WO2011136371A1

WO2011136371A1 - Liquid crystal aligning agent, liquid crystal alignment film using same, and liquid crystal display element

Info

Publication number: WO2011136371A1
Application number: PCT/JP2011/060468
Authority: WO
Inventors: 尚士鉄谷; 尚宏野田; 皇晶筒井
Original assignee: 日産化学工業株式会社
Priority date: 2010-04-30
Filing date: 2011-04-28
Publication date: 2011-11-03
Also published as: CN102947754A; TWI549990B; KR101819769B1; KR20130059354A; TW201300438A; CN102947754B; JPWO2011136371A1; JP5900328B2

Abstract

Disclosed is a liquid crystal aligning agent which is capable of providing a liquid crystal alignment film that has excellent in-plane uniformity of pretilt angles, while exhibiting excellent resistance to high temperatures and high humidities and excellent resistance to the heat and light generated by the backlight. Specifically disclosed is a liquid crystal aligning agent which contains a soluble polyimide that is obtained by imidizing a polyamic acid component that is obtained by causing a diamine component that contains a diamine represented by general formula (1) and a diamine represented by general formula (2) to react with a tetracarboxylic acid dianhydride. (In general formula (1), X represents an aromatic ring; R₁ represents an alkylene group having 1-5 carbon atoms; and R₂ represents a hydrocarbon group having 1-4 carbon atoms.) (In general formula (2), R¹ represents a single bond or a divalent organic group; X¹, X² and X³ each independently represents a benzene ring or a cyclohexane ring; p, q and r each independently represents an integer of 0 or 1; and R² represents a hydrogen atom, an alkyl group having 1-22 carbon atoms or a divalent organic group having a steroid skeleton and 12-25 carbon atoms.)

Description

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using the same

The present invention relates to a liquid crystal aligning agent excellent in high-temperature and high-humidity resistance, light resistance, and in-plane uniformity of a pretilt angle, a liquid crystal alignment film and a liquid crystal display element using the same.

A liquid crystal display element has a structure in which liquid crystal molecules are sandwiched between liquid crystal alignment films formed on a substrate, and is a display element utilizing the fact that liquid crystal molecules aligned in a certain direction by a liquid crystal alignment film respond with voltage. is there.
Conventionally, a polyimide film has been mainly used as the liquid crystal alignment film, but as a means for forming the polyimide film on the substrate with electrodes of the liquid crystal display element, a solution of a polyimide precursor such as polyamic acid is used. A method of forming a coating film and imidizing on a substrate, and a method of using a solution containing a soluble polyimide that has been imidized in advance are known. In addition, the solution of the polyimide precursor, soluble polyimide, etc. which form these liquid crystal aligning films are called the liquid crystal aligning agent (liquid crystal aligning agent).

Among these, the method using a solution containing a soluble polyimide is capable of forming a polyimide film with good characteristics when used as a liquid crystal alignment film, even when firing at a relatively low temperature. The solubility is lower than that of polyamic acid, which is inferior in coating and film-forming properties, and the formed liquid crystal alignment film often has insufficient strength. There is a difficulty that peeling easily occurs.
In addition, due to the increase in size and brightness of liquid crystal display elements, the in-plane uniformity of the pretilt angle becomes a problem as the liquid crystal display elements are used in various places and fields. In addition, aging resistance to the heat generated from the backlight is a problem, and countermeasures against these are required.

Various proposals have been made for countermeasures against these problems. For example, a liquid crystal aligning agent containing a soluble polyimide obtained by imidizing a polyamic acid using a specific diamine component, which improves the solubility of polyimide in an organic solvent and does not easily cause scratches or peeling of the film due to rubbing treatment. Has been proposed (Patent Document 1).
On the other hand, the liquid crystal alignment film also plays an important role of imparting a pretilt angle to the liquid crystal, but the uniformity and stability of the pretilt angle are important issues. For example, as a method for imparting a pretilt angle or preventing a decrease in the pretilt angle, a liquid crystal aligning agent using a diamine having an alkyl side chain as a raw material (for example, see Patent Document 2), a diamine having a steroid skeleton in the side chain is used. A liquid crystal aligning agent (for example, see Patent Document 3) used as a raw material, a liquid crystal aligning agent (for example, see Patent Document 4) using a diamine having a ring structure as a side chain as a raw material, and the like have been proposed.
However, with the increase in size and brightness of the liquid crystal display elements, and the liquid crystal display elements have been used in various places and fields for a long time, further stability of the pretilt angle and in-plane uniformity are important. In addition, the deterioration of the element under high temperature and high humidity, the heat and light generated from the backlight, and the deterioration of the element due to the light from sunlight and room lights, etc. Countermeasures are needed.

International Publication No. 2006/126555 Pamphlet Japanese Patent Laid-Open No. 05-043687 Japanese Patent Laid-Open No. 04-281427 Japanese Patent Laid-Open No. 02-223916

In general, a liquid crystal aligning agent using a diamine having an alkyl side chain has good liquid crystal alignment, but is inferior in thermal stability of the pretilt angle, and the pretilt angle decreases as the temperature increases. In addition, a liquid crystal aligning agent using a diamine having a steroid skeleton or a ring structure in the side chain is excellent in thermal stability of a pretilt angle, but tends to decrease liquid crystal alignment and solubility in an organic solvent.
In view of the above situation, an object of the present invention is to form a liquid crystal alignment film that is excellent in in-plane uniformity of a pretilt angle, and that is excellent in resistance to high temperature and high humidity, and heat and light generated from a backlight. And providing a liquid crystal aligning agent having sufficient solubility in an organic solvent, a liquid crystal alignment film using the same, and a liquid crystal display element.

As a result of intensive studies to achieve the above object, the present inventor has reached the present invention, and the present invention has the following gist.
1. A polyamic acid component obtained by reacting a diamine represented by the following general formula [1] and a diamine component containing the diamine represented by the following general formula [2] with tetracarboxylic dianhydride: A liquid crystal aligning agent comprising an imidized soluble polyimide.

(In the formula, X represents an aromatic ring, R ₁ represents alkylene having 1 to 5 carbon atoms, and R ₂ represents a hydrocarbon group having 1 to 4 carbon atoms.)

(In the formula, R ¹ represents a single bond or a divalent organic group, X ¹ , X ² , and X ³ each independently represent a benzene ring or a cyclohexane ring, and p, q, and r each independently represents 0. Or an integer of 1 and R ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton.)

2. _2. The liquid crystal aligning agent according to 1 above, wherein X in the general formula [1] is a phenylene group, R ₁ is a linear alkylene group having 1 to 5 carbon atoms, and R ₂ is a methyl group or an ethyl group.
3. 3. The liquid crystal aligning agent according to 1 or 2 above, wherein X in the general formula [1] is a phenylene group, and R ₁ is a methylene group or an ethylene group.
4). In the general formula [2], R ¹ is a divalent organic group selected from —O—, —NHCO—, —COO— and —CH ₂ O—, and R ² is a hydrogen atom or a linear alkyl having 1 to 18 carbon atoms. 4. The liquid crystal aligning agent according to any one of the above 1 to 3, which is a group.
5. R ¹ in the general formula [2] is a divalent organic group selected from —O— and —NHCO—, p is 0 to 1, q is 0 to 1, r is 0, R 5. The liquid crystal aligning agent according to any one of 1 to 4 above, wherein ² is a hydrogen atom or a linear alkyl group having 1 to 18 carbon atoms.
6). 6. The liquid crystal aligning agent according to any one of 1 to 5 above, wherein the general formula [2] is a diamine represented by the formula [3].

7). 7. The liquid crystal aligning agent according to any one of 1 to 6, wherein the diamine component contains 5 to 95 mol% of the diamine represented by the formula [1].
8). The diamine component contains 5 to 60 mol% of the diamine represented by the formula [2], and 0.1 to 1.2 mol per 1 mol of the diamine represented by the formula [1]. 7. The liquid crystal aligning agent according to any one of 6 to 6.
9. 9. The liquid crystal aligning agent according to any one of 1 to 8, wherein the soluble polyimide is a polyimide obtained by imidizing polyamic acid with an imidization ratio of 10 to 85%.
10. 10. The liquid crystal aligning agent according to any one of 1 to 9 above, wherein the soluble polyimide is contained by being dissolved in an organic solvent, and the soluble polyimide is contained by 1 to 10% by mass.
11. Furthermore, the polyamic acid obtained by reacting the diamine component not containing the diamine represented by the formula [1] and the diamine represented by the formula [2] and the tetracarboxylic dianhydride component at the same time is contained. The liquid crystal aligning agent according to any one of 1 to 10.
12 12. The liquid crystal aligning agent according to 11 above, wherein the polyamic acid is contained in an amount of 10 to 10,000 parts by mass with respect to 100 parts by mass of the soluble polyimide.

13. The organic solvent is N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinylpyrrolidone, dimethyl 13. The liquid crystal aligning agent according to any one of the above 10 to 12, which is sulfoxide, tetramethylurea, dimethylsulfone, hexamethylphosphoric triamide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, or a mixture thereof.
14 14. A liquid crystal alignment film obtained using the liquid crystal aligning agent according to any one of 1 to 13 above.
15. 15. A liquid crystal display device comprising the liquid crystal alignment film as described in 14 above.

According to the present invention, the in-plane uniformity of the pretilt angle over the entire screen, which becomes a more and more problem due to the increase in size and brightness of the liquid crystal display element, is excellent in high-temperature and high-humidity resistance, heat generated from the backlight, A liquid crystal aligning agent that can form a liquid crystal alignment film excellent in light resistance and has sufficient solubility in an organic solvent is provided.

<Soluble polyimide>
As described above, the liquid crystal aligning agent of the present invention contains a specific soluble polyimide, or the specific soluble polyimide and a polyamic acid. A polyamic acid obtained by reacting a diamine component containing the diamine represented by the formula [2] with tetracarboxylic dianhydride can be obtained by chemical imidization or the like. By using together the diamines represented by the above formulas [1] and [2], the in-plane uniformity of the pretilt angle is excellent, the resistance to heat and humidity under high temperature and high humidity, and the heat from the backlight. In addition, a liquid crystal alignment film having excellent resistance to light and light can be formed, and the solubility in organic solvents is also improved. In addition, in this invention, a soluble polyimide means the polyimide soluble in the organic solvent used for the liquid crystal aligning agent of this invention.

