KR20090123898A - Diamine compound, polyamic acid, polyimide and liquid crystal aligning agent - Google Patents

Abstract

Disclosed is a novel diamine which has an effect of increasing the pretilt angle of a liquid crystal when used as a raw material for a liquid crystal aligning agent. This diamine enables to vertically align a liquid crystal even when used in a small amount.In addition, this diamine hardly precipitates even when a poor solvent is mixed in a liquid crystal aligning agent solution for improving coatability of the agent. Specifically disclosed is a diamine represented by the following formula (1). (1) (In the formula (1), Rrepresents a phenylene or a cyclohexylene; and Rrepresents an alkyl group having 3-12 carbon atoms, a fluoroalkyl group having 3-12 carbon atoms, an alkoxy group having 3-12 carbon atoms or a fluoroalkoxy group having 3-12 carbon atoms.)

Description

Diamine compound, polyamic acid, polyimide and liquid crystal aligning agent {DIAMINE COMPOUND, POLYAMIC ACID, POLYIMIDE AND LIQUID CRYSTAL ALIGNING AGENT}

The present invention relates to a novel diamine compound (also referred to simply as a diamine in the present invention) useful as a raw material for a polymer used in a liquid crystal alignment film, a polyamic acid, a polyimide, and a liquid crystal alignment treatment agent obtained using the diamine.

Currently, a polyimide film is used for the liquid crystal aligning film used for a liquid crystal display element in many cases, and this polyimide film is a method of apply | coating and baking the solution of the polyamic acid which is a precursor of a polyimide, or the solution of solvent-soluble polyimide to a board | substrate. Is being taken. This polyamic acid or solvent-soluble polyimide is synthesize | combined by reaction of tetracarboxylic acid derivatives, such as tetracarboxylic dianhydride, and diamine generally.

One of the characteristics required for the liquid crystal alignment film is the so-called pretilt angle control of the liquid crystal, which maintains the alignment inclination angle of the liquid crystal molecules with respect to the substrate surface at an arbitrary value. It is known that the magnitude | size of this pretilt angle can be changed by selecting the structure of the polyimide which comprises the liquid crystal aligning film.

Among the techniques for controlling the pretilt angle by the structure of the polyimide, the method of using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle according to the use ratio of the diamine, and thus the desired pretilt It is relatively easy to set the angle and is useful as a means for increasing the pretilt angle. As a side chain structure of diamine which enlarges the pretilt angle of a liquid crystal, a long-chain alkyl group or a fluoroalkyl group (for example, refer patent document 1), a combination of a cyclic group or a cyclic group and an alkyl group (for example, patent document 2) Steroid skeletons (see, eg, Patent Document 3), and the like.

In addition, the diamine for increasing the pretilt angle of the liquid crystal is also examined for a structure for improving the stability and process dependency of the pretilt angle. As the side chain structure used herein, a phenyl group, a cyclohexyl group, or the like is used. It is proposed to contain a ring structure (see Patent Documents 4 and 5, for example). Moreover, the diamine which has such a ring structure in 3-4 side chain is also proposed (for example, refer patent document 6).

In recent years, liquid crystal display devices have been widely used in large-area liquid crystal televisions and high-definition mobile applications (display portions of digital cameras and mobile phones). ) Unevenness is increasing. Even in such a situation, it has been required to apply the liquid crystal alignment film uniformly to a large substrate and a step in view of display characteristics.

In the liquid crystal aligning film manufacturing process, when apply | coating the solution of a polyamic acid and the solution of solvent-soluble polyimide to a board | substrate, it is industrially performed by flexographic printing etc. normally. The solvent of the coating liquid is added to N-methyl-2-pyrrolidone, γ-butyrolactone, or the like which is a solvent having excellent solubility in resin (hereinafter, also referred to as a good solvent), in order to increase the coating film uniformity. Butyl cellosolve etc. which are solvents of low solubility (henceforth a poor solvent) are mixed. However, since the poor solvent has a poor ability to dissolve polyamic acid and polyimide, precipitation occurs when mixed in a large amount (see Patent Document 7, for example). In particular, this problem is remarkable in solutions of solvent soluble polyimides. Moreover, since the polyimide obtained by using the diamine which has such a side chain has a tendency for the application uniformity of a solution to fall, it is necessary to increase the mixing amount of a poor solvent, and the mixing tolerance of such a solvent is also important. Becomes a characteristic.

