alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkoxyl group an alkoxyl group or having 1 to 18 carbon atoms having 1 to 18 carbon atoms, n is an integer from 0-4. )

(2) The composition according to (1), wherein the diamine having the structure represented by the formula [1] is a diamine having a structure represented by the following formula [1A].

(In the formula [1A], R ₁ is a linear or branched hydrocarbon group having 1 to 12 carbon atoms, and R ₅ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R ₃ and R ₄ is independently a hydrogen atom or a methyl group.)

(3) The composition according to (2) above, wherein the diamine having the structure represented by the formula [1A] is a diamine having a structure represented by the following formula [1B].

(4) The composition according to (1) above, wherein the diamine having the structure represented by the formula [1] is a diamine having a structure represented by the following formula [1C].

(5) The composition according to any one of the above (1) to (4), wherein the diamine having the structure represented by the formula [1] is 20 to 80 mol% among the diamine components.
(6) The composition according to any one of the above (1) to (4), wherein the diamine having the structure represented by the formula [2] is 10 to 80 mol% among the diamine components.
(7) The composition according to any one of (1) to (6), wherein the tetracarboxylic dianhydride is a compound represented by the following formula [3].

(In Formula [3], 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.)

(8) The composition according to the above (7), wherein Z ₁ in the formula [3] is a structure represented by the following formulas [3a] to [3j].

(In the formula [3a], Z ₂ to Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In the formula [3g], Z ₆ and Z ₇ Are hydrogen atoms or methyl groups, which may be the same or different.

(9) The composition according to any one of (1) to (8), wherein the cyclic ketone solvent contains at least one cyclic ketone of a 5-membered ring and a 6-membered cyclic ketone.
(10) A liquid crystal aligning agent comprising the composition according to any one of (1) to (9) above.
(11) A liquid crystal alignment film obtained from the liquid crystal aligning agent according to (10).
(12) A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to (11), which is used for a liquid crystal display device produced through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(13) A liquid crystal display device having the liquid crystal alignment film according to (11).
(14) A polymerizable compound having a liquid crystal layer between a pair of substrates provided with an electrode and the liquid crystal alignment film, and polymerized by at least one of active energy rays and heat between the pair of substrates. The liquid crystal display element according to the above (13), which is produced through a step of polymerizing the polymerizable compound while disposing a liquid crystal composition and applying a voltage between the electrodes.

ADVANTAGE OF THE INVENTION According to this invention, the composition which is excellent in applicability | paintability, and is free from the defect at the time of printing application, such as a repellency and a pinhole, can form the high quality polyimide-type film | membrane of a more uniform characteristic by low heat processing temperature is provided. The
In particular, according to the present invention, there is provided a liquid crystal aligning agent capable of forming a liquid crystal alignment film having excellent electrical properties without defects because it has excellent coating properties and can be fired at a low temperature. From the liquid crystal alignment film obtained by using the liquid crystal aligning agent of the present invention, a liquid crystal display element having high reliability can be obtained because of excellent electrical characteristics.

The diamine component and tetracarboxylic dianhydride used to obtain the polyimide precursor and / or polyimide imidized with the polyimide precursor used in the present invention (hereinafter collectively referred to as the polyimide of the present invention). The components will be described.

<First diamine>
The 1st diamine used in order to obtain the polyimide of this invention is shown by following formula [1]. The diamine represented by the formula [1] is used for improving the solubility of the polyimide in the solvent.

In the formula [1], R ₁ and R ₂ are each independently a hydrocarbon group having 1 to 12 carbon atoms.

The amount of the first diamine used is preferably 10% by mass or more of the entire diamine component used in the reaction for obtaining the polyimide. From the relationship with the usage amount of the second diamine represented by the formula [2] described later, it is preferably 90% by mass or less. A more preferable amount of the first diamine is 30 to 80% by mass.

Preferable examples of the first diamine include a compound having an N-allylaniline structure, for example, a compound of the following formula [1A].

In the formula [1A], R ₁ represents a hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group preferably contains a carbon-carbon double bond, and more preferably the double bond is between the second and third carbons from the nitrogen atom. The number of carbon atoms of R ₁ is 6 or less are preferred from the viewpoint of printability of the liquid crystal alignment treating agent, and more preferably 3 or less.
R ₅ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. This hydrocarbon group may contain a carbon-carbon double bond. Further, R ₅ preferably has 6 or less carbon atoms, more preferably 3 or less. Particularly preferred R ₅ is a hydrogen atom.
R ₃ and R ₄ are independently a hydrogen atom or a methyl group. R ₃ and R ₄ are preferably hydrogen atoms.
In the formula [1A], preferred positions of the two amino groups are the 2,4 position, the 2,5 position, or the 3,5 position on the benzene ring with respect to the N-allyl group.

Preferable examples of the diamine represented by the formula [1A] include the structure of the following formula [1B].

More specifically, it is a compound represented by the following formulas [1B-1] to [1B-8]. Of these, diamines of the formula [1B-1] are particularly preferred. The diamine having the structure represented by the formula [1A] is not limited to these examples.

Moreover, as another example of the diamine represented by the formula [1], for example, a diamine having a structure of the following formula [1C] can be exemplified.

More specifically, it is a compound represented by the following formulas [1C-1] to [1C-6]. Of these, diamines of the formula [1C-1] are particularly preferred. The diamine represented by the formula [1C] is not limited to these examples.

The diamine represented by the formula [1] is one or two types depending on the properties such as solubility in a solvent when polyimide is used, liquid crystal orientation when a liquid crystal alignment film is used, voltage holding ratio, accumulated charge, and the like. A mixture of more than one can also be used.

<Second diamine>
The 2nd diamine used in order to obtain the polyimide used by this invention is shown by following formula [2]. The second diamine is used for the purpose of improving the solubility of the resulting polyimide in a solvent, or for the purpose of imparting vertical alignment when the polyimide film is used as a liquid crystal alignment film.