Since the soluble polyimide used in the present invention can leave many N-substituted amic acid sites having high polarity, it is highly compatible with polyamic acid having high polarity and aggregates despite containing side chain components. And separation is difficult to occur. Moreover, since the varnish using this soluble polyimide is less likely to precipitate due to water absorption, it is excellent in printability.
On the other hand, the amic acid part in the conventional soluble polyimide, that is, the part where the imide can be ring-closed easily undergoes decomposition such as hydrolysis, causing a decomposition reaction when the coating film is baked, resulting in a decrease in electrical characteristics, which is a long-term reliability. Adversely affect. On the other hand, if a soluble polyimide with a high imidization rate is used, the degradation of characteristics due to decomposition as described above can be reduced. However, a soluble polyimide with a high imidization rate becomes hydrophobic in nature. The compatibility with the acid deteriorates and aggregation and separation are likely to occur. As a result, the uniformity of the pretilt angle cannot be obtained.

In the present invention, when the diamine of the formula [1] is used, the N-substituted amic acid moiety is less likely to hydrolyze than ordinary amic acid, and the molecular weight reduction during firing can be reduced. Since it is possible to prevent further decomposition by increasing the conversion rate, it is possible to obtain good reliability over a short period and a long period. Moreover, since it has a structure in which many highly polar amic acid sites remain, a pretilt excellent in in-plane uniformity can be obtained even when blended with polyamic acid.

In the above formula [1], X, R ₁ and R ₂ are as defined above. X in the formula is a site for giving the diamine an aromatic amine site, and is not particularly limited as long as it is an aromatic ring. From the viewpoints of availability of raw materials, ease of synthesis, liquid crystal alignment, and the like, phenylene, naphthalene and the like are preferable, and phenylene is particularly preferable from the viewpoint of versatility. When X is phenylene, that is, aminobenzene, the substitution position of R ₁ is preferably a meta position or a para position.
R ₁ represents an alkylene having 1 to 5 carbon atoms, for R ₁ is that act on imparting solubility in a solvent when it is used for a soluble polyimide, R ₁ in view of the solubility of granted so long as the number of carbon atoms It may be branched or have a ring structure. On the other hand, a linear structure is preferable from the viewpoint of liquid crystal alignment and rubbing resistance, and alkylene having 1 to 2 carbon atoms is most preferable from the viewpoint of availability of reagents.

R ₂ represents an alkyl group having 1 to 4 carbon atoms, which is considered to contribute mainly to inhibition of imide ring closure and imparting solubility of soluble polyimide, and may have a linear or branched structure. On the other hand, from the viewpoint of liquid crystal alignment and diamine reactivity, a group as small as possible is preferable, and a methyl group and an ethyl group are particularly preferable.
Particularly preferred examples of the diamine represented by the formula [1] are shown below, but are not limited thereto.

The content of the diamine represented by the formula [1] is not necessarily limited, but it is preferably 5 to 95 mol% of the total diamine component, and is particularly preferably 20 to 20% because the in-plane uniformity of the pretilt is improved. It is preferably 90 mol%.

In the above formula [2], R ¹ , X ¹ , X ² , X ³ , p, q, r and R ² are as defined above. The diamine of the above formula [2] contributes to increasing the pretilt angle of the liquid crystal, and these diamines include a long-chain alkyl group, a perfluoroalkyl group, an aromatic cyclic group, an aliphatic cyclic group, A diamine having a substituent obtained by combining these groups or a steroid skeleton group is preferable.

Although the preferred magnitude of the pretilt angle varies depending on the mode, a preferred pretilt angle can be obtained by variously selecting the structure and amount of the diamine.
In the side chain diamine represented by the formula [2], a tilt is exhibited in a TN mode in which a relatively low pretilt angle of 3 to 5 ° is required and an OCB mode in which a relatively high pretilt of 8 to 20 ° is required. Side chain-containing diamines with relatively low performance are preferred.
As a structure having a relatively small tilting ability, R ¹ is preferably —O— or —NHCO— (—CONH—), wherein p is 0 to 1, q is 0 to 1, and r is preferably 0. When p and / or q is 1, R ² is preferably a linear alkyl group having 1 to 12 carbon atoms, and when p = q = r = 0, R ² is a linear alkyl group having 10 to 22 carbon atoms or a steroid A divalent organic group selected from organic groups having 12 to 25 carbon atoms having a skeleton is preferable. Specific structures of side chain diamines having a small tilting ability are shown in Table 1, but are not limited thereto.

From the viewpoint of electrical properties, long-chain alkyl side chains such as [2-1] to [2-3] in Table 1 are preferred. From the viewpoint of liquid crystal orientation and pretilt stability, [2-25] in Table 1 Diamines represented by [2-27] are preferred. In particular, the diamine represented by [2-25] is preferably used in combination with the diamine represented by the formula [A] because a liquid crystal aligning agent having excellent in-plane uniformity of the pretilt angle can be obtained.
On the other hand, in the VA mode or the like, vertical alignment can be obtained by using a side chain having a large tilting ability. As a preferable structure of the formula [2] in the VA mode, R ¹ is preferably —O—, —COO—, or —CH ₂ O—, p is 0 to 1, q is 0 to 1, and r is 0 to 1 is preferable, and R ² is preferably 2 to 22. When p = q = r = 0, R ² is preferably a linear alkyl group having 18 to 22 carbon atoms or a divalent organic group that is an organic group having 12 to 25 carbon atoms having a steroid skeleton. Specific structures of side chain diamines having a high tilting ability are shown in Tables 2-1 and 2-2.

These diamines have high tilting ability and are preferable when used in the VA mode. In particular, diamines such as [2-43] and [2-92] are preferable because they have a high ability to develop a tilt and exhibit vertical alignment with a relatively small amount of side chains, and are particularly preferred as [2-52] and [2-101]. Diamine is preferable in terms of printability of the aligning agent because it has a very high ability to develop a tilt and can obtain vertical alignment with a very small amount of side chain.
On the other hand, in the diamine represented by the above formula [2], R ¹ is preferably —NHCO—, and R ² is preferably from the viewpoints of high pretilt expression ability, improved pretilt stability, improved liquid crystal orientation, and the like. An alkyl group having 1 to 16 carbon atoms, preferably 3 to 10 carbon atoms is preferred. Further, X ¹ , X ² , X ³ and p, q, r are appropriately selected. In such a diamine structure, the position of each substituent on the benzene ring is not particularly limited, but the positional relationship between the two amino groups is preferably meta or para.

Examples of preferred diamines represented by the above formula [2] include diamines represented by the following formula (3).

(In formula (3), n is an integer of 0 to 21, preferably an integer of 0 to 15.)

Although the preferable specific example of the diamine represented by the said Formula (3) is given to the following, it is not limited to this.

Here, n is an integer from 0 to 19. When n is small, the pretilt angle does not appear, and when it is large, the solubility of soluble polyimide decreases. Preferred n is an integer of 2 to 15, more preferably an integer of 4 to 10.
The content of the diamine represented by the above [2] is preferably 5 to 60 mol% in the total amine component, and is particularly preferably 5 to 30 mol% from the viewpoint of pretilt uniformity and printability.
Further, the diamine represented by the formula [2] is preferably contained in an amount of 0.1 to 1.2 mol, more preferably 0.3 to 1 with respect to 1 mol of the diamine represented by the formula [1]. 0.0 mole. When the diamine of the formula [2] is within this range, an appropriate pretilt angle can be obtained and good orientation can be obtained.

In the above diamine component, the diamine represented by the formula [1] and the diamine represented by [2] may be only these, but other diamines may be used in combination. Although not limited, Preferably, the diamine used for manufacture of the polyamic acid used by mixing with the soluble polyimide mentioned later is mentioned. In addition, the tetracarboxylic dianhydride component used for producing a soluble polyimide by reacting with a diamine is also preferably a tetracarboxylic acid used for producing a polyamic acid used by mixing with a soluble polyimide described later. Carboxylic dianhydrides are mentioned.
The molecular weight of the soluble polyimide contained in the liquid crystal aligning agent of the present invention is not particularly limited, but from the viewpoint of the strength of the coating film and ease of handling as the liquid crystal aligning agent, the weight average molecular weight is 2,000 to 200,000. And more preferably 5,000 to 50,000.

<Polyamic acid>
In a preferred embodiment of the liquid crystal aligning agent of the present invention, a polyamic acid is contained together with a soluble polyimide. Since the liquid crystal aligning agent containing polyamic acid together with soluble polyimide has the advantage of reducing the charge accumulated in the liquid crystal alignment film and facilitating the removal of the accumulated charge compared to the case containing only soluble polyimide. preferable.
Such polyamic acid does not contain both the diamine represented by the above formula [1] and the diamine represented by [2], but any one of the diamines may contain a diamine component and a tetracarboxylic dianhydride component. Can be obtained by polycondensation of these. Usually, the diamine component used as the raw material of the polyamic acid mixed with the soluble polyimide contains one or more of any of the diamines described below.
<Diamine component>
As the diamine component used as the raw material for the polyamic acid, alicyclic diamine, aromatic diamine, aromatic-aliphatic diamine, heterocyclic diamine, aliphatic diamine, and other diamines are used.
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone Examples include diamines.

Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino -2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 '-Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane 4,4′-diamino-3,3′-dimethyldiphenylmethane, 2,2′-diaminostilbene, 4,4′-dia Nostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'- Diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis (4- Aminophenoxy) benzoic acid, 4,4'-bis (4-aminophenoxy) bibenzyl, 2,2-bis [(4-aminophenoxy) methyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, α, α′-bis (4- Aminophenyl) -1,4-diisopropylbenzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) Hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1,6 -Diaminopyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4-amino Phenyl) tetramethyldisiloxane, benzidine, 2,2′-dimethylbenzidine, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4 -Aminophenyl) butane, 1,5-bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis (4-aminophenyl) octane, 1,9-bis (4-aminophenyl) nonane, 1,10-bis (4-aminophenyl) decane, 1,3-bis (4-aminophenoxy) propane, 1,4 -Bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4 -Aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, di (4-amino) Phenyl) propane-1,3-dioate, di (4-aminophenyl) butane-1,4-dioate, di (4-aminophenyl) pentane-1,5-dioate, di (4-aminophenyl) hexane-1 , 6-dioate, di (4-aminophenyl) heptane-1,7-dioate, di (4-aminophenyl) octane-1,8-dioate, di (4-aminophenyl) nonane-1,9-dioate, Di (4-aminophenyl) decane-1,10-dioate, 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 1,4- [4- (4-aminophenoxy) phenoxy] butane, 1,5-bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] hexane, 1,7-bis [4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- (4-aminophenoxy) phenoxy] octane, 1,9-bis [4- (4-aminophenoxy) Phenoxy] nonane, 1,10-bis [4- (4-aminophenoxy) phenoxy] decane, and the like.