Patent Document 1: Japanese Patent Application Laid-Open No. 2-282726

Patent Document 2: Japanese Patent Application Laid-Open No. 3-179323

Patent Document 3: Japanese Patent Application Laid-Open No. 4-281427

Patent Document 4: Japanese Patent Application Laid-Open No. 9-278724

Patent Document 5: International Publication No. 2004/52962 Pamphlet

Patent Document 6: Japanese Unexamined Patent Publication No. 2004-67589

Patent Document 7: Japanese Patent Application Laid-Open No. 2-37324

Disclosure of Invention

Problems to be Solved by the Invention

The present invention has the effect of increasing the pretilt angle of the liquid crystal when used as a raw material of the polyamic acid and / or polyimide (hereinafter also referred to as polymer) constituting the liquid crystal alignment film, and the liquid crystal is vertically used even at a small use ratio. An object of the present invention is to provide a novel diamine that can be aligned and that is a raw material of polyamic acid and / or polyimide in which precipitation hardly occurs when a poor solvent is mixed with a coating liquid of a liquid-crystal aligning agent.

Moreover, an object of this invention is to provide the liquid crystal display element which has a polymer obtained from the said novel diamine, the liquid-crystal aligning agent containing this polymer, and also the liquid-crystal aligning film obtained using this liquid-crystal aligning agent.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM The present inventor progressed earnest research, and reached | attained this invention which can achieve the said objective, and this invention has the following summary.

1. Diamine represented by following formula (1).

[Formula 1]

(In formula (1), R <_1> is phenylene or cyclohexylene, R <_2> is a C3-C12 alkyl group, a C3-C12 fluoroalkyl group, a C3-C12 alkoxy group, or C3-C12. Fluoroalkoxy group)

2. The diamine according to the above 1, wherein R ₁ is 1,4-phenylene or 1,4-cyclohexylene in formula (1).

3. Diamine as described in said 1 or said 2 represented by following formula (2-1).

[Formula 2]

(In Formula (2-1), n is an integer of 2-11, and the cis-trans isomer of 1, 4- cyclohexylene is a trans isomer, respectively.)

4. Diamine as described in said 1 or said 2 represented by following formula (2-2).

[Formula 3]

(In formula (2-2), n is an integer of 2-11, and the cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer.)

5. Polyimide obtained by dehydrating and ring-closing the polyamic acid obtained by making the diamine component containing the diamine in any one of said 1-4, and tetracarboxylic dianhydride react, or this polyamic acid.

6. Polyamic acid or polyimide of said 5 whose 10 mol% or more in a diamine component is the diamine in any one of said 1-4.

7. Liquid-crystal aligning agent containing at least 1 sort (s) of compound in polyamic acid and polyimide of said 5 or 6.

8. Liquid-crystal aligning agent of said 7 containing organic solvent containing 5-60 mass% poor solvent.

9. Liquid crystal aligning film obtained using said liquid-crystal aligning agent of 7 or said 8.

10. The liquid crystal display element which has the liquid crystal aligning film of 9 said.

Effects of the Invention

The diamine of this invention has the effect which remarkably enlarges the pretilt angle of a liquid crystal, when used as a raw material of the polymer which comprises a liquid crystal aligning film. For example, as shown later in Table 2, the pretilt angle of the liquid crystal aligning film obtained from the diamine (PBCH5DAB) of this invention represented by Formula (2-1) is about 82 degrees of the liquid crystal aligning film obtained from diamine (PBCH7DAB). Although the pretilt angle is about 83 °, the pretilt angle of the liquid crystal aligning film obtained from the conventional diamine (PCH7DAB) described in Patent Document 4 having a similar structure is about 22 °, which is about four times larger, which is unexpected.

For this reason, the liquid-crystal aligning agent obtained from the diamine of this invention can provide a large pretilt angle to a liquid crystal with a small use ratio, and can also orientate a liquid crystal perpendicularly.