In the formula [2], X is a hydrocarbon group having 8 to 22 carbon atoms or a group represented by the following formula [2A]. N is an integer of 1 to 4. The substituent X preferably forms a hydrophobic side chain structure.
The amount of the second diamine used is preferably 10% by mass or more based on the total amount of the diamine component used in the reaction for obtaining the polyimide, and is preferably 90% by mass or less in relation to the amount of the first diamine used. A more preferable amount of the second diamine is 25 to 80% by mass.

Next, in the second diamine, when the substituent X is represented by the following formula [2A], the specific structure will be described.

In the formula [2A], Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— and OCO—. One of them. Among them, any one of a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, and COO— is a synthesis of a side chain structure. From the viewpoint of facilitating the process. Further, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O—, and COO— are more preferable.

In the formula [2A], Y ² is any one of a single bond and (CH ₂ ) _b — (b is an integer of 1 to 15). Among these, a single bond or (CH ₂ ) _b — (b is an integer of 1 to 10) is preferable.
Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— and OCO—. Among these, any one of a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— and OCO— It is preferable from the viewpoint of facilitating the synthesis of the chain structure. Further, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O—, —COO— and OCO— are more preferable.

In the formula [2A], Y ⁴ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon Any one of an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms and a fluorine atom), or a steroid skeleton And a divalent organic group selected from organic groups having 12 to 25 carbon atoms. Among these, a divalent organic group having 12 to 25 carbon atoms and having any one of a benzene ring, a cyclohexane ring, and a steroid skeleton is preferable.

In the formula [2A], Y ⁵ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl having 1 to 3 carbon atoms. The group may be substituted with any one of a group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, and a fluorine atom.
In the formula [2A], n is an integer of 0 to 4. Preferably, it is an integer of 0-2.

In the formula [2A], Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. One of them. Among them, it is one of an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 10 carbon atoms. Is preferred. More preferably, it is any one of an alkyl group having 1 to 12 carbon atoms and an alkoxyl group having 1 to 12 carbon atoms. More preferably, it is any one of an alkyl group having 1 to 9 carbon atoms and an alkoxyl group having 1 to 9 carbon atoms.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in formula [2A] for constituting substituent X of formula [2] are shown in Tables 1 to 42 below. 2-1 to 2-629.

c is an integer having 1 to 10 carbon atoms

Next, although the specific example of the diamine of the structure shown by Formula [2] is given, it is not limited to these examples.
2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6 In addition to -diaminotoluene, diamines represented by the following formulas [2-1] to [2-31] can be mentioned.

(In the formulas [2-1] to [2-3], R ₁ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, or CH ₂ OCO—, and R ₂ represents the number of carbon atoms. A linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or 1 to 22 carbon atoms A linear or branched fluorine-containing alkoxyl group.)

(In the formulas [2-4] to [2-6], R ₃ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ — or CH ₂ R ₄ is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, or a linear or branched fluorine group having 1 to 22 carbon atoms. A contained alkyl group or a linear or branched fluorine-containing alkoxyl group having 1 to 22 carbon atoms.)

(In the formulas [2-7] and [2-8], R ₅ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, — CH ₂ — or O—, and R ₆ represents a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.

(In Formula [2-9] and Formula [2-10], R ₇ is a linear or branched alkyl group having 3 to 12 carbon atoms, and cis-trans isomerism of 1,4-cyclohexylene is Trans isomer.)

(In the formulas [2-11] and [2-12], R ₈ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is Trans isomer.)

(In the formula [2-13], A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₃ is a 1,4-cyclohexylene group or A ₂ -phenylene group, A ₂ is an oxygen atom or COO— * (where a bond marked with “*” is bonded to A ₃ ), and A ₁ is an oxygen atom or COO — * ( However, a bond marked with “*” is combined with (CH ₂ ) a ₂ ). 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. )

The diamine represented by the formula [2] may be one kind or two depending on properties such as solubility in a solvent when polyimide is used, liquid crystal orientation when a liquid crystal alignment film is used, voltage holding ratio, accumulated charge, and the like. A mixture of more than one can also be used.

<Other diamines>
The composition of the present invention contains a polyimide obtained by reacting a diamine component containing a first diamine and a second diamine with a tetracarboxylic dianhydride component having an alicyclic structure. At this time, as long as the effects of the present invention are not impaired, diamines other than the above (also referred to as other diamines) can be used in combination.
Specific examples of the other diamines are listed below.

Other diamines include, for example, m-phenylenediamine, p-phenylenediamine, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4 -Diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl, 3,3'-dimethyl -4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4 '-Diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4 4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3 ' -Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diamino Diphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-amino Phenyl) silane, dimethyl-bis ( -Aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4 '-Diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diaminodiphenyl) amine, N -Methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3 , 3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-dia Minonaphthalene, 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-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4aminophenyl) butane, 1,4-bis (3-aminophenyl) butane Bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bi (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)] dianiline, 4,4 ′-[1,3-phenylenebis (methylene)] dianiline, 3,4 '-[1,4-phenylenebis (methylene)] dianiline, 3,4'-[1,3-phenylenebis (methylene)] dianiline, 3,3 '-[1,4-phenylenebis (methylene)] dianiline 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophen L) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis ( 3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis (4-aminobenzamide), N, N '-(1,3-phenylene) bis (4-aminobenzamide), N, N'-(1,4-phenylene) bis ( 3-aminobenzamide), N, N ′-(1,3-phenylene) bis (3-aminobenzamide), N, N′-bis (4-aminophenyl) terephthalamide, N, N′-bis (3- Aminophenyl) terephthalamide, N, N′-bis (4-aminophenyl) isophthalamide, N, N′-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4 , 4′-bis (4-aminophenoxy) diphenylsulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoro Lopan, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-aminophenyl) propane, 2,2′-bis (3-amino-4-methylphenyl) propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis ( 4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6- Bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophen Xyl) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3 -Aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-amino Aromatic diamines such as phenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane; bis (4-aminocyclohexyl) methane, bis (4-amino-3- Cycloaliphatic diamines such as methylcyclohexyl) methane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc. An aliphatic diamine;

Examples of other diamines include those having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring in the diamine side chain, or those having a macrocyclic substituent composed of these. . Specifically, diamines represented by the following formulas [DA1] to [DA15] can be exemplified.