Examples of aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminobenzylamine, Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4-methyl Aminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopentyl) Aniline, 3- (5-methylaminopentyl) aniline, 4- (5-methylaminopentyl) aniline, 2- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- (6 -Aminonaphthyl) ethylamine, 3- (6-aminonaphthyl) ethylamine and the like.

Examples of heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diamino Examples thereof include carbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole.
Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7 -Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diamino Examples include dodecane, 1,18-diaminooctadecane, and 1,2-bis (3-aminopropoxy) ethane.

You may use together the diamine compound which has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or the macrocyclic substituent which consists of them in a side chain. Specifically, diamines represented by the following formulas [DA1] to [DA26] can be exemplified.

(In the formulas [DA1] to [DA5], R ₆ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.)

(In the formulas [DA6] to [DA9], S ₅ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO—, or —NH—. R ₆ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.)

(In Formula [DA10] and Formula [DA11], S ₆ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, or —CH ₂ OCO—, and R ₇ represents the number of carbon atoms. 1 to 22 alkyl groups, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups.)

(In the formulas [DA12] to [DA14], S ₇ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, — OCH ₂ — or —CH ₂ —, and R ₈ represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

(In Formula [DA15] and Formula [DA16], S ₈ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, — OCH ₂ —, —CH ₂ —, —O—, or —NH—, wherein R ₉ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group .)

(In the formulas [DA17] to [DA20], R ₁₀ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)

When aligning the liquid crystal aligning agent of the present invention with light, a more stable pretilt can be obtained by using the diamine of the general formula [1] in combination with the diamines of the above [DA-1] to [DA-26]. Is preferable. More preferred diamines are those of the formulas [DA-10] to [DA-26], and more preferred are diamines of [DA-10] to [DA-16]. The preferred content of these diamines is not particularly limited, but is preferably 5 to 50 mol%, and preferably 5 to 30 from the viewpoint of printability.

Moreover, the diamine of General formula [1] can also use the following diamine together.

In the formula [DA31], m is an integer of 0 to 3, and in the formula [DA34], n is an integer of 1 to 5.) [DA-27], [DA-28], [DA-35], [DA-36], [DA-37] and the like are preferable because they are effective in improving VHR and improving rubbing resistance. In addition, [DA-29] to [DA-34] are preferable because they are effective in reducing the storage electrification.

The diaminosiloxane etc. which are shown by the following formula [DA27] can also be mentioned.

(In the formula [DA27], m is an integer of 1 to 10.)

<Tetracarboxylic dianhydride>
As the tetracarboxylic dianhydride component used as a raw material for the soluble polyimide and polyamic acid, the following are used. The tetracarboxylic dianhydride component may be one type or a mixture of two or more types.
As the tetracarboxylic dianhydride component, it is preferable to use a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure from the viewpoint that the voltage holding ratio of the liquid crystal cell can be increased. Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1, , 3,4-Butanetetracarboxylic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetra Carboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride , Tricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dianhydride, hexacyclo [6.6.0.1 ^{2 , 7} . 0 ^3,6 . 1 ^9,14 . 0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-dianhydride, 4- (2,5-di-oxo-tetrahydrofuran-3-yl) -1,2 3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride and the like.

Furthermore, when an aromatic tetracarboxylic dianhydride is used in addition to the tetracyclic dianhydride having the alicyclic structure or aliphatic structure, the liquid crystal alignment is improved and the accumulated charge of the liquid crystal cell is reduced. Since it can reduce, it is preferable. Aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4-benzophenonetetra Carboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride And 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.

If each characteristic such as orientation of liquid crystal alignment film, voltage holding ratio, accumulated charge is taken into consideration, tetracarboxylic dianhydride having alicyclic structure or aliphatic structure, aromatic tetracarboxylic dianhydride, Are preferably used in combination. In this case, the former / latter molar ratio is preferably 90/10 to 50/50, more preferably 80/20 to 60/40.
The weight average molecular weight of the polyamic acid is preferably 10,000 to 305,000, and more preferably 20,000 to 210,000. The number average molecular weight is preferably 5,000 to 152,500, and more preferably 10,000 to 105,000.

<Production of soluble polyimide and polyamic acid>
The soluble polyimide and polyamic acid contained in the liquid crystal aligning agent of the present invention are produced as follows. The soluble polyimide is obtained by imidizing the precursor polyamic acid, but the difference between the polyamic acid which is the precursor of the soluble polyimide and the polyamic acid mixed with the soluble polyimide is that the former is the raw material As the diamine component, the diamines of the above formulas (1) and (2) are used.
The polyamic acid mixed with the soluble polyimide and the polyamic acid which is a precursor of the soluble polyimide are both produced by polycondensing a diamine component and a tetracarboxylic dianhydride component in an organic solvent.

As a method of polycondensing a tetracarboxylic dianhydride component and a diamine component in an organic solvent, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or A method of adding by dispersing or dissolving in an organic solvent, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, a tetracarboxylic dianhydride component and a diamine component, A method of alternately adding can be mentioned. Further, when the tetracarboxylic dianhydride component or the diamine component is composed of a plurality of types of compounds, they may be subjected to a polycondensation reaction in a state in which these plural types of compounds are mixed in advance, or may be sequentially subjected to a polycondensation reaction individually. Good.

The temperature for the polycondensation reaction of the tetracarboxylic dianhydride component and the diamine component in an organic solvent is usually 0 to 150 ° C., preferably 5 to 100 ° C., more preferably 10 to 80 ° C. The higher the temperature, the faster the polycondensation reaction is completed, but if the temperature is too high, a high molecular weight polymer may not be obtained.
The polycondensation reaction can be carried out at any concentration. However, if the concentration of the total mass of the tetracarboxylic dianhydride component and the diamine component is too low, it becomes difficult to obtain a high molecular weight polymer. If the concentration of the total mass of the acid dianhydride component and the diamine component is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult, so 1 to 50% by mass, more preferably 5 to 30% is preferable. % By mass. The initial stage of the polycondensation reaction may be performed at a high concentration, and then an organic solvent may be added.

The organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid dissolves. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , Γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl 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, dipropylene glycol 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, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, 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, ethyl 3-methoxypropionate, 3-ethoxypropion , 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy -N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like. These may be used alone or in combination. Furthermore, even if the solvent does not dissolve the polyamic acid, it may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate. The water in the organic solvent inhibits the polycondensation reaction, and Causes hydrolysis of the produced polyamic acid, so that it is preferable to use an organic solvent that has been dehydrated and dried as much as possible.

The ratio of the tetracarboxylic dianhydride component and the diamine component used for the polycondensation polycondensation reaction is preferably 1: 0.8 to 1: 1.2 in molar ratio, and this molar ratio is 1: 1. The closer the molecular weight of the polyamic acid obtained, the greater.
The polyamic acid is produced as described above, and the polyamic acid mixed with the soluble polyimide is used as one component of the liquid crystal aligning agent of the present invention. On the other hand, polyamic acid which is a precursor of soluble polyimide is imidized. The imidization of the polyamic acid is performed by stirring in an organic solvent, preferably in the presence of a basic catalyst and an acid anhydride, preferably for 1 to 100 hours.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because 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 the obtained polyimide can be easily purified after imidization. As an organic solvent, the solvent used at the time of the polycondensation reaction of the polyamic acid mentioned above can be used.
The imidation ratio of the soluble polyimide can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time. The amount of the basic catalyst at this time is preferably 0.2 to 10 times mol, more preferably 0.5 to 5 times mol of the amic acid group. Further, the amount of the acid anhydride is preferably 1 to 30 times mol, more preferably 1 to 10 times mol of the amic acid group. The reaction temperature is preferably −20 to 250 ° C., more preferably 0 to 180 ° C. The reaction time is preferably 1 to 100 hours, preferably 1 to 20 hours.

The imidization ratio of the soluble polyimide is not particularly limited, but is preferably 10% or more, more preferably 40% or more, more preferably 60% or more, and particularly preferably 80% or more in order to obtain a high voltage holding ratio. Even if it is a fool, the imidation rate is preferably 10 to 85%, more preferably 20 to 75%.
In addition, since the added catalyst etc. remain in the solution of the obtained soluble polyimide, it is preferable to use the liquid crystal aligning agent of the present invention after recovering and washing the soluble polyimide.
The soluble polyimide can be recovered by putting the solution after imidization into a poor solvent that is being stirred, and precipitating the polyimide, followed by filtration. Examples of the poor solvent at this time include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. The recovered soluble polyimide can be washed with this poor solvent.
The polyimide recovered and washed in this way can be powdered by drying at normal temperature or under reduced pressure at room temperature or by heating.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention contains said soluble polyimide or the soluble polyimide and polyamic acid in the form melt | dissolved in the organic solvent. The liquid crystal aligning agent preferably contains 3 to 10% by mass of soluble polyimide, more preferably 4 to 7% by mass. Further, when the liquid crystal aligning agent contains a polyamic acid, the polyamic acid is preferably contained in an amount of 3 to 10% by mass, more preferably 4 to 7% by mass. The total content of soluble polyimide and polyamic acid in the liquid crystal aligning agent is preferably 3 to 10% by mass, more preferably 4 to 7% by mass.
When the liquid crystal aligning agent contains a polyamic acid, the polyamic acid is preferably contained in an amount of 10 to 1000 parts by mass, more preferably 10 to 800 parts by mass with respect to 100 parts by mass of the soluble polyimide. The soluble polyimide contained in the liquid crystal aligning agent and the organic solvent used for dissolving the polyamic acid are preferably 90 to 97% by mass, more preferably 93 to 96% by mass.

Examples of the organic solvent used in the liquid crystal aligning agent of the present invention include N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, dipentene, ethyl amyl ketone, methyl nonyl ketone, Examples thereof include methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, and 4-hydroxy-4-methyl-2-pentanone. Two or more kinds of these solvents may be mixed and used.