Moreover, when preparing the coating liquid for obtaining a liquid crystal aligning film, even if many poor solvents are used with a good solvent in order to improve applicability, the liquid-crystal aligning agent obtained from the diamine of this invention does not precipitate a polymer well, Even when apply | coating to the board | substrate of a 2nd, a uniform thin film can be formed and the liquid crystal aligning film of the outstanding characteristic can be manufactured.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.

1.diamine

Diamines of the present invention is the diamino to a benzene ring via a bonding group (-O-), phenylene-cyclohexylene is a combined side chain having the structure -R ₂ compound-phenylene or cyclohexylene ring. That is, it is a novel diamino benzene derivative represented by following formula (1).

[Formula 4]

In formula (1), R <_1> is phenylene or cyclohexylene. The ring of phenylene or cyclohexylene may have a substituent as needed. Preferably, it is 1, 4- phenylene or 1, 4- cyclohexylene. In the ring of 1, 4- phenylene or 1, 4- cyclohexylene, you may have a substituent as needed.

R <_2> is a C3-C12 alkyl group, a C3-C12 fluoroalkyl group, a C3-C12 alkoxy group, or a C3-C12 fluoroalkoxy group. Although an alkyl group, a fluoroalkyl group, an alkoxy group, and a fluoroalkoxy group may be linear or branched type, a linear type is preferable and may have a suitable substituent. Especially, R <_2> is a C3-C12 alkyl group or a C3-C12 fluoroalkyl group, More preferably, it is a C3-C12 alkyl group, More preferably, it is a C3-C9 alkyl group, Especially Is a C3-C7 alkyl group.

The bonding position of the amino group in the benzene ring which comprises the said diamino benzene ring is not limited. Specifically, 2,3, 2,4, 2,5, 2,6, 3,4, and 3,5 positions on the benzene ring with respect to the side chain linking group (-O-) Can be mentioned. Especially, from a viewpoint of the reactivity at the time of synthesize | combining a polyamic acid, 2, 4 position, 2, 5 position, and 3, 5 position are preferable. If the ease of diamine synthesis is also included, the 2,4 position or the 2,5 position is more preferable.

Among the diamines of the above formula (1), the diamine represented by the following formula (2-1) and formula (2-2), wherein R ₁ is 1,4-trans-cyclohexylene, has a pretilt angle of the liquid crystal at a small use ratio. It is preferable at the point that the effect which can enlarge is large. In particular, since the effect is excellent, the diamine represented by Formula (2-1) is more preferable.

[Formula 5]

In formula (2-1), n is an integer of 2-11, and the isomer of the cis-trans isomer of 1, 4- cyclohexylene is respectively preferable.

[Formula 6]

In formula (2-2), n is an integer of 2-11, and the isomer of the cis-trans isomer of 1, 4- cyclohexylene is respectively preferable.

Preferable specific examples of the diamine represented by the formula (1) of the present invention are as follows. In addition, n in the following formula is an integer of 2-11, Preferably it is an integer of 2-8, More preferably, it is an integer of 2-6. In addition, the cis-trans isomer of 1, 4- cyclohexylene in a formula is a trans isomer, respectively.

[Formula 7]

Although the method of manufacturing the diamine represented by the said Formula (1) of this invention is not specifically limited, The following method is mentioned as a preferable method.

[Formula 8]

It is obtained by synthesize | combining the dinitro compound of said Formula (3), reducing a nitro group by a conventional method, and converting into an amino group. R <_1> , R <_2> in Formula (3) is the same as what was defined in Formula (1).

The dinitro compound of Formula (3) can be obtained by reaction, such as a hydroxyl group containing compound represented by following formula (4), dinitrobenzene. In addition, R <_1> , R <_2> in Formula (4) is the same as what was defined by Formula (1).

[Formula 9]

Although the hydroxyl group containing compound represented by said Formula (4) can be manufactured by the method shown by following Reaction Formula [1]-Reaction Formula [2], this invention is not limited to this.