(Wherein _{[DA1] ~ [DA6],} A 2 is -COO -, - OCO -, - CONH -, - NHCO -, - CH 2 -, - O -, - CO- or a NH-, _{A 3} Is a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.)

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

(In the formula [DA11], m is an integer of 0 to 3, and in the formula [DA15], n is an integer of 1 to 5.)

Furthermore, as long as the effects of the present invention are not impaired, a diamine having a carboxyl group in the molecule represented by the following formulas [DA16] to [DA20] can also be used.

(In the formula [DA16], m1 is an integer of 1 to 4. In the formula [DA17], 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) a CO-, _{m 2} and _{m 3} is an integer of 0 to 4, _and, m 2 + _{m 3} Is an integer from 1 to 4.
In the formula [DA18], m ₄ and m ₅ are each an integer of 1 to 5.
In the formula [DA19], A ₅ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m ₆ is an integer of 1 to 5.
In the formula [DA20], A ₆ represents 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—, and m ₇ is an integer of 1 to 4. )

In addition, a diamine represented by the following formula [DA21] or [DA22] can be used as long as the effects of the present invention are not impaired.

In addition, diamines represented by the following formulas [DA23] to [DA27] can be used as long as the effects of the present invention are not impaired.

(In the formulas [DA23] to [DA27], A ₁ is a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.)

One of the other diamines described above depends on important properties of the liquid crystal alignment film, such as solubility in a solvent when used as a polyimide, liquid crystal alignment when used as a liquid crystal alignment film, voltage holding ratio, and accumulated charge. Alternatively, two or more types can be mixed and used.

<Tetracarboxylic dianhydride>
In order to obtain the polyimide of the present invention, a tetracarboxylic dianhydride having an alicyclic structure (also referred to as a specific tetracarboxylic dianhydride) is used as the tetracarboxylic dianhydride component. As the specific tetracarboxylic dianhydride, a tetracarboxylic dianhydride having an alicyclic structure represented by the following formula [3] is preferable.

In the formula [3], 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.
Specifically, the structure is represented by the following formulas [3a] to [3j].

In the formula [3a], Z ₂ to Z ₅ are groups selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring, and may be the same or different.
In the formula [3g], Z ₆ and Z ₇ are a hydrogen atom or a methyl group, and may be the same or different.
In the formula [3], particularly preferred structure of Z ₁ is the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] or the formula from the viewpoint of polymerization reactivity and ease of synthesis. [3g]. Among these, the formula [3a] or the formula [3f] is preferable, and the formula [3a] is most preferable.
When the tetracarboxylic dianhydride represented by the formula [3] is used, the amount used is preferably 40% by mass or more, more preferably 50% by mass or more, of the total tetracarboxylic dianhydride component. . All of the tetracarboxylic dianhydride components used for the polyimide synthesis may be tetracarboxylic dianhydrides of the formula [3].

In this invention, unless the effect of this invention is impaired, other tetracarboxylic dianhydrides other than specific tetracarboxylic dianhydride can be used.
Specific examples of other tetracarboxylic dianhydrides include, for example, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,4 5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) ) Sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro 2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5- Pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, Examples include 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

In the composition of the present invention, among the above-mentioned other tetracarboxylic dianhydrides, for example, in the case of a liquid crystal alignment film, in consideration of characteristics such as liquid crystal alignment properties, voltage holding characteristics and accumulated charges, one type or two More than one type can be selected and used.

<Polyimide precursor and polyimide>
The polyimide precursor and polyimide used in the composition of the present invention are preferably obtained as follows. Here, the polyimide precursor represents polyimide acid (also referred to as polyamic acid). That is, the polyimide precursor includes a diamine component containing the first diamine represented by the above formula [1] and the second diamine represented by the above formula [2], and a tetracarboxylic acid having the above alicyclic structure. It is obtained by reacting with an acid dianhydride component.

In this case, the amount of the first diamine used is preferably 20 mol% or more, more preferably 30 mol% or more of the entire diamine component. Moreover, 80 mol% or less is preferable from the relationship with the preferable usage-amount of a 2nd diamine. Moreover, the usage-amount of 2nd diamine has preferable 10 mol% or more of the whole diamine component, More preferably, it is 25 mol% or more. Moreover, it is preferable to set it as 80 mol% or less from the relationship with the preferable usage-amount of a 1st diamine.

As a specific method for producing a polyimide precursor by a reaction between a diamine component and tetracarboxylic dianhydride, a known synthesis method can be used. For example, it is possible to use a method in which a diamine component and tetracarboxylic dianhydride are reacted in an organic solvent. This method is preferable in that the reaction proceeds relatively efficiently in an organic solvent and generation of by-products is small.

The organic solvent used for the reaction between the diamine component and tetracarboxylic dianhydride is not particularly limited as long as the produced polyamic acid is soluble. Specific examples thereof include, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl. -Imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.

Further, even a solvent that does not dissolve the polyimide precursor can be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate. In addition, since the water | moisture content in an organic solvent inhibits a polymerization reaction and causes the produced | generated polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.

When the diamine component and tetracarboxylic dianhydride are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride is used as it is or in the organic solvent. It is possible to use a method of adding it after being dispersed or dissolved. Conversely, a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, a method of adding tetracarboxylic dianhydride and a diamine component alternately, etc. Can do. In the present invention, any of these methods may be used. In addition, when the diamine component or tetracarboxylic dianhydride is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. It is good also as a high molecular weight body by carrying out a mixing reaction.

The temperature at which the diamine component and tetracarboxylic dianhydride are reacted can be arbitrarily selected within the range of −20 to 150 ° C., but in the range of −5 to 100 ° C. in consideration of the reaction efficiency. It is preferable. Moreover, reaction can be performed by arbitrary density | concentrations. However, if the concentration is too low, it is difficult to obtain a high molecular weight polyimide precursor. On the other hand, if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. In addition, it is also possible to carry out at a high concentration at the initial stage of the reaction and then add an organic solvent.