When the polyimide is dissolved in the organic solvent, heating may be performed for the purpose of promoting the dissolution of the polyimide. If the heating temperature is too high, the molecular weight of the polyimide may decrease, so the temperature is preferably 30 to 100 ° C, more preferably 50 to 90 ° C.

<Other ingredients>
The liquid crystal aligning agent of the present invention has, as other components, a solvent and an additive that improve the film thickness uniformity and surface smoothness when the liquid crystal aligning agent is applied, and the adhesion between the liquid crystal aligning film and the substrate. You may contain the additive etc. which improve. These additive components may be added in the middle of dissolving the soluble polyimide and polyamic acid in the organic solvent, or may be added after dissolution.

<Solvent that improves film thickness uniformity and surface smoothness>
Specific examples of the solvent for improving the film thickness uniformity and the surface smoothness 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 monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, 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 A solvent etc. are mentioned.

These solvents include solvents that cannot dissolve polyamic acid or soluble polyimide alone, but can be mixed with the liquid crystal aligning agent of the present invention as long as polyamic acid or polyimide does not precipitate. . In particular, it is known that the coating film uniformity is improved upon application to a substrate by appropriately mixing a solvent having a low surface tension, and it is also suitably used in the liquid crystal aligning agent of the present invention.
These solvents may be used alone or in combination. When the above solvent is used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal aligning agent.

<Additives that improve film thickness uniformity and surface smoothness>
Examples of substances that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
More specifically, for example, 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.). The use ratio of these substances 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 component (B) contained in the liquid crystal aligning agent. .

<Additive for improving adhesion between liquid crystal alignment film and substrate>
Specific examples of the substance that improves the adhesion between the liquid crystal alignment 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-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra Glycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N Examples include ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane.

When these additives are used, the amount is preferably 0.1 to 30 parts by weight, more preferably 1 to 30 parts by weight based on 100 parts by weight of the soluble polyimide or soluble polyimide and polyamic acid contained in the liquid crystal alignment treatment agent. 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.
In the liquid crystal alignment treatment agent of the present invention, in addition to the above, as long as the effects of the present invention are not impaired, polymer components other than the specific polymer, and electrical characteristics such as dielectric constant and conductivity of the liquid crystal alignment film are provided. Substances to be changed (dielectrics, conductive substances, etc.), and further crosslinkable substances for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.
For example, the following phenoplast-based additives are particularly preferred because they are expected to have an effect of preventing deterioration of electrical characteristics due to the backlight in addition to improving the adhesion between the substrate and the film. Specific compounds are listed below, but are not limited thereto.

When the compound that improves the adhesion to the substrate is used in the liquid crystal aligning agent of the present invention, the amount used is 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent. The amount is preferably 1 to 20 parts by mass. If the amount used is less than 0.1 parts 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.
The manufacturing method of the liquid crystal aligning agent of this invention is not specifically limited. Usually, it manufactures by mixing the solution of the said soluble polyimide, or the solution of a soluble polyimide, and the solution of a polyamic acid. In the case of polyamic acid, the reaction solution of polyamic acid obtained by polycondensation may be used as it is, or once polyamic acid is obtained, it is redissolved in an organic solvent to form a polyamic acid solution. Can be used. The polyamic acid solution may be used after diluted to a desired concentration.

On the other hand, in the case of soluble polyimide, the reaction solution of soluble polyimide obtained by imidization may be used as it is, or once polyimide powder is obtained, it is redissolved in an organic solvent as a polyimide solution. Can be used. The polyimide solution may be used after diluting to a desired concentration.
The solid content concentration in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the thickness of the liquid crystal alignment film to be formed, but is preferably 0.5 to 10% by mass, and 1 to 8% by mass. More preferably. If the solid content concentration is less than 0.5% by mass, it is difficult to form a uniform and defect-free coating film, and if it exceeds 10% by mass, the storage stability of the solution may be deteriorated. The solid content here means a component obtained by removing the solvent from the liquid crystal aligning agent, and means a polymer such as soluble polyimide and polyamic acid, and various additives described above.
The liquid crystal aligning agent of the present invention is preferably filtered before being applied to the substrate, then applied to the substrate, dried and baked to form a coating film. It is used as a liquid crystal alignment film by performing an alignment treatment such as

At this time, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used, and an ITO electrode for driving a liquid crystal is formed. It is preferable to use a new substrate from the viewpoint of simplification of the process. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as aluminum can be used as the electrode.

Examples of the method for applying the liquid crystal aligning agent include a spin coating method, a printing method, and an ink jet method, but the flexographic printing method is widely used industrially from the viewpoint of productivity. In the liquid crystal aligning agent of the present invention, Are also preferably used.
The drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, a drying process is included. Is preferred. This drying is not particularly limited as long as the solvent is evaporated to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like. As a specific example, a method of drying on a hot plate at 50 to 150 ° C., preferably 80 to 120 ° C., for 0.5 to 30 minutes, preferably 1 to 5 minutes is employed.

The substrate coated with the liquid crystal aligning agent can be baked at an arbitrary temperature of 100 to 350 ° C., preferably 150 to 300 ° C., more preferably 180 to 250 ° C. The polyamic acid contained in the liquid crystal aligning agent changes the conversion rate from the amic acid to the imide by this firing, but the polyamic acid does not necessarily need to be 100% imidized. However, baking is preferably performed at a temperature that is 10 ° C. or more higher than the heat treatment temperature required for the manufacturing process of the liquid crystal cell, such as curing of the sealant.
If the thickness of the coating film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. 50 to 100 nm.
An existing rubbing apparatus can be used for rubbing the coating surface formed on the substrate as described above. Examples of the material of the rubbing cloth at this time include cotton, rayon, and nylon.

The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
As an example of liquid crystal cell fabrication, a pair of substrates on which a liquid crystal alignment film is formed is preferably an arbitrary rubbing direction of 0 to 270 ° with a spacer of preferably 1 to 30 μm, more preferably 2 to 10 μm sandwiched between them. In general, the angle is set so that the angle is fixed, the periphery is fixed with a sealant, and the liquid crystal is injected and sealed. The method for enclosing the liquid crystal is not particularly limited, and examples thereof include a vacuum method of injecting liquid crystal after reducing the pressure inside the produced liquid crystal cell, and a dropping method of sealing after dropping the liquid crystal.
The liquid crystal display device thus obtained has good liquid crystal orientation, and display defects associated with scratches and peeling of the liquid crystal alignment film that occur during rubbing treatment, and alignment defects due to a decrease in pretilt angle at high temperatures are reduced. And a highly reliable liquid crystal display device.

<Example>
Hereinafter, the present invention will be described with reference to examples, but the present invention is of course not limited to these examples. The abbreviations of the compounds used in Examples and Comparative Examples are as follows.
<Tetracarboxylic dianhydride>
A-1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride A-2: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride A- 3: pyromellitic dianhydride A-4: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride A-5: 2,3,5-tricarboxycyclopentylacetic acid 1,4: 2,3-dianhydride

<Diamine>
B-1: 3-((N-methylamino) methyl) aniline B-2: 4-((N-methylamino) methyl) aniline B-3: 4-((N-methylamino) ethyl) aniline B- 4: p-phenylenediamine B-5: 3-aminobenzylamine

B-6: 3,5-diaminobenzyl-2-furorate B-7: 4-hexadecyloxy-1,3-diaminobenzene B-8: 4- (trans-4-pentylcyclohexyl) benzamide-2 ′, 4 '-Phenylenediamine B-9: Cholesteryl 3,5-diaminobenzoate

B-10: N-methyl-4,4′-diaminodiphenylamine B-11: 4,4′-diaminodiphenylmethane B-12: 1,5-bis (4-aminophenoxy) pentane

<Organic solvent>
NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BC: Butyl cellosolve The evaluation method performed in this example is described below.

<Measurement of molecular weight>
The molecular weight of the polyamic acid and the polyimide was determined by measuring the polyimide with a GPC (room temperature gel permeation chromatography) apparatus, and calculating the number average molecular weight and the weight average molecular weight as polyethylene glycol and polyethylene oxide equivalent values.
GPC device: manufactured by Shodex (GPC-101)
Column: manufactured by Shodex (series of KD803 and KD805)
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additive, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L , Tetrahydrofuran (THF) at 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, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratory .

<Measurement of imidization ratio>
The imidation ratio of polyimide was measured as follows. 20 mg of polyimide powder was put into an NMR sample tube, and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixed product) was added and completely dissolved. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNM-ECA500) manufactured by JEOL Datum.
The imidization rate was calculated by the following formula. In addition, the imidation ratio of the polyimide which does not use the diamine represented by the formula [1] was calculated by setting the value of the “formula [1] diamine introduction amount during polyamic acid polymerization” in the following formula to zero.
Imidization rate (%) =
(100-Polyamic acid polymerization formula [1] Amount of diamine introduced (mol%) / 2) × α
In the formula, α is a proton derived from a structure that does not change before and after imidation as a reference proton, and the proton peak integrated value and a proton peak derived from the NH group of the amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by following Formula using the integrated value.
α = (1−α · x / y)
In the above formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is one NH group proton of the amic acid in the case of polyamic acid (imidation rate is 0%). The number ratio of the reference protons.

<Production of liquid crystal cell>
A liquid crystal aligning agent is spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 70 ° C. for 70 seconds, and then baked on a hot plate at 210 ° C. for 10 minutes to form a coating film having a thickness of 100 nm. It was. This coating film surface was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film.
Prepare two sheets of this substrate, spray a 6μm spacer on the surface of the liquid crystal alignment film, print a sealant on it, and the other substrate faces the liquid crystal alignment film and the rubbing direction is perpendicular. After the lamination, the sealing agent was cured to produce an empty cell. Liquid crystal MLC-2003 (manufactured by Merck Japan) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a twisted nematic liquid crystal cell.

<High temperature and high humidity test>
A voltage of 4 V is applied for 60 μs at a temperature of 90 ° C. to the twisted nematic liquid crystal cell manufactured by the method described in <Preparation of liquid crystal cell> above, and the voltage after 166.7 ms is measured. It was calculated as voltage holding ratio. The voltage holding ratio was measured using a VHR-1 voltage holding ratio measuring device manufactured by Toyo Technica. Furthermore, it was left in a high-temperature and high-humidity device at a temperature of 70 ° C. and a humidity of 80% for 168 hours, and how much voltage was maintained was calculated as a voltage holding ratio (%).