When R <_1> is cyclohexylene, the synthetic route of reaction formula [1] is mentioned. R <_1> , R < ₂ > in reaction formula [1] is as having defined by Formula (1), X <_1> represents protecting groups, such as a methyl group or benzyl group, X <_2> represents MgBr, MgCl, Li, etc.

Examples of the reagent used for the dehydration reaction include inorganic acids such as hydrochloric acid or sulfuric acid, organic acids such as p-toluene sulfonic acid, and acid anhydrides such as acetic anhydride or trifluoro acetic anhydride.

Examples of the reduction reaction include a hydrogenation reaction using palladium (Pd) or platinum (Pt) as a catalyst, or a catalytic reduction reaction using a metal such as iron, tin, or zinc. With a de-protecting group reaction there may be mentioned boron tribromide (BBr ₃₎ to ride by hydrogenation using a catalyst such as Pd or elimination reaction of the methyl group using benzylation reaction.

[Formula 10]

By the said reaction formula [1], the hydroxyl group containing compound represented by the said Formula (4) shown below can be manufactured.

When R <_1> is phenylene, the synthetic route of reaction formula [2] is mentioned. R <_1> , R < ₂ > in Reaction Formula [1] is the same as what was defined by Formula (1), X <_1> represents protecting groups, such as a methyl group or a benzyl group, X <_3> is a halogen atom, methanesulfonyloxy group, benzenesulfonyloxy group, Trifluoromethanesulfonyloxy group, B (OH) ₂ , MgBr, MgCl or Li and the like, X ₄ represents a halogen atom, methanesulfonyloxy group, benzenesulfonyloxy group, trifluoromethanesulfonyloxy group, B (OH ) ₂ , MgBr, MgCl or Li and the like. With a de-protecting reaction, etc. using a desorption reaction or a Pd catalyst of the methyl group with BBr ₃ and the like can be de-benzylated by hydrogenation reaction.

[Formula 11]

By the said Reaction formula [2], the hydroxyl group containing compound represented by the said Formula (4) shown below can be manufactured.

[Formula 12]

The diamine of this invention can obtain the polyamic acid which has a specific structure in a side chain by making it react with tetracarboxylic acid or its derivatives, such as tetracarboxylic acid, tetracarboxylic-acid dihalide, tetracarboxylic dianhydride, etc. Furthermore, By dehydrating and ring-closing this polyamic acid, the polyimide which has a structure specific to a side chain can be obtained.

2. Polyamic Acid

The polyamic acid of this invention is a polyamic acid obtained by reaction of the diamine component and the tetracarboxylic dianhydride containing the diamine represented by Formula (1). The polyimide of this invention is a polyimide obtained by dehydrating and ring-closing this polyamic acid. Both such polyamic acid and polyimide are useful as a polymer for obtaining a liquid crystal aligning film.

In the diamine component (henceforth a diamine component) for obtaining a polyamic acid by reaction with the said tetracarboxylic dianhydride, there is no restriction | limiting in the content rate of the diamine represented by Formula (1). In the liquid crystal aligning film obtained using the polyamic acid or polyimide of this invention, the pretilt angle of a liquid crystal becomes large, so that the content rate of the diamine represented by Formula (1) in the said diamine component increases.

It is preferable that 1 mol% or more of a diamine component is the diamine represented by Formula (1) for the purpose of enlarging the pretilt angle of a liquid crystal. It is preferable that 10 mol% or more of a diamine component is the diamine represented by Formula (1) for the purpose of orienting a liquid crystal perpendicularly | vertically, More preferably, it is 15 mol% or more.

Although the diamine represented by Formula (1) may be sufficient as 100 mol% of a diamine component in the objective of orienting a liquid crystal perpendicularly, the diamine represented by Formula (1) from a viewpoint of uniform applicability at the time of apply | coating the liquid-crystal aligning agent mentioned later is 80 mol% or less of a diamine component is preferable, More preferably, it is 40 mol% or less.