In the polymerization reaction for obtaining the polyimide precursor, the ratio between the total number of moles of the diamine component and the total number of moles of the tetracarboxylic dianhydride is preferably 0.8 to 1.2. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polymer produced. Therefore, it is possible to determine the total molar ratio by appropriately selecting depending on the case.

The polyimide used in the present invention is obtained by dehydrating and ring-closing the above polyimide precursor to imidize it. In this case, the dehydration cyclization rate (imidation rate) of the polyimide precursor is not necessarily 100%, and is, for example, in the range of 35 to 95%, more preferably 45 to 80%, depending on the application and purpose. It can be adjusted within the range.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, and catalyst imidization in which a catalyst is added to the polyimide precursor solution.
The temperature when the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C. The imidization of the polyimide precursor is preferably performed while removing water generated by the imidization reaction from the reaction system.
The catalytic imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amido group. 30 mole times.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like, and among them, pyridine is preferable in that it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferable because purification after the completion of the reaction is easy. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

When the produced polyimide is recovered from the polyimide reaction solution, the reaction solution may be poured into a poor solvent and precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. In addition, when the polymer recovered by precipitation is redissolved in a solvent and re-precipitation recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these to further improve the efficiency of purification.

The molecular weight of the polyimide precursor and polyimide is the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the coating film obtained by using this, the workability during coating film formation, and the uniformity of the coating film. It is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<Composition for film formation>
The composition for forming a film of the present invention, for example, a liquid crystal aligning agent is a composition containing the imide polymer of the present invention obtained as described above and a solvent in which the polyimide polymer is dissolved. The content of the polyimide polymer of the present invention contained in the composition is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass.
In the present invention, all of the polymer components contained in the composition may be the polyimide of the present invention, but in addition to the polyimide of the present invention, the diamine component containing the first diamine and the second diamine described above, Other than the polyimide synthesized from tetracarboxylic dianhydride having an alicyclic structure, a polyimide having another structure may be contained. In that case, the content of the polyimide having another structure in the polymer component can be 0.5 to 15% by mass, preferably 1 to 10% by mass.

In the composition of the present invention, the polymer component containing the polyimide of the present invention is contained in a dissolved state. As the solvent, a cyclic ketone is used. Cyclic ketone is a solvent that dissolves the polyimide of the present invention, has a lower boiling point than NMP, and has low surface tension characteristics. The cyclic ketone is preferably a ketone having a 4- to 10-membered ring, particularly preferably a 5- to 7-membered alicyclic structure. Preferred specific examples include cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, Examples thereof include cyclononanone and cyclodecanone. Of these, any of cyclohexanone and cyclopentanone, or a mixture thereof is particularly preferable.

In the case of the composition of the present invention, for example, a liquid crystal aligning agent using the same, the solvent content is preferably 70 to 99% by mass from the viewpoint of forming a uniform film by coating. This content can be appropriately changed depending on the desired thickness of the film. As the solvent, it is possible to use only a cyclic ketone solvent. For example, as long as it does not interfere with low-temperature baking and improvement in coating properties required when obtaining a liquid crystal alignment film, other solvents are appropriately used. It is also possible to mix organic solvents.

Specific examples of other organic solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, , 3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.
Even when these other organic solvents are contained, the content of the cyclic ketone solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more in the total solvent. It is.

The composition of the present invention, for example, a liquid crystal aligning agent is another organic solvent for improving coating properties for the purpose of further improving the uniformity of film thickness and surface smoothness, as long as the effects of the present invention are not impaired. (Hereinafter also referred to as a poor solvent).
Specific examples include the following. For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl 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, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate 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, 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, dihexyl Ether, n-hexane, n-pentane, n-octane, diethyl ether Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxy Ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy- 2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether Ter-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactyl isoamyl ester, etc. have low surface tension Such as a solvent. These poor solvents may be used alone or in combination.

Even when the above poor solvent is contained, the content of the cyclic ketone solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

Furthermore, the composition of the present invention improves the adhesion between the formed film and the substrate, a compound that improves the thickness uniformity and surface smoothness of the coated film, as long as the effects of the present invention are not impaired. Compounds can be included.

Examples of the compound that improves the uniformity of the film thickness and the surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. For example, specifically, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the composition.

Specific examples of the compound that improves the adhesion between the formed film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-tri Toxisilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxy Silane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Lopylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl -2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N′-tetraglycidyl-4, 4′-diaminodiphenylmethane and the like.

When a compound that improves the adhesion between the formed film and the substrate is used, the amount of the compound added is 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the composition. The amount is preferably 1 to 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.

As long as the effects of the present invention are not impaired, the composition of the present invention comprises a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group. It is also possible to contain a crosslinkable compound having at least one selected substituent or a crosslinkable compound having a polymerizable unsaturated bond.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine. Tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) ) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobifu Nyl, triglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3 -Epoxypropoxy) phenyl) ethyl) phenyl) propane, 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2 , 3-epoxypropoxyphenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

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

Specifically, it is a crosslinkable compound represented by the following formulas [4-1] to [4-11].

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

Specifically, it is a crosslinkable compound represented by the following formulas [5-1] to [5-37].

(In the formula [5-24], n is an integer of 1 to 5, and in the formula [5-25], n is an integer of 1 to 5, and in the formula [5-36], n is 1 to 100. (In the formula [5-37], n is an integer of 1 to 10.)

Furthermore, polysiloxanes having at least one structure represented by the following formulas [5-38] to [5-40] can also be mentioned.

(In the formulas [5-38] to [5-40], R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represents a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, An alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic ring, at least one of which is a structure represented by the formula [5]).

More specifically, compounds of the following formulas [5-41] and [5-42] can be mentioned.