<Backlight aging resistance>
A voltage of 4V is applied for 60 μs at a temperature of 90 ° C. to the twisted nematic liquid crystal cell manufactured by the method described in <Preparation of liquid crystal cell> above, and the voltage after 166.7 ms is measured. It was calculated as voltage holding ratio. Furthermore, it was left on the backlight module for 40 inch type liquid crystal TV for 168 hours, and how much voltage could be held was calculated as a voltage holding ratio. The voltage holding ratio (%) was measured using the same device as described in <High temperature and high humidity test>.

<Measurement of pretilt angle>
A liquid crystal cell obtained in the same manner as in the above <Production of liquid crystal cell> was heated at 105 ° C. for 10 minutes, and then used to measure the pretilt angle. For the measurement, an Axo Scan Mueller matrix polarimeter manufactured by Optometrics was used. The measurement was performed at three points on the cell, and the tilt angle uniformity within the surface was confirmed with variations in the values.

(Synthesis Example 1)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 4.71 g (24.13 mmol) of A-1 as the tetracarboxylic dianhydride component and 3.00 g (22.05 mmol) of B-1 as the diamine component ), 0.85 g (2.45 mmol) of B-7 was reacted in 48.7 g of NMP in a nitrogen atmosphere at room temperature for 24 hours to obtain a polyamic acid solution (PAA-1) having a concentration of 15% by mass. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 162 mPa · s. The polyamic acid had a number average molecular weight of 12465 and a weight average molecular weight of 29304.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the resulting polyamic acid solution (PAA-1) was weighed, diluted by adding 43.8 g of NMP, acetic anhydride 10.92 g (106.95 mmol) and pyridine 8 .46 g (106.95 mmol) was added and reacted at 70 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 388.5 ml of methanol to recover the precipitated solid. Further, the solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-1). The number average molecular weight of this polyimide was 11323, and the weight average molecular weight was 26879. Moreover, the imidation ratio was 52%.

(Synthesis Example 2)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 4.73 g (24.13 mmol) of A-1 as the tetracarboxylic dianhydride component and 3.00 g (22.05 mmol) of B-2 as the diamine component ), 0.85 g (2.45 mmol) of B-7 was reacted in 48.7 g of NMP in a nitrogen atmosphere at room temperature for 24 hours to obtain a polyamic acid solution (PAA-2) having a concentration of 15% by mass. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 198 mPa · s. The polyamic acid had a number average molecular weight of 13482 and a weight average molecular weight of 33283.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-2) was weighed and diluted by adding 43.8 g of NMP, acetic anhydride 10.92 g (106.95 mmol) and pyridine 8 .46 g (106.95 mmol) was added and reacted at 70 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 388.5 ml of methanol to recover the precipitated solid. Further, the solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-2). The number average molecular weight of this polyimide was 12663, and the weight average molecular weight was 27320. The imidation ratio was 53%.

(Synthesis Example 3)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, A-1 as 3.38 g (17.25 mmol) and A-4 as 1.88 g (7.50 mmol) diamine component as tetracarboxylic dianhydride components , B-4 1.22 g (11.25 mmol), B-3 1.69 g (11.25 mmol), B-7 0.87 g (2.50 mmol) and NMP 51.2 g in a nitrogen atmosphere. For 24 hours at 40 ° C. to obtain a polyamic acid solution (PAA-3) having a concentration of 15% by mass. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 205 mPa · s. The number average molecular weight of this polyamic acid was 16632, and the weight average molecular weight was 39420.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the resulting polyamic acid solution (PAA-3) was weighed, diluted by adding 43.8 g of NMP, acetic anhydride 10.59 g (103.72 mmol) and pyridine 8 .21 g (103.72 mmol) was added and reacted at 70 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 388.5 ml of methanol to recover the precipitated solid. Further, the solid was washed twice with methanol and dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-3). The number average molecular weight of this polyimide was 15663, and the weight average molecular weight was 33256. Moreover, the imidation ratio was 50%.

(Synthesis Example 4)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 5.55 g (24.75 mmol) of A-5 was used as the tetracarboxylic dianhydride component, and 1.22 g (11.25 mmol) of B-4 was used as the diamine component. ), 1.53 g (11.25 mmol) of B-2, 0.87 g (2.50 mmol) of B-7, and reacted for 24 hours at 40 ° C. in a nitrogen atmosphere in 52.0 g of NMP. % Polyamic acid solution (PAA-4) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 133 mPa · s. The number average molecular weight of this polyamic acid was 17212, and the weight average molecular weight was 40192.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-4) was weighed and diluted by adding 43.8 g of NMP, acetic anhydride 10.38 g (101.67 mmol) and pyridine 9 .51 g (101.67 mmol) was added and reacted at 110 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 333.5 ml of methanol to recover the precipitated solid. Further, the solid was washed twice with methanol and dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-4). The number average molecular weight of this polyimide was 14949, and the weight average molecular weight was 38211. The imidation ratio was 57%.

(Synthesis Example 5)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 7.51 g (38.42 mmol) of A-1 as the tetracarboxylic dianhydride component and 3.98 g (29.25 mmol) of B-1 as the diamine component ), 1.81 g (7.80 mmol) of B-6 and 0.79 g (1.95 mmol) of B-8, and reacted for 8 hours at room temperature in a nitrogen atmosphere in 80.0 g of NMP. A polyamic acid solution (PAA-5) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 152 mPa · s. The polyamic acid had a number average molecular weight of 11987 and a weight average molecular weight of 43283.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-5) was weighed and diluted by adding 43.8 g of NMP, acetic anhydride 10.55 g (103.23 mmol) and pyridine 8 .18 g (103.23 mmol) was added and reacted at 70 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 393.6 ml of methanol to recover the precipitated solid. Further, the solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-5). The number average molecular weight of this polyimide was 11859, and the weight average molecular weight was 28493. Further, the imidization ratio was 59%.

(Synthesis Example 6)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 7.72 g (39.40 mmol) of A-1 as a tetracarboxylic dianhydride component and 3.81 g (28.00 mmol) of B-1 as a diamine component ), 1.86 g (8.00 mmol) of B-6 and 1.63 g (4.00 mmol) of B-8, and reacted in NMP 88.0 g for 24 hours at room temperature in a nitrogen atmosphere. A polyamic acid solution (PAA-6) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 156 mPa · s. The polyamic acid had a number average molecular weight of 12276 and a weight average molecular weight of 44911.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-6) was weighed, diluted by adding 43.8 g of NMP, and acetic anhydride 10.55 g (103.23 mmol) and pyridine 8 .18 g (103.23 mmol) was added and reacted at 70 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 393.6 ml of methanol to recover the precipitated solid. Further, the solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-6). The number average molecular weight of this polyimide was 11332, and the weight average molecular weight was 24325. The imidation ratio was 58%.

(Synthesis Example 7)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 7.72 g (39.40 mmol) of A-1 as the tetracarboxylic dianhydride component, 2.17 g (16.00 mmol) of B-1 as the diamine component ), B-6 (4.64 g, 0.020 mol) and B-8 (1.63 g, 4.00 mmol) were reacted in 91.7 g of NMP in a nitrogen atmosphere at room temperature for 24 hours to obtain a concentration of 15% by mass. A polyamic acid solution (PAA-7) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 136 mPa · s. The polyamic acid had a number average molecular weight of 12871 and a weight average molecular weight of 46548.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-7) was weighed, diluted by adding 43.8 g of NMP, 9.43 g (92.36 mmol) of acetic anhydride and pyridine 7 .31 g (92.36 mmol) was added and reacted at 70 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 393.6 ml of methanol to recover the precipitated solid. The solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-7). The number average molecular weight of this polyimide was 11566, and the weight average molecular weight was 27827. Moreover, the imidation ratio was 73%.

(Synthesis Example 8)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 7.69 g (39.20 mmol) of A-1 as a tetracarboxylic dianhydride component and 4.09 g (30.00 mmol) of B-1 as a diamine component ), 1.86 g (8.00 mmol) of B-6, 0.69 g (2.00 mmol) of B-7, and reacted in 91.7 g of NMP in a nitrogen atmosphere at room temperature for 24 hours, concentration of 15% by mass A polyamic acid solution (PAA-8) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 136 mPa · s. The number average molecular weight of this polyamic acid was 13602, and the weight average molecular weight was 45068.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-8) was weighed and diluted by adding 43.8 g of NMP, acetic anhydride 10.68 g (104.60 mmol) and pyridine 8 .28 g (104.60 mmol) was added and reacted at 70 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 393.6 ml of methanol to recover the precipitated solid. The solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-8). The number average molecular weight of this polyimide was 12566, and the weight average molecular weight was 28865. Further, the imidization ratio was 59%.

(Synthesis Example 9)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 7.68 g (39.16 mmol) of A-1 as a tetracarboxylic dianhydride component and 3.81 g (28.00 mmol) of B-1 as a diamine component ), 1.85 g (8.00 mmol) of B-6 and 1.39 g (4.00 mmol) of B-7, and reacted in 83.55 g of NMP in a nitrogen atmosphere at room temperature for 24 hours to obtain a concentration of 15% by mass. A polyamic acid solution (PAA-9) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 150 mPa · s. The polyamic acid had a number average molecular weight of 13301 and a weight average molecular weight of 43912.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-9) was weighed, diluted by adding 43.8 g of NMP, and 10.38 g (101.67 mmol) of acetic anhydride and pyridine 8 0.04 g (101.67 mmol) was added, and the mixture was reacted at 70 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 392.6 ml of methanol to recover the precipitated solid. Further, the solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-9). The number average molecular weight of this polyimide was 12736, and the weight average molecular weight was 27858. The imidation ratio was 58%.