In the said diamine component, diamines other than the diamine represented by Formula (1) used when the diamine represented by Formula (1) is less than 100 mol% are not specifically limited. The specific example is given as follows.

p-phenylenediamine

m-phenylenediamine

2,4-diaminotoluene

2,5-diaminotoluene

2,6-diaminotoluene

2,4-dimethyl-1,3-diaminobenzene

2,5-dimethyl-1,4-diaminobenzene

2,3,5,6-tetramethyl-1,4-diaminobenzene

2,4-diaminophenol

2,5-diaminophenol

4,6-diaminoresorcinol

2,5-diaminobenzoic acid

3,5-diaminobenzoic acid

N, N-diallyl-2,4-diaminoaniline

N, N-diallyl-2,5-diaminoaniline

4-aminobenzylamine

3-aminobenzylamine

2- (4-aminophenyl) ethylamine

2- (3-aminophenyl) ethylamine

1,5-naphthalenediamine

2,7-naphthalenediamine

4,4'-diaminobiphenyl

3,4'-diaminobiphenyl

3,3'-diaminobiphenyl

2,2'-dimethyl-4,4'-diaminobiphenyl

3,3'-dimethyl-4,4'-diaminobiphenyl

3,3'-dimethoxy-4,4'-diaminobiphenyl

3,3'-dihydroxy-4,4'-diaminobiphenyl

3,3'-dicarboxy-4,4'-diaminobiphenyl

3,3'-difluoro-4,4'-diaminobiphenyl

2,2'-trifluoromethyl-4,4'-diaminobiphenyl

3,3'-trifluoromethyl-4,4'-diaminobiphenyl

4,4'-diaminodiphenylmethane

3,3'-diaminodiphenylmethane

3,4'-diaminodiphenylmethane

4,4'-diaminodiphenyl ether

3,3'-diaminodiphenyl ether

3,4'-diaminodiphenyl ether

4,4'-diaminodiphenylsulfone

3,3'-diaminodiphenylsulfone

4,4'-diaminodiphenylamine

3,3'-diaminodiphenylamine

3,4'-diaminodiphenylamine

N-methyl (4,4'-diaminodiphenyl) amine

N-methyl (3,3'-diaminodiphenyl) amine

N-methyl (3,4'-diaminodiphenyl) amine

4,4'-diaminobenzophenone

3,3'-diaminobenzophenone

3,4'-diaminobenzophenone

4,4'-diaminobenzanilide

1,2-bis (4-aminophenyl) ethane

1,2-bis (3-aminophenyl) ethane

4,4'-diaminotolan

1,3-bis (4-aminophenyl) propane

1,3-bis (3-aminophenyl) propane

2,2-bis (4-aminophenyl) propane

2,2-bis (3-aminophenyl) propane

2,2-bis (3-amino-4-methylphenyl) propane

2,2-bis (4-aminophenyl) hexafluoropropane

2,2-bis (3-aminophenyl) hexafluoropropane

2,2-bis (3-amino-4-methylphenyl) hexafluoropropane

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

1,11-bis (4-aminophenoxy) undecane

1,12-bis (4-aminophenoxy) dodecane

Bis (4-aminophenyl) propanedioate

Bis (4-aminophenyl) butanedioate

Bis (4-aminophenyl) pentanedioate

Bis (4-aminophenyl) hexanedioate

Bis (4-aminophenyl) heptanedioate

Bis (4-aminophenyl) octanedioate

Bis (4-aminophenyl) nonanddioate

Bis (4-aminophenyl) decanedioate

1,4-bis (4-aminophenyl) benzene

1,3-bis (4-aminophenyl) benzene

1,4-bis (4-aminophenoxy) benzene

1,3-bis (4-aminophenoxy) benzene

1,4-bis (4-aminobenzyl) benzene

1,3-bis (4-aminobenzyl) benzene

Bis (4-aminophenyl) terephthalate

Bis (3-aminophenyl) terephthalate

Bis (4-aminophenyl) isophthalate

Bis (3-aminophenyl) isophthalate

1,4-phenylenebis [(4-aminophenyl) methanone]

1,4-phenylenebis [(3-aminophenyl) methanone]

1,3-phenylenebis [(4-aminophenyl) methanone]

1,3-phenylenebis [(3-aminophenyl) methanone]

1,4-phenylenebis (4-aminobenzoate)

1,4-phenylenebis (3-aminobenzoate)

1,3-phenylenebis (4-aminobenzoate)