(In the formula [5-41], R ₆ is a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic ring, One is a structure represented by the formula [5]. In the formula [5-42], n is an integer of 1 to 10.)

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril. -Formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin and the like. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group and / or an alkoxymethyl group can be used. These melamine derivatives or benzoguanamine derivatives can also exist as dimers or trimers. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

Examples of melamine derivatives or benzoguanamine derivatives include MX-750 with an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5.8 substituted methoxymethyl groups per triazine ring. MW-30 (manufactured by Sanwa Chemical Co., Ltd.) and Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and the like, methoxymethylated melamine, Cymel 235, 236, 238, Methoxymethylated butoxymethylated melamine such as 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, methoxymethyl such as Cymel 1123 Ethoxymethylation Nzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 (Mitsui Cyanamid Co., Ltd.) Manufactured).

Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, methoxymethylolated glycoluril such as Powderlink 1174, and the like.
Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.
Specifically, it is a crosslinkable compound represented by the following formulas [6-1] to [6-48].

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol. Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane and glycerin polyglycidyl ether poly (meth) acrylate; ethylene glycol di (meth) 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, butylene glycol di (me ) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) ) Acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, neopentyl glycol dihydroxypivalate Crosslinkable compounds having two polymerizable unsaturated groups in the molecule such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropylene (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl ( Crosslinkable compounds having one polymerizable unsaturated group in the molecule such as (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate ester, N-methylol (meth) acrylamide; Can be mentioned.

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

In Formula [7], E ₁ is a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring, and E ₂ is It is a group selected from the following formula [7a] and formula [7b], and n is an integer of 1 to 4.

The said compound is an example of a crosslinkable compound, It is not limited to these. Moreover, the crosslinkable compound contained in the composition of the present invention may be one kind or a combination of two or more kinds.
The content of the crosslinkable compound in the composition of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the polymer component. In order for the crosslinking reaction to proceed and to exhibit the desired effect and not to lower the orientation of the liquid crystal, the amount is more preferably 0.1 to 100 parts by weight, particularly 1 to 50 parts by weight, based on 100 parts by weight of the polymer component. Part is most preferred.
In the composition of the present invention, in addition to the above, as long as the effects of the present invention are not impaired, a dielectric for the purpose of changing the electrical properties such as the resistance of the film and the dielectric constant and conductivity of the liquid crystal alignment film, A conductive substance may be added.

Furthermore, when the composition of the present invention is a liquid crystal alignment treatment agent, the compound represented by the following formula is used as a compound that promotes charge transfer in a liquid crystal alignment film to be formed and promotes charge release of a liquid crystal cell using the liquid crystal alignment film Nitrogen-containing heterocyclic amines represented by M1] to [M156] can also be added. These amines may be added directly to the solution of the composition, but it is preferable to add them after making a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent. The solvent is not particularly limited as long as it is an organic solvent that dissolves polyimide in addition to the cyclic ketone solvent described above.

<Liquid crystal alignment film and liquid crystal display element>
The case where a liquid crystal aligning agent is formed from a liquid crystal aligning agent will be described using a liquid crystal aligning agent which is one of the compositions of the present invention as an example. The liquid crystal alignment treatment agent is applied onto a substrate, fired by heat treatment, and then subjected to alignment treatment by rubbing treatment or light irradiation to form a liquid crystal alignment film. In the case of vertical alignment use, a liquid crystal alignment film can be formed without alignment treatment.
The substrate is not particularly limited as long as it is a highly transparent substrate. In addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.

The method for applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and ink jet methods are generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose. The liquid crystal aligning agent of the present invention has good coating properties even when the above coating method is used.

After the liquid crystal alignment treatment agent is applied on the substrate, the solvent is evaporated at 50 ° C. to 180 ° C., preferably 80 ° C. to 150 ° C. by a heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven. It can be made into a coating film. If the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it 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 100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.

The liquid crystal display element is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
As a liquid crystal cell manufacturing method, a pair of substrates on which a liquid crystal alignment film is formed are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside, so that the other Examples include a method in which substrates are attached and liquid crystal is injected under reduced pressure, or a method in which liquid crystal is dropped onto a liquid crystal alignment film surface on which spacers are dispersed and then a substrate is attached and sealed.

The liquid crystal alignment film has a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. And it is preferably used also for the liquid crystal display element manufactured through the process of superposing | polymerizing a polymeric compound by at least one of irradiation of an active energy ray, and a heating, applying a voltage between electrodes. Here, ultraviolet rays are suitable as the active energy ray.

The above liquid crystal display element controls the pretilt of 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 after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound. The pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. The PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process.

That is, in the liquid crystal display element, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, a liquid crystal cell is prepared, and a polymerizable compound is polymerized by at least one of ultraviolet irradiation and heating. Thus, the alignment of liquid crystal molecules can be controlled.
To give an example of manufacturing a PSA type liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded together, the liquid crystal is injected under reduced pressure and sealed, and the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed. .

In the liquid crystal, a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed. Examples of the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. In that case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled, and when it exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases and the liquid crystal display The burn-in characteristic of the element is deteriorated.
After the liquid crystal cell is produced, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of liquid crystal molecules can be controlled.

In addition, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured through a step of disposing a liquid crystal alignment film containing a group and applying a voltage between the electrodes. Here, ultraviolet rays are suitable as the active energy ray. The wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C.

In order to obtain a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat, a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent, A method using a coalescing component may be mentioned. Since the liquid crystal alignment treatment agent of the present invention contains a specific compound having a double bond site that reacts by irradiation with heat or ultraviolet rays, the alignment of liquid crystal molecules can be controlled by at least one of ultraviolet irradiation and heating. it can.

If an example of liquid crystal cell production is given, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is bonded and liquid crystal is injected under reduced pressure to seal, and a method in which the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is bonded and sealed.
A liquid crystal display element is obtained through the above steps. Since these liquid crystal display elements use the liquid crystal alignment film of the present invention as the liquid crystal alignment film, the manufacturing process becomes lower temperature, excellent in reliability, and suitable for a large-screen, high-definition liquid crystal television. Is available.