(Synthesis Example 10)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 5.76 g (29.40 mmol) of A-1 as a tetracarboxylic dianhydride component, 2.93 g (19.50 mmol) of B-3 as a diamine component ), 1.74 g (7.50 mmol) of B-6 and 1.22 g (3.00 mmol) of B-8, and reacted in 66.1 g of NMP at room temperature in a nitrogen atmosphere for 24 hours. A polyamic acid solution (PAA-10) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 188 mPa · s. The number average molecular weight of this polyamic acid was 11254, and the weight average molecular weight was 29483.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-10) was weighed and diluted by adding 43.8 g of NMP. 9.60 g (94.02 mmol) of acetic anhydride and pyridine 7 .44 g (94.02 mmol) was added and reacted at 70 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 387.8 ml of methanol to recover the precipitated solid. Further, the solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-10). The number average molecular weight of this polyimide was 10983, and the weight average molecular weight was 22321. Moreover, the imidation ratio was 63%.

(Synthesis Example 11)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 7.39 g (37.73 mmol) of A-1 as the tetracarboxylic dianhydride component, 4.33 g (28.88 mol) of B-3 as the diamine component ), B-6 (1.79 g (7.70 mmol)) and B-9 (1.00 g (1.93 mmol)) were reacted in NMP (82.3 g) in a nitrogen atmosphere at room temperature for 24 hours. A polyamic acid solution (PAA-11) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 176 mPa · s. The polyamic acid had a number average molecular weight of 12462 and a weight average molecular weight of 28219.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-11) was weighed, diluted by adding 43.8 g of NMP, acetic anhydride 10.41 g (101.96 mmol) and pyridine 8 0.07 g (101.96 mmol) was added, and the mixture was reacted at 70 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 391.0 ml of methanol to recover the precipitated solid. Further, the solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-11). The number average molecular weight of this polyimide was 12143, and the weight average molecular weight was 25345. Moreover, the imidation ratio was 60%.

(Synthesis Example 12)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 10.2 g (34.30 mmol) of A-2 as a tetracarboxylic dianhydride component and 3.41 g (31.50 mmol) of B-4 as a diamine component ), 1.22 g (3.50 mmol) of B-7 and 1.39 g (4.00 mmol) of B-7, and reacted in 59.7 g of NMP in a nitrogen atmosphere at room temperature for 24 hours to obtain a concentration of 15% by mass. A polyamic acid solution (PAA-12) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 1023 mPa · s. The number average molecular weight of this polyamic acid was 9890, and the weight average molecular weight was 24302.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-12) was weighed and diluted by adding 116.7 g of NMP, and 28.43 g (278.45 mmol) of acetic anhydride and pyridine 13 were added. .22 g (167.01 mmol) was added and reacted at 40 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 729.1 ml of methanol to recover the precipitated solid. Further, the solid was washed twice with methanol and dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-12). The number average molecular weight of this polyimide was 9630, and the weight average molecular weight was 20013. Moreover, the imidation ratio was 85%.

(Synthesis Example 13)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 8.32 g (42.43 mmol) of A-1 as a tetracarboxylic dianhydride component and 4.76 g (38.97 mmol) of B-5 as a diamine component Then, 1.51 g (4.33 mmol) of B-7 was reacted in 82.7 g of NMP in a nitrogen atmosphere at room temperature for 24 hours to obtain a polyamic acid solution (PAA-13) having a concentration of 15% by mass. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 188 mPa · s. The polyamic acid had a number average molecular weight of 15284 and a weight average molecular weight of 46032.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-13) was weighed, diluted by adding 43.8 g of NMP, 6.80 g (66.60 mmol) of acetic anhydride and pyridine 2 .91 g (36.77 mmol) was added and reacted at 50 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 392.1 ml of methanol to recover the precipitated solid. The solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-13). The number average molecular weight of this polyimide was 12436, and the weight average molecular weight was 28954. The imidation ratio was 82%.

(Synthesis Example 14)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 8.32 g (42.43 mmol) of A-1 as a tetracarboxylic dianhydride component and 4.76 g (38.97 mmol) of B-5 as a diamine component , B-8 (1.76 g, 4.33 mmol) was reacted in 64.1 g of NMP in a nitrogen atmosphere at room temperature for 24 hours to obtain a polyamic acid solution (PAA-14) having a concentration of 15% by mass. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 163 mPa · s. The polyamic acid had a number average molecular weight of 11382 and a weight average molecular weight of 27679.
In a 200 ml eggplant type flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-14) was weighed and diluted by adding 57.1 g of NMP, and then 6.65 g (65.13 mmol) of acetic anhydride and pyridine 2 .85 g (36.02 mmol) was added and reacted at 50 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 408.3 ml of methanol to recover the precipitated solid. Further, the solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-14). The number average molecular weight of this polyimide was 10932, and the weight average molecular weight was 23243. The imidation ratio was 82%.

(Synthesis Example 15)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 7.69 g (39.20 mmol) of A-1 as the tetracarboxylic dianhydride component and 3.42 g (28.00 mmol) of B-5 as the diamine component , B-6 1.86 g (8.00 mmol) and B-7 1.39 g (4.00 mmol) were reacted in 81.4 g of NMP at room temperature in a nitrogen atmosphere for 24 hours. A polyamic acid solution (PAA-15) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 152 mPa · s. The number average molecular weight of this polyamic acid was 15372, and the weight average molecular weight was 45205.
In a 200 ml eggplant type flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-15) was weighed, diluted by adding 43.75 g of NMP, 9.40 g (92.07 mmol) of acetic anhydride and pyridine 7 .23 g (91.36 mmol) was added and reacted at 50 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 380.5 ml of methanol to recover the precipitated solid. The solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-15). The number average molecular weight of this polyimide was 14092, and the weight average molecular weight was 28301. The imidation ratio was 80%.

(Synthesis Example 16)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 8.26 g (42.14 mmol) of A-1 as a tetracarboxylic dianhydride component and 3.68 g (30.10 mmol) of B-5 as a diamine component , B-6 (2.00 g (8.60 mmol)) and B-8 (1.75 g (4.30 mmol)) were reacted in NMP 88.9 g at room temperature in a nitrogen atmosphere for 24 hours. A polyamic acid solution (PAA-16) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 156 mPa · s. The polyamic acid had a number average molecular weight of 16,332 and a weight average molecular weight of 46963.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-16) was weighed, diluted by adding 43.75 g of NMP, 9.79 g (95.89 mmol) of acetic anhydride and pyridine 7 .58 g (95.79 mmol) was added and reacted at 50 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 388.5 ml of methanol to recover the precipitated solid. The solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-16). The number average molecular weight of this polyimide was 15302, and the weight average molecular weight was 34024. The imidation ratio was 80%.

(Synthesis Example 17)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, as tetracarboxylic dianhydride components, 3.92 g (0.037 mmol) of A-1, 3.66 g (0.017 mmol) of A-3, a diamine component As a result, 7.93 g (0.040 mmol) of B-11 was reacted in NMP 44.2 g and γ-BL 44.2 g for 24 hours at room temperature in a nitrogen atmosphere, and a polyamic acid solution (PAA- 17) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 331 mPa · s. The number average molecular weight of this polyamic acid was 13603, and the weight average molecular weight was 34217.
In a 300 ml eggplant-shaped flask equipped with a stir bar, 80.0 g of the obtained polyamic acid solution (PAA-17) solution was weighed, 90.0 g of GBL and 30.0 g of BC were added, and the mixture was stirred at room temperature for 2 hours. A polyamic acid solution (PAA-17S) containing 6.0% by mass, NMP 20% by mass, GBL 59% and BC 15% by mass was obtained.

(Synthesis Example 18)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 6.38 g (32.55 mmol) of A-1 as a tetracarboxylic dianhydride component, 5.23 g (24.50 mmol) of B-10 as a diamine component ), And B-12 (3.01 g, 10.50 mmol) in NMP (41.4 g) and γ-BL (41.4 g) for 6 hours at room temperature in a nitrogen atmosphere to obtain a 15% strength by weight polyamic acid solution (PAA- 18) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 350 mPa · s. The number average molecular weight of this polyamic acid was 10221, and the weight average molecular weight was 25850.
In a 300 ml eggplant-shaped flask equipped with a stir bar, 80.0 g of the obtained polyamic acid solution (PAA-18) solution was weighed, 60.0 g of GBL and 60.0 g of BC were added, and the mixture was stirred at room temperature for 2 hours. A polyamic acid solution (PAA-18S) containing 6.0% by mass, NMP 20% by mass, GBL 44% and BC 30% by mass was obtained.

(Synthesis Example 19)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 6.38 g (32.55 mmol) of A-1 as a tetracarboxylic dianhydride component, 5.23 g (24.50 mmol) of B-10 as a diamine component ) And B-11 in 2.08 g (10.50 mmol) and reacted in NMP 38.8 g and γ-BL 38.8 g for 6 hours at room temperature in a nitrogen atmosphere to obtain a polyamic acid solution (PAA- 19) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 350 mPa · s. The polyamic acid had a number average molecular weight of 11476 and a weight average molecular weight of 35850.
In a 300 ml eggplant-shaped flask equipped with a stir bar, 80.0 g of the obtained polyamic acid solution (PAA-19) solution was measured, 60.0 g of GBL and 60.0 g of BC were added, and the mixture was stirred at room temperature for 2 hours. A polyamic acid solution (PAA-19S) containing 6.0% by mass, NMP 20% by mass, GBL 44% and BC 30% by mass was obtained.

(Synthesis Example 20)
Using a 100 ml four-necked flask equipped with a mechanical stirrer, 4.82 g (24.63 mmol) of A-1 as a tetracarboxylic dianhydride component and 2.29 g (18.75 mmol) of B-5 as a diamine component , B-6 (1.16 g, 5.00 mmol) and B-9 (1.25 g, 1.25 mmol) were reacted in NMP (50.6 g) at room temperature in a nitrogen atmosphere at room temperature for 15 hours. A polyamic acid solution (PAA-20) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 207 mPa · s. The number average molecular weight of this polyamic acid was 1,5992, and the weight average molecular weight was 40463.
In a 200 ml eggplant-shaped flask equipped with a stir bar, 50 g of the obtained polyamic acid solution (PAA-20) was weighed and diluted by adding 43.8 g of NMP, and 10.72 g (105.00 mmol) of acetic anhydride and pyridine 8 .30 g (105.00 mmol) was added and reacted at 50 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 388.5 ml of methanol to recover the precipitated solid. Further, the solid was washed twice with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide (SPI-17). The number average molecular weight of this polyimide was 14883, and the weight average molecular weight was 33025. Moreover, the imidation ratio was 84%.