1,3-phenylenebis (3-aminobenzoate)

N, N '-(1,4-phenylene) bis (4-aminobenzamide)

N, N '-(1,3-phenylene) bis (4-aminobenzamide)

N, N '-(1,4-phenylene) bis (3-aminobenzamide)

N, N '-(1,3-phenylene) bis (3-aminobenzamide)

Bis (4-aminophenyl) terephthalamide

Bis (3-aminophenyl) terephthalamide

Bis (4-aminophenyl) isophthalamide

Bis (3-aminophenyl) isophthalamide

2,2-bis [4- (4-aminophenoxy) phenyl] propane

2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane

4,4'-bis (4-aminophenoxy) diphenylsulfone

2,6-diaminopyridine

2,4-diaminopyridine

2,4-diamino-1,3,5-triazine

2,6-diaminodibenzofuran

2,7-diaminodibenzofuran

3,6-diaminodibenzofuran

2,6-diaminocarbazole

2,7-diaminocarbazole

3,6-diaminocarbazole

2,4-diamino-6-isopropyl-1,3,5-triazine

2,5-bis (4-aminophenyl) -1,3,4-oxadiazole

1,3-diaminopropane

1,4-diaminobutane

1,5-diaminopentane

1,6-diaminohexane

1,7-diaminoheptane

1,8-diaminooctane

1,9-diaminononane

1,10-diaminodecane

1,11-diaminoundecane

1,12-diaminododecane

1,4-diaminocyclohexane

1,3-diaminocyclohexane

Bis (4-aminocyclohexyl) methane

Bis (4-amino-3-methylcyclohexyl) methane

In order to obtain the polyamic acid of this invention, the tetracarboxylic dianhydride made to react with a diamine component is not specifically limited. By the way, the specific example is as follows.

Pyromellitic Acid 2 Anhydride

2,3,6,7-naphthalenetetracarboxylic dianhydride

1,2,5,6-naphthalenetetracarboxylic dianhydride

1,4,5,8-naphthalenetetracarboxylic dianhydride

2,3,6,7-anthracenetetracarboxylic dianhydride

1,2,5,6-anthracenetetracarboxylic dianhydride

3,3 ', 4,4'-biphenyltetracarboxylic dianhydride

2,2 ', 3,3'-biphenyltetracarboxylic dianhydride

2,3,3 ', 4'-biphenyltetracarboxylic dianhydride

3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride

2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride

Bis (3,4-dicarboxyphenyl) methane 2 anhydride

Bis (3,4-dicarboxyphenyl) ether 2 anhydride

Bis (3,4-dicarboxyphenyl) sulfon 2 anhydride

2,2-bis (3,4-dicarboxyphenyl) propane 2 anhydride

2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride

2,5-dicarboxymethylterephthalic acid dianhydride

4,6-dicarboxymethylisophthalic acid dianhydride

4- (2,5-dioxotetrahydro-3-furanyl) phthalic anhydride

1,4-bis (2,5-dioxotetrahydro-3-furanyl) benzene

1,4-bis (2,6-dioxotetrahydro-4-pyranyl) benzene

1,4-bis (2,5-dioxotetrahydro-3-methyl-3-furanyl) benzene

1,4-bis (2,6-dioxotetrahydro-4-methyl-4-pyranyl) benzene

1,2,3,4-butanetetracarboxylic dianhydride

1,2,3,4-cyclobutanetetracarboxylic dianhydride

1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride

1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride

1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride

1,2,3,4-cyclopentanetetracarboxylic dianhydride

2,3,4,5-tetrahydrofurantetracarboxylic dianhydride

2,3,5-tricarboxycyclopentyl acetic acid anhydride

1,2,4,5-cyclohexanetetracarboxylic dianhydride

4- (2,5-Dioxotetrahydro-3-furanyl) -cyclohexane-1,2-dicarboxylic acid anhydride

5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride

Bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride

3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride

3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride

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

3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride

2,3,5,6-norbornane tetracarboxylic dianhydride

3,5,6-tricarboxynorbornane-2-acetic acid dianhydride,

Tricyclo [4.2.1.O ^2,5 ] nonane-3,4,7,8-tetracarboxylic dianhydride

Tetracyclo [4.4.1.0 ^2,5 .0 ^7,10 ] undecane-3,4,8,9-tetracarboxylic dianhydride

Hexahydro cyclo ^{[6.6.0.1 2,7 .0 3,6 .1 9,14 .0} 10,13] hexadecane -4,5,11,12- tetracarboxylic dianhydride