Examples are described below, but the present invention is not construed as being limited thereto. Abbreviations used in Examples and Comparative Examples are as follows.

<First diamine having a structure represented by the formula [1]>
D1: N, N-diallyl-2,4-diaminoaniline

<Second diamine having a structure represented by the formula [2]>
D2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

<Other diamines>
D3: p-phenylenediamine

<Tetracarboxylic dianhydride>
M1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride M2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride M3: pyromellitic dianhydride object

<Cyclic ketone solvent>
CHN: cyclohexanone CPN: cyclopentanone <other organic solvent>
NMP: N-methyl-2-pyrrolidone BCS: Ethylene glycol monobutyl ether PGME: Propylene glycol monomethyl ether

In addition, physical properties such as molecular weight and imidization rate of polyimide were evaluated as follows.
(Measurement of molecular weight of polyimide)
The molecular weight of polyimide in the synthesis example is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and columns (KD-803, KD-805) (manufactured by Shodex). The measurement was performed as described above.
Column temperature: 50 ° C.
Eluent: N, N′-dimethylformamide (as additive, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol) / L, tetrahydrofuran (THF) 10 ml / L).
Flow rate: 1.0 ml / min.
Standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000) 000 and 1,000) (manufactured by Polymer Laboratory).

(Measurement of imidization rate)
The imidation ratio of polyimide in the synthesis example was measured as follows.
Polyimide powder (20 mg) is put into an NMR sample tube (NMR sampling tube standard φ5 (manufactured by Kusano Kagaku)) and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) ( 0.53 ml) was added and completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR (nuclear magnetic resonance) measuring instrument (JNW-ECA500) (manufactured by JEOL Datum). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidization rate (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

<Synthesis of polyimide>
<Synthesis Example 1>
M2 (2.75 g, 11.0 mmol), D1 (2.68 g, 13.2 mmol), and D2 (3.35 g, 8.8 mmol) were mixed in NMP (26.4 g) and at 80 ° C. for 5 hours. After the reaction, M1 (2.14 g, 10.9 mmol) and NMP (17.3 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (4.11 g) and pyridine (1.59 g) were added as an imidization catalyst and reacted at 100 ° C. for 3 hours. It was. This reaction solution was put into methanol (253 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (A). The imidation ratio of this polyimide was 80%, the number average molecular weight was 21,500, and the weight average molecular weight was 68,700.

<Synthesis Example 2>
M1 (3.61 g, 18.4 mmol), D1 (2.81 g, 13.8 mmol), and D2 (3.50 g, 9.2 mmol) were mixed in NMP (29.7 g) and at 25 ° C. for 15 hours. After the reaction, M3 (0.95 g, 4.4 mmol) and NMP (13.7 g) were added and reacted at 25 ° C. for 4 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (2.58 g) and pyridine (1.07 g) were added as imidization catalysts, and the mixture was heated at 40 ° C. for 1 hour 30 minutes. Reacted. This reaction solution was put into methanol (246 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (B). The imidation ratio of this polyimide was 51%, the number average molecular weight was 18,700, and the weight average molecular weight was 57,800.

<Synthesis Example 3>
M1 (4.29 g, 21.9 mmol), D1 (3.13 g, 15.4 mmol), and D2 (2.51 g, 6.6 mmol) were mixed in NMP (39.7 g) and 24 hours at 25 ° C. Reaction was performed to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.35 g) and pyridine (0.56 g) were added as imidization catalysts and reacted at 40 ° C. for 2 hours. It was. This reaction solution was poured into methanol (123 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (C). The imidation ratio of this polyimide was 53%, the number average molecular weight was 19,800, and the weight average molecular weight was 55,900.

<Synthesis Example 4>
M1 (4.61 g, 23.5 mmol), D1 (1.95 g, 9.6 mmol), D2 (2.74 g, 7.2 mmol), and D3 (0.78 g, 7.2 mmol) were converted to NMP (40.3 g). ) And reacted at 25 ° C. for 24 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.44 g) and pyridine (0.60 g) were added as an imidization catalyst and reacted at 40 ° C. for 2 hours. It was. This reaction solution was poured into methanol (124 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (D). The imidation ratio of this polyimide was 48%, the number average molecular weight was 17,200, and the weight average molecular weight was 48,100.

<Synthesis Example 5>
M2 (5.63 g, 22.5 mmol) and D3 (3.24 g, 30.0 mmol) were mixed in NMP (26.6 g), reacted at 40 ° C. for 5 hours, and then M1 (1.24 g, 6.3 mmol) and NMP (13.8 g) were added and reacted at 25 ° C. for 6 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (20.0 g) and diluting to 5% by mass, acetic anhydride (2.96 g) and pyridine (2.29 g) were added as imidization catalysts, and the mixture was stirred at 90 ° C. for 2.5 hours. Reacted. This reaction solution was poured into methanol (298 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (E). The imidation ratio of this polyimide was 51%, the number average molecular weight was 15,300, and the weight average molecular weight was 68,800. Moreover, this polyimide does not use the 1st and 2nd diamine for a diamine component.
Table 43 summarizes the compositions and imidization ratios of the polyimides obtained in Synthesis Examples 1 to 5.

<Polyimide solubility test>
<Examples 1 to 4 and Comparative Example 1>
Using the polyimide powders obtained in Synthesis Examples 1 to 5, the solubility in cyclohexanone (CHN) and cyclopentanone (CPN), which are cyclic ketone solvents, was tested.
CHN (15.7 g) was added to each polyimide powder (1.0 g) of polyimide powders (A) to (E) and stirred at 25 ° C. for 24 hours, and the presence or absence of turbidity or precipitation was visually confirmed. .

Next, CPN (15.7 g) is added to each polyimide powder (1.0 g) of polyimide powders (A) to (E), and stirred at 25 ° C. for 24 hours to visually check for turbidity and precipitation. Confirmed with.
The results of the solubility test are shown in Table 44.