Example 1
To 2.00 g of the polyimide (SPI-1) obtained in Synthesis Example 1, 14.67 g of GBL was added and stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, GBL 3.32 g, NMP 6.67 g BC 6.67 g were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. The solid content (SPI-1) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC A 20% by weight polyimide solution was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared by the method of Synthesis Example 18 were stirred at room temperature for 20 hours, and the solid content (mass ratio of SPI-1 and PAA-18 was 3: 7) was 6 mass%, NMP 20 mass%, GBL 47 mass%, and BC 27 mass%.

(Example 2)
To 2.00 g of the polyimide (SPI-2) obtained in Synthesis Example 2, 14.67 g of GBL was added and stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-2) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight polyimide solution was obtained.
30.0 g of this polyimide solution and 70.0 g of polyamic acid solution (PAA-18S) prepared by the method of Synthesis Example 18 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-2 and PAA-18 was 3: 7) was 6 mass%, NMP 20 mass%, GBL 47 mass%, and BC 27 mass%.

(Example 3)
To 2.00 g of the polyimide (SPI-3) obtained in Synthesis Example 3, 14.67 g of GBL was added and stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, 3.32 g of GBL and 6.67 g of NMP were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. The solid content (SPI-3) was 6 mass%, GBL was 54 mass%, NMP was 20 mass%, and BC was A 20% by weight polyimide solution was obtained.
20.0 g of this polyimide solution and 80.0 g of the polyamic acid solution (PAA-17S) prepared in Synthesis Example 17 were stirred at room temperature for 20 hours, and the solid content (mass ratio of SPI-3 and PAA-17 was 2: A liquid crystal aligning agent-3 having 6% by mass of 8), 20% by mass of NMP, 58% by mass of GBL, and 16% by mass of BC was obtained.

Example 4
14.67 g of GBL was added to 2.00 g of polyimide (SPI-4) obtained in Synthesis Example 4, and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-4) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight polyimide solution was obtained.
20.0 g of this polyimide solution and 80.0 g of the polyamic acid solution (PAA-17S) prepared by the method of Synthesis Example 17 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-4 to PAA-17 was 2: 8) was 6 mass%, NMP 20 mass%, GBL 58 mass%, and BC 16 mass%.

(Example 5)
14.67 g of GBL was added to 2.00 g of polyimide (SPI-5) obtained in Synthesis Example 5, and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-5) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight polyimide solution was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared by the method of Synthesis Example 18 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-5 and PAA-18 was 3: 7) was 6 mass%, NMP 20 mass%, GBL 47 mass%, and BC 27 mass%.

(Example 6)
14.67 g of GBL was added to 2.00 g of polyimide (SPI-6) obtained in Synthesis Example 6, and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-6) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight polyimide solution was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared by the method of Synthesis Example 18 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-6 and PAA-18 was 3: 7) was obtained, 6% by mass of NMP, 20% by mass of NMP, 47% by mass of GBL, and 27% by mass of BC, and liquid crystal aligning agent-6 was obtained.

(Example 7)
14.67 g of GBL was added to 2.00 g of the polyimide (SPI-7) obtained in Synthesis Example 7, and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, 3.32 g of GBL, 6.67 g of NMP, and 6.67 g of BC were added to this solution, followed by stirring at 50 ° C. for 20 hours. The solid content (SPI-7) was 6% by mass, GBL was 54% by mass, NMP was 20% by mass, A polyimide solution having a BC of 20% by mass was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared by the method of Synthesis Example 18 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-7 and PAA-18 was 3: 7) was 6 mass%, NMP 20 mass%, GBL 47 mass%, and BC 27 mass%.

(Example 8)
14.67 g of GBL was added to 2.00 g of the polyimide (SPI-8) obtained in Synthesis Example 8, and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-8) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight polyimide solution was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared by the method of Synthesis Example 18 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-8 to PAA-18 was 3: 7) was 6 mass%, NMP 20 mass%, GBL 47 mass%, and BC 27 mass%.

Example 9
To 2.00 g of the polyimide (SPI-9) obtained in Synthesis Example 9, 14.67 g of GBL was added and stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-9) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight polyimide solution was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared by the method of Synthesis Example 19 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-9 to PAA-18 was 3: 7) was 6 mass%, NMP 20 mass%, GBL 47 mass%, and BC 27 mass%.

(Example 10)
SPI-6 polyimide solution obtained by the method described in Example 6 (solid content 6 mass%, GBL 54 mass%, NMP 20 mass%, BC 20 mass%) 30.0 g, 70.0 g of the polyamic acid solution (PAA-17S) prepared by the method was stirred at room temperature for 20 hours, the solid content (mass ratio of SPI-10 and PAA-17 was 3: 7) was 6% by mass, and NMP was 20% by mass. Thus, a liquid crystal aligning agent-10 having a GBL of 57.5% by mass and a BC of 16.5% by mass was obtained.

(Example 11)
To 2.00 g of the polyimide (SPI-10) obtained in Synthesis Example 10, 14.67 g of GBL was added and stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-10) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight solution was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-17S) prepared by the method of Synthesis Example 17 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-10 to PAA-17 was 3: 7) was 6 mass%, NMP 20 mass%, GBL 57.5 mass%, and BC 16.5 mass%.

(Example 12)
To 2.00 g of the polyimide (SPI-11) obtained in Synthesis Example 11, 14.67 g of GBL was added and stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-11) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight solution was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-17S) prepared by the method of Synthesis Example 17 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-11 to PAA-17 was 3: 7) was 6 mass%, NMP 20 mass%, GBL 57.5 mass%, and BC 16.5 mass% liquid crystal aligning agent-12.

(Example 13)
SPI-6 polyimide solution obtained by the method described in Example 6 (solid content 6% by mass, GBL 54% by mass, NMP 20% by mass, BC 20% by mass) 30.0 g, 30.0 g of the polyamic acid solution (PAA-19S) prepared by the method was stirred at room temperature for 20 hours, the solid content (mass ratio of SPI-6 and PAA-19 was 5: 5) was 6% by mass, and NMP was 20% by mass. Thus, a liquid crystal aligning agent-13 having a GBL of 45.0% by mass and a BC of 25.0% by mass was obtained.

(Example 14)
SPI-10 polyimide solution obtained by the method described in Example 11 (solid content 6% by mass, GBL 54% by mass, NMP 20% by mass, BC 20% by mass) 30.0 g, 30.0 g of the polyamic acid solution (PAA-17S) prepared by the method was stirred at room temperature for 20 hours, the solid content (mass ratio of SPI-10 and PAA-17 was 5: 5) was 6% by mass, and NMP was 20% by mass. Thus, a liquid crystal aligning agent-14 having a GBL of 56.5% by mass and a BC of 17.5% by mass was obtained.

(Example 15)
0.4 g of the polyimide (SPI-5) obtained in Synthesis Example 5 and 1.6 g of the polyimide (SPI-6) obtained in Synthesis Example 6 were mixed, 14.67 g of GBL was added, and the mixture was stirred at 50 ° C. for 20 hours. . The polyimide was completely dissolved at the end of stirring. Further, 3.32 g of GBL and 6.67 g of NMP were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. A solution containing 20% by mass, 20% by mass of NMP and 20% by mass of BC was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared in Synthesis Example 18 were stirred at room temperature for 20 hours to obtain a solid content (SPI-5 / SPI-6 / PAA-18: mass). Ratio = 6/24/70) was 6 mass%, NMP 20 mass%, GBL 47 mass%, and BC 27 mass%.

(Example 16)
0.4 g of the polyimide (SPI-5) obtained in Synthesis Example 5 and 1.6 g of the polyimide (SPI-7) obtained in Synthesis Example 7 were mixed, 14.67 g of GBL was added, and the mixture was stirred at 50 ° C. for 20 hours. . The polyimide was completely dissolved at the end of stirring. Further, 3.32 g of GBL and 6.67 g of NMP were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. A solution containing 20% by mass, 20% by mass of NMP and 20% by mass of BC was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared in Synthesis Example 18 were stirred at room temperature for 20 hours to obtain a solid content (SPI-5 / SPI-7 / PAA-18: mass). Ratio = 6/24/70) was 6 mass%, NMP 20 mass%, GBL 47 mass%, and BC 27 mass%.

(Example 17)
0.4 g of the polyimide (SPI-8) obtained in Synthesis Example 8 and 1.6 g of the polyimide (SPI-9) obtained in Synthesis Example 9 were mixed, 14.67 g of GBL was added, and the mixture was stirred at 50 ° C. for 20 hours. . The polyimide was completely dissolved at the end of stirring. Further, 3.32 g of GBL and 6.67 g of NMP were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. A solution containing 20% by mass, 20% by mass of NMP and 20% by mass of BC was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared in Synthesis Example 18 were stirred at room temperature for 20 hours to obtain a solid content (SPI-8 / SPI-9 / PAA-18: mass). Ratio = 6/24/70) was 6 mass%, NMP 20 mass%, GBL 47 mass%, and BC 27 mass%.

(Example 18)
1.6 g of polyimide (SPI-5) obtained in Synthesis Example 5 and 0.4 g of polyimide (SPI-6) obtained in Synthesis Example 6 were mixed, 14.67 g of GBL was added, and the mixture was stirred at 50 ° C. for 20 hours. . The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g and NMP 6.67gBC 6.67g were added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (mass ratio of SPI-4 and SPI-5 is 2: 8) is 6 mass%, GBL is 54 A solution containing 20% by mass, 20% by mass of NMP and 20% by mass of BC was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared in Synthesis Example 18 were stirred at room temperature for 20 hours to obtain a solid content (SPI-5 / SPI-6 / PAA-18: mass). Ratio = 24/6/70) was 6 mass%, NMP 20 mass%, GBL 47 mass%, and BC 27 mass%.

(Example 19)
Mixed polyimide solution of SPI-5 and SPI-6 obtained by the method described in Example 18 (SPI-5: SPI-6 = 8: 2, solid content 6 mass%, GBL 54 mass%, NMP 20 mass) %, BC is 20% by mass) and 30.0 g of the polyamic acid solution (PAA-19S) prepared in Synthesis Example 19 were stirred at room temperature for 20 hours to obtain a solid content (SPI-5 / SPI-6 / PAA-19: mass ratio = 24/6/70) was 6 mass%, NMP 20 mass%, GBL 47 mass%, and BC 27 mass%.