1,4-bis (2,5-dioxotetrahydro-3-furanyl) hexane

1,4-bis (2,6-dioxotetrahydro-4-pyranyl) hexane

As a method of making the said diamine component and tetracarboxylic dianhydride react, the method of mixing a diamine component and tetracarboxylic dianhydride in an organic solvent is simple.

The organic solvent is not particularly limited as long as the produced polyamic acid is dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide and γ-butyrolactone. These may be used alone or in combination. Furthermore, even if it is a poor solvent which does not melt | dissolve a polyamic acid alone, you may mix and use it with the said solvent in the range in which the produced polyamic acid does not precipitate. In addition, since moisture in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use an organic solvent that is dehydrated and dried as much as possible.

As a method of mixing a diamine component and tetracarboxylic dianhydride in an organic solvent, the solution which disperse | distributed or dissolved diamine in the organic solvent is stirred, and tetracarboxylic dianhydride is disperse | distributed or dissolved in the organic solvent as it is, The method of adding, on the contrary, the method of adding diamine to the solution which disperse | distributed or dissolved tetracarboxylic dianhydride in an organic solvent, the method of adding tetracarboxylic dianhydride and diamine to an organic solvent alternately or simultaneously, etc. are mentioned. Any of these methods may be used.

Although the reaction temperature at the time of the said polyamic acid synthesis | combination can select arbitrary temperature of -20-150 degreeC, Preferably it is the range of -5-100 degreeC.

The reaction can be carried out at an arbitrary concentration. If the concentration of the diamine component and tetracarboxylic dianhydride as raw materials is too low, it is difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution is excessive. Since it becomes high and uniform stirring becomes difficult, Preferably it is 1-50 mass%, More preferably, it is 5-30 mass%. The reaction initial stage may be performed in high concentration | density, and may add an organic solvent after that.

In the synthesis reaction of a polyamic acid, it is preferable that ratio of the mole number of tetracarboxylic dianhydride with respect to the mole number of a diamine component is 0.8-1.2. As in the conventional polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyamic acid.

The molecular weight of the polyamic acid of the present invention is not particularly limited. When considering the workability at the time of coating the liquid-crystal aligning agent mentioned later, the uniformity of a coating film, and the intensity | strength of the coating film obtained, it is preferable to set it as 5,000-300,000 by the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method, Preferably, it is 10,000-150,000.

3. Polyimide

The polyimide of this invention is a polyimide obtained by dehydrating and ring-closing the said polyamic acid, and is useful as a polymer for obtaining a liquid crystal aligning film.

In the polyimide of the present invention, the dehydration ring closure rate (imidization rate) of the amic acid group does not necessarily need to be 100%, and may be arbitrarily adjusted according to the use or the purpose.

As a method of dehydrating and ring-closing a polyamic acid, the heat | fever imidation which heats a polyamic acid without using a catalyst, and the catalyst imidation which uses a catalyst are mentioned.

When heat-imidizing a polyamic acid, it is preferable to carry out heating a solution of polyamic acid to 100-400 degreeC, Preferably it is 120-250 degreeC, removing the water produced | generated by the imidation reaction out of system.

Catalytic imidization of polyamic acid can be performed by adding a basic catalyst and an acid anhydride to a solution of polyamic acid, and stirring at -20-250 degreeC, Preferably it is 0-180 degreeC. The amount of the basic catalyst is 0.5 to 30 mole times, preferably 2 to 20 mole times, of the amic acid group, and the amount of the acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times, of the amic acid group.

Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst, Especially, since pyridine has suitable basicity for advancing reaction, it is preferable.

Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, and among them, acetic anhydride is preferred because the purification after completion of the reaction is facilitated. The imidation ratio by catalyst imidation can be controlled by adjusting catalyst amount, reaction temperature, and reaction time.