From the above results, it was confirmed that the polyimide powders of Examples 1 to 4 were uniformly dissolved in the cyclic ketone solvent. On the other hand, the polyimide powder (E) of Comparative Example 1 was insoluble in the cyclic ketone solvent.

<Preparation of a composition containing a polyimide and a solvent and a liquid crystal alignment treatment agent>
<Examples 5 to 8>
CHN (27.57 g) was added to each of the polyimide powders (A) to (D) of Synthesis Examples 1 to 4 (1.0 g each) and stirred at 50 ° C. for 24 hours to dissolve each polyimide. In any of the polyimide solutions, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
Next, the obtained polyimide solutions were pressure filtered through a membrane filter having a pore diameter of 1 μm to obtain liquid crystal aligning agents (1) to (4) having a polyimide component content of 3.5% by mass.

<Examples 9 to 12>
CPN (27.6 g) was added to each of the polyimide powders (A) to (D) (1.0 g each) of Synthesis Examples 1 to 4, and stirred at 50 ° C. for 24 hours to dissolve each polyimide. In any of the polyimide solutions, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
Next, the obtained polyimide solutions were subjected to pressure filtration through a membrane filter having a pore diameter of 1 μm to obtain liquid crystal aligning agents (5) to (8) having a polyimide component content of 3.5% by mass.

<Examples 13 to 15>
CHN (13.3 g) was added to each of the polyimide powders (A) to (C) of Synthesis Examples 1 to 3 (1.0 g each) and stirred at 50 ° C. for 24 hours to dissolve each polyimide. Thereafter, NMP (14.3 g) was further added to each of the obtained solutions and stirred to obtain each polyimide solution containing CHN and NMP. In any of the polyimide solutions, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
Next, each polyimide solution containing CHN and NMP is subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm, and the liquid crystal aligning agents (9) to (11) having a polyimide component content of 3.5% by mass. Got.

<Examples 16 to 18>
CPN (13.3 g) was added to each of the polyimide powders (A) to (C) of Synthesis Examples 1 to 3 (1.0 g each) and stirred at 50 ° C. for 24 hours to dissolve each polyimide. Then, NMP (14.3g) was further added and stirred with respect to each obtained solution, and each polyimide solution containing CPN and NMP was obtained. In any of the polyimide solutions, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
Next, each polyimide solution containing CPN and NMP is subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm, and the liquid crystal aligning agent (12) to (14) having a polyimide component content of 3.5% by mass. Got.

<Examples 19 to 21>
CHN (13.3 g) was added to each of the polyimide powders (A) to (C) of Synthesis Examples 1 to 3 (1.0 g each) and stirred at 50 ° C. for 24 hours to dissolve each polyimide. Thereafter, NMP (5.72 g) and BCS (8.57 g) were further added to each of the obtained solutions and stirred to obtain each polyimide solution containing CHN, NMP, and BCS. In any of the polyimide solutions, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
Next, each polyimide solution containing CHN, NMP, and BCS is subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm, and the liquid crystal aligning agent (15) to (15) to (15) to ( 17) was obtained.

<Examples 22 to 24>
CPN (13.3 g) was added to each of the polyimide powders (A) to (C) of Synthesis Examples 1 to 3 (1.0 g each) and stirred at 50 ° C. for 24 hours to dissolve each polyimide. Thereafter, NMP (5.72 g) and BCS (8.57 g) were further added to each of the obtained solutions and stirred to obtain polyimide solutions containing CPN, NMP, and BCS. In any of the polyimide solutions, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
Next, each polyimide solution containing CPN, NMP, and BCS is pressure filtered through a membrane filter having a pore size of 1 μm, and the liquid crystal alignment treatment agent (18) to (18)-( 20) was obtained.

<Examples 25 to 27>
CHN (19.0 g) was added to each of the polyimide powders (A) to (C) of Synthesis Examples 1 to 3 (1.0 g each) and stirred at 50 ° C. for 24 hours to dissolve each polyimide. Then, PGME (8.57g) was further added and stirred with respect to each obtained solution, and each polyimide solution containing CHN and PGME was obtained. In any of the polyimide solutions, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
Next, each polyimide solution containing CHN and PGME is subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm, and the liquid crystal aligning agent (21) to (23) having a polyimide component content of 3.5% by mass. Got.

<Examples 28 to 30>
CPN (19.0 g) was added to each of the polyimide powders (A) to (C) of Synthesis Examples 1 to 3 (1.0 g each) and stirred at 50 ° C. for 24 hours to dissolve each polyimide. Then, PGME (8.57g) was further added and stirred with respect to each obtained solution, and each polyimide solution containing CPN and PGME was obtained. In any of the polyimide solutions, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
Next, each polyimide solution containing CPN and PGME is subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm, and the liquid crystal aligning agent (24) to (26) having a polyimide component content of 3.5% by mass. Got.

<Comparative Examples 2 to 4>
NMP (31.3 g) was added to each of the polyimide powders (A) to (C) of Examples 1 to 3 (2.0 g each) and stirred at 50 ° C. for 24 hours to dissolve each polyimide. In any of the polyimide solutions, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
Next, the obtained polyimide solutions were subjected to pressure filtration through a membrane filter having a pore diameter of 1 μm to obtain liquid crystal aligning agents (27) to (29) having a polyimide component content of 6% by mass.
Tables 45 to 47 show the types and solubility of polyimides and solvents of the liquid crystal aligning agents obtained in Examples 5 to 30 and Comparative Examples 2 to 4.