(Example 20)
A polyimide solution of SPI-1 obtained by the method described in Example 1 (solid content: 6% by mass, GBL: 54% by mass, NMP: 20% by mass, BC: 20% by mass) Liquid crystal aligning agent-20 of the present invention Used for evaluation.

(Example 21)
A polyimide solution of SPI-6 (solid content: 6% by mass, GBL: 54% by mass, NMP: 20% by mass, BC: 20% by mass) obtained by the method described in Example 6 is the liquid crystal aligning agent-21 of the present invention. Used for evaluation.

(Comparative Example 1)
To 2.00 g of the polyimide (SPI-12) obtained in Synthesis Example 12, 14.67 g of GBL was added and stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, 18.66 g of GBL was added to this solution and stirred at 50 ° C. for 20 hours to obtain a solution having a solid content (SPI-12) of 6 mass% and a GBL of 94 mass%.
20.0 g of this polyimide solution and 80.0 g of a polyamic acid solution (PAA-17S) prepared by the method of Synthesis Example 17 were stirred at room temperature for 20 hours, and the solid content (mass ratio of SPI-12 and PAA-17 was 2: 8) was 6 mass%, NMP 18 mass%, GBL 62.0 mass%, and BC 12.0 mass%.

(Comparative Example 2)
14.67 g of GBL was added to 2.00 g of the polyimide (SPI-13) obtained in Synthesis Example 13, and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-13) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight solution was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared by the method of Synthesis Example 18 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-13 to PAA-18 was 3: 7) was 6 mass%, NMP 20 mass%, GBL 47.0 mass%, and BC 27.0 mass%.

(Comparative Example 3)
14.67 g of GBL was added to 2.00 g of polyimide (SPI-14) obtained in Synthesis Example 14, and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-14) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight solution was obtained.
30.0 g of this polyimide solution and 70.0 g of polyamic acid solution (PAA-18S) prepared by the method of Synthesis Example 18 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-14 to PAA-18 was 3: 7) was obtained, 6% by mass of NMP, 20% by mass of NMP, 47.0% by mass of GBL, and 27.0% by mass of BC.

(Comparative Example 4)
14.67 g of GBL was added to 2.00 g of the polyimide (SPI-15) obtained in Synthesis Example 15, and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-15) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight solution was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared by the method of Synthesis Example 18 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-15 to PAA-18 was A liquid crystal aligning agent-25 having a ratio of 3: 7) of 6% by mass, NMP of 20% by mass, GBL of 47.0% by mass, and BC of 27.0% by mass was obtained.

(Comparative Example 5)
14.67 g of GBL was added to 2.00 g of the polyimide (SPI-16) obtained in Synthesis Example 16, and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-16) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight solution was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared by the method of Synthesis Example 18 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-16 to PAA-18 was 3: 7) was 6 mass%, NMP 20 mass%, GBL 47.0 mass%, and BC 27.0 mass%.

(Comparative Example 6)
SPI-16 polyimide solution obtained by the method described in Comparative Example 5 (solid content 6% by mass, GBL 54% by mass, NMP 20% by mass, BC 20% by mass) 30.0 g, 70.0 g of the polyamic acid solution (PAA-17S) prepared by the above method was stirred at room temperature for 20 hours, the solid content (mass ratio of SPI-16 and PAA-17 was 3: 7) was 6% by mass, and NMP was 20% by mass. Thus, a liquid crystal aligning agent-27 having a GBL content of 57.5 mass% and a BC content of 16.5 mass% was obtained.

(Comparative Example 7)
SPI-16 polyimide solution obtained by the method described in Comparative Example 5 (solid content 6% by mass, GBL 54% by mass, NMP 20% by mass, BC 20% by mass) 30.0 g, 70.0 g of the polyamic acid solution (PAA-19S) prepared by the method was stirred at room temperature for 20 hours, the solid content (mass ratio of SPI-16 to PAA-19 was 3: 7) was 6% by mass, and NMP was 20% by mass. Thus, a liquid crystal aligning agent-28 having a GBL of 47.0% by mass and a BC of 27.0% by mass was obtained.

(Comparative Example 8)
14.67 g of GBL was added to 2.00 g of the polyimide (SPI-17) obtained in Synthesis Example 20, and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Furthermore, GBL 3.32g, NMP 6.67gBC 6.67g was added to this solution, and it stirred at 50 degreeC for 20 hours, solid content (SPI-20) was 6 mass%, GBL 54 mass%, NMP 20 mass%, and BC. A 20% by weight solution was obtained.
30.0 g of this polyimide solution and 70.0 g of the polyamic acid solution (PAA-18S) prepared by the method of Synthesis Example 18 were stirred at room temperature for 20 hours, and the solid content (the mass ratio of SPI-16 to PAA-18 was A liquid crystal aligning agent-29 having 3: 7) of 6% by mass, NMP of 20% by mass, GBL of 47.0% by mass and BC of 27.0% by mass was obtained.

(Comparative Example 9)
Evaluation of SPI-13 polyimide solution (solid content 6% by mass, GBL 54% by mass, NMP 20% by mass, BC 20% by mass) obtained by the method described in Comparative Example 2 as liquid crystal aligning agent-30 Using.

(Comparative Example 10)
Evaluation of SPI-16 polyimide solution (solid content 6 mass%, GBL 54 mass%, NMP 20 mass%, BC 20 mass%) obtained by the method described in Comparative Example 5 as liquid crystal aligning agent-31 Using.

Two tetracarboxylic acids for polyamic acids: PAA-1 to PAA-20 and polyimides: SPI-1 to SPI-17 used in the preparation of the liquid crystal aligning agents of Examples 1 to 21 and Comparative Examples 1 to 10 above. Table 3 shows the water component, the diamine component, and the imidization ratio.
Tables 4-1 and 4-2 show the mixing ratio of polyamic acid and polyimide in each of the liquid crystal aligning agents of Examples 1 to 21 and Comparative Examples 1 to 10.
Further, Table 5 shows the results of the pretilt angle, the high-temperature and high-humidity test, and the backlight aging resistance obtained with the liquid crystal cells produced using the liquid crystal aligning agents of Examples 1 to 21 and Comparative Examples 1 to 10. It was.

Examples 1 to 21 show the characteristics of the liquid crystal alignment film using the liquid crystal aligning agent of the present invention, but they have good high temperature and high humidity tests evaluated by voltage holding ratio and backlight aging resistance, and pretilt. A result with little variation in the above is obtained. On the other hand, Comparative Examples 1 to 10 are inferior in the high-temperature / high-humidity test and backlight aging resistance evaluated by the voltage holding ratio, and the pretilt angle varies greatly.

The liquid crystal display element produced using the liquid crystal aligning agent of the present invention can be a highly reliable liquid crystal display device, such as a TN liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, an OCB liquid crystal display element, It is suitably used for display elements using various methods.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2010-105933 filed on April 30, 2010 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims

A polyamic acid component obtained by reacting a diamine represented by the following general formula [1] and a diamine component containing the diamine represented by the following general formula [2] with tetracarboxylic dianhydride: A liquid crystal aligning agent comprising an imidized soluble polyimide.

(In the formula, X represents an aromatic ring, R 1 represents alkylene having 1 to 5 carbon atoms, and R 2 represents a hydrocarbon group having 1 to 4 carbon atoms.)

(In the formula, R 1 represents a single bond or a divalent organic group, X 1 , X 2 , and X 3 each independently represent a benzene ring or a cyclohexane ring, and p, q, and r each independently represents 0. Or an integer of 1 and R 2 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton.)
2. The liquid crystal aligning agent according to claim 1, wherein X in the general formula [1] is a phenylene group, R 1 is a linear alkylene group having 1 to 5 carbon atoms, and R 2 is a methyl group or an ethyl group.
The liquid crystal aligning agent according to claim 1 , wherein X in the general formula [1] is a phenylene group, and R 1 is a methylene group or an ethylene group.
In the general formula [2], R 1 is a divalent organic group selected from —O—, —NHCO—, —COO— and —CH 2 O—, and R 2 is a hydrogen atom or a linear alkyl having 1 to 18 carbon atoms. The liquid crystal aligning agent according to any one of claims 1 to 3, which is a group.
R 1 in the general formula [2] is a divalent organic group selected from —O— and —NHCO—, p is 0 to 1, q is 0 to 1, r is 0, R 4. The liquid crystal aligning agent according to claim 1, wherein 2 is a hydrogen atom or a linear alkyl group having 1 to 18 carbon atoms.
6. The liquid crystal aligning agent according to claim 1, wherein the general formula [2] is a diamine represented by the formula [3].
The liquid crystal aligning agent according to any one of claims 1 to 6, wherein the diamine component contains 5 to 95 mol% of the diamine represented by the formula [1].
The diamine component contains 5 to 60 mol% of the diamine represented by the formula [2] and 0.1 to 1.2 mol relative to 1 mol of the diamine represented by the formula [1]. The liquid crystal aligning agent according to any one of 1 to 6.
The liquid crystal aligning agent according to any one of claims 1 to 8, wherein the soluble polyimide is a polyimide obtained by imidizing polyamic acid at an imidization ratio of 10 to 85%.
10. The liquid crystal aligning agent according to claim 1, wherein the soluble polyimide is contained by being dissolved in an organic solvent, and the soluble polyimide is contained in an amount of 1 to 10% by mass.
And a polyamic acid obtained by reacting a diamine component not containing the diamine represented by the formula [1] and the diamine represented by the formula [2] with a tetracarboxylic dianhydride component. Item 11. The liquid crystal aligning agent according to any one of Items 1 to 10.
The liquid crystal aligning agent according to claim 11, wherein the polyamic acid is contained in an amount of 10 to 10,000 parts by mass with respect to 100 parts by mass of the soluble polyimide.
The organic solvent is N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinylpyrrolidone, dimethyl The liquid crystal aligning agent according to any one of claims 10 to 12, which is sulfoxide, tetramethylurea, dimethylsulfone, hexamethylphosphoric triamide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, or a mixture thereof.
A liquid crystal alignment film obtained using the liquid crystal aligning agent according to any one of claims 1 to 13.
A liquid crystal display device comprising the liquid crystal alignment film according to claim 14.