<Production of liquid crystal alignment film and liquid crystal display element>
A liquid crystal alignment film was prepared using the liquid crystal alignment treatment agents obtained in Examples 5 to 30, and a liquid crystal surface element using the liquid crystal alignment film was prepared. As the liquid crystal display element, a vertically aligned liquid crystal cell was produced corresponding to the characteristics of the liquid crystal alignment film.
A liquid crystal cell was prepared by spin-coating a liquid crystal aligning agent on a glass substrate with an ITO electrode (length 40 mm × width 30 mm, thickness 0.7 mm), and heat-circulating clean for 5 minutes on a hot plate at 80 ° C. After heat-treating at 220 ° C. for 30 minutes in an oven, a liquid crystal alignment film was formed as a coating film having a thickness of 100 nm to obtain a substrate with a liquid crystal alignment film. It was found that all the liquid crystal alignment films formed on the substrate were excellent in film thickness uniformity, and the liquid crystal alignment treatment agent showed excellent coating properties.

Two substrates with this liquid crystal alignment film were prepared, 6 μm spacers were sprayed on one liquid crystal alignment film surface, and then a sealant (XN-1500T, manufactured by Mitsui Chemicals) was printed thereon. Next, after bonding the other substrate and the liquid crystal alignment film face each other, the sealing agent was cured by heat treatment at 150 ° C. for 90 minutes in a heat-circulating clean oven to produce an empty cell. . A nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a vertically aligned liquid crystal cell (liquid crystal display element).
About the obtained liquid crystal cell, when the alignment state of the liquid crystal was observed with a polarizing microscope (ECLIPSE E600WPOL, manufactured by Nikon Corporation), it was confirmed that a uniform vertical alignment of liquid crystals without defects was formed.

Tables 48 and 49 show the results of the alignment state of the liquid crystal of the liquid crystal display element.

Next, liquid crystal display elements were produced using the liquid crystal alignment treatment agents of Examples 5 to 11 and Comparative Examples 2 to 4. The liquid crystal display element was produced by the method described above. A voltage of 1 V was applied to these liquid crystal display elements at a temperature of 80 ° C. at 60 μm, the voltage after 50 ms was measured, and how much the voltage was held compared to immediately after the application was shown as a voltage holding ratio. The measurement was performed using a VHR-1 voltage holding ratio measuring device (manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ± 1 V, Pulse Width: 60 μs, and Frame Period: 50 ms.
Table 50 shows the results of the voltage holding ratio of the liquid crystal display element.

From the above results, it can be seen that the liquid crystal aligning agent of the present invention can be provided, and the liquid crystal aligning agent is excellent in coatability. Moreover, it turns out that the liquid crystal aligning film using the liquid-crystal aligning agent of this invention is possible by low-temperature baking.

The composition of the present invention can be widely used for the formation of films such as interlayer insulating films and protective films in electronic devices and the like, and in particular, as a liquid crystal alignment treatment agent, it has excellent coating properties and can be fired at a low temperature. It is used for forming a liquid crystal alignment film used for a highly reliable liquid crystal display element.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2011-049430 filed on March 7, 2011 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims

A polyimide obtained by reacting a diamine component containing a first diamine represented by the following formula [1] and a second diamine represented by the following formula [2] with a tetracarboxylic dianhydride component having an alicyclic structure A composition comprising a precursor and / or a polyimide obtained by imidizing the polyimide precursor, and a cyclic ketone solvent for dissolving the polyimide precursor and / or the polyimide.

(In the formula [1], R 1 and R 2 are each independently a linear or branched hydrocarbon group having 1 to 12 carbon atoms.)

(In the formula [2], X represents a substituent, which is a hydrocarbon group having 8 to 22 carbon atoms or a group represented by the following formula [2A], and n is an integer of 1 to 4.)

(In the formula [2A], Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—. , Y 2 is a single bond or (CH 2 ) b — (b is an integer of 1 to 15), Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15) ), —O—, —CH 2 O—, —COO— or OCO—.
Y 4 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl having 1 to 3 carbon atoms) Or a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, or an organic group having 12 to 25 carbon atoms having a steroid skeleton. Y 5 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring (any hydrogen atom on these cyclic groups has 1 to 3 carbon atoms). And an alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. 6 carbon Alkyl group of 1 to 18, fluorine-containing alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkoxyl group an alkoxyl group or having 1 to 18 carbon atoms having 1 to 18 carbon atoms, n is an integer from 0-4. )
The composition according to claim 1, wherein the diamine represented by the formula [1] is a diamine represented by the following formula [1A].

(In the formula [1A], R 1 is a linear or branched hydrocarbon group having 1 to 12 carbon atoms, and R 5 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R 3 and R 4 is independently a hydrogen atom or a methyl group.)
The composition according to claim 2, wherein the diamine having the structure represented by the formula [1A] is a diamine represented by the following formula [1B].
The composition according to claim 1, wherein the diamine having the structure represented by the formula [1] is a diamine represented by the following formula [1C].
The composition according to any one of claims 1 to 4, wherein, of the diamine component, the diamine having the structure represented by the formula [1] is 20 to 80 mol%.
The composition according to any one of claims 1 to 4, wherein, of the diamine component, the diamine having the structure represented by the formula [2] is 10 to 80 mol%.
The composition according to any one of claims 1 to 6, wherein the tetracarboxylic dianhydride is a compound represented by the following formula [3].

(In Formula [3], 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.)
The composition according to claim 7, wherein Z 1 in the formula [3] has a structure represented by the following formulas [3a] to [3j].

(In the formula [3a], Z 2 to Z 5 are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In the formula [3g], Z 6 and Z 7 Are hydrogen atoms or methyl groups, which may be the same or different.
The composition according to any one of claims 1 to 8, wherein the cyclic ketone solvent contains at least one cyclic ketone of a 5-membered ring and a 6-membered cyclic ketone.
A liquid crystal aligning agent comprising the composition according to any one of claims 1 to 9.
A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to claim 10.
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the electrodes The liquid crystal aligning film of Claim 11 used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric compound, applying a voltage in between.
A liquid crystal display element having the liquid crystal alignment film according to claim 11.
A liquid crystal composition comprising a polymerizable compound having a liquid crystal layer between a pair of substrates provided with an electrode and the liquid crystal alignment film and polymerized between at least one of active energy rays and heat between the pair of substrates. The liquid crystal display element according to claim 13, wherein the liquid crystal display element is manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.