The molecular weight of the polyimide of this invention is not specifically limited. When considering the workability at the time of coating the liquid-crystal aligning agent mentioned later, the uniformity of a coating film, and the intensity | strength of the coating film obtained, it is preferable to set it as 5,000-300,000 by the weight average molecular weight measured by GPC method, More preferably, it is 10,000- 150,000.

When recovering a polymer component from the reaction solution of polyamic acid or polyimide, what is necessary is just to throw a reaction solution into a poor solvent and to precipitate. Examples of the poor solvent used for the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by being poured into the poor solvent is recovered by filtration, and then dried under normal pressure or reduced pressure, followed by normal temperature or heating.

4. Liquid-crystal aligning agent

The liquid-crystal aligning agent of this invention is a coating liquid for manufacturing a liquid crystal aligning film, The main component is a composition containing the resin component for forming a resin film, and the organic solvent which melt | dissolves this resin component.

As the above-mentioned resin component, the liquid-crystal aligning agent of this invention contains the polyamic acid and polyimide of the said at least any one (henceforth the polymer of this invention). It is preferable that content of the polymer of this invention in a resin component is 5 mass% or more, More preferably, it is 10 mass% or more.

As for the said resin component, the polymer of this invention may be sufficient as the whole, and the other polymer other than that may be mixed with the polymer of this invention. As an example of such another polymer, the polyamic acid or polyimide obtained using diamines other than the diamine represented by Formula (1) as a diamine component made to react with tetracarboxylic dianhydride is mentioned.

The organic solvent which melt | dissolves a resin component is not specifically limited. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, γ-butyrolactone, and the like. have. These organic solvents become a good solvent with high solubility of resin.

Moreover, in addition to the said good solvent, in order to make coating uniformity of a liquid-crystal aligning agent high, it is preferable to use the poor solvent with low solubility of a polymer. In the present invention, preferred poor solvents include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Ethylcarbitol acetate, ethylene glycol, ethylene glycol monohexyl ether, 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-2-acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n- Butyl ester and lactic acid isoamyl ester are mentioned. It is preferable that this poor solvent is 5-60 mass% of the organic solvent contained in a liquid-crystal aligning agent, More preferably, it is 10-50 mass%.

The density | concentration of the resin component in the liquid-crystal aligning agent of this invention can be suitably adjusted suitably according to the film thickness of the liquid crystal aligning film to obtain, the apparatus used for application | coating of a liquid-crystal aligning agent, etc. As general resin concentration of a liquid-crystal aligning agent, 1-20 mass%, Preferably 2-10 mass% can be illustrated.

You may contain the component of that excepting the above in the liquid-crystal aligning agent of this invention. Examples thereof include a functional silane-containing compound and an epoxy group-containing compound for improving the adhesion between the liquid crystal aligning film and the substrate, and a fluorine-based surfactant, silicone-based surfactant, and nonionic-based surfactant for improving the flatness of the coating film.

When it contains a functional silane containing compound and an epoxy group containing compound, it is preferable that all the amounts are 0.1-30 mass parts with respect to 100 mass parts of resin components, More preferably, it is 1-20 mass parts, Especially preferably, 1- 10 parts by mass.

In the case of containing a surfactant, the amount thereof is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component.

5. Liquid crystal aligning film and liquid crystal display element

The liquid crystal aligning agent of the present invention is coated with a substrate and baked on a substrate in the same manner as a commercially available polyimide liquid crystal aligning agent, and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like, or in some vertical alignment applications, without the alignment treatment. It can be set as an alignment film.

Although the coating method of the liquid-crystal aligning agent of this invention is not specifically limited, The method of performing by screen printing, flexographic printing, offset printing, an inkjet, etc. is common. In addition, as a method of using a coating liquid, there exist a dip, a roll coater, a slit coater, a spinner, etc., You may use these according to the objective. After apply | coating on a board | substrate by these methods, a solvent can be evaporated by heating means, such as a hotplate, and a coating film can be formed.

Although baking after apply | coating a liquid-crystal aligning agent can be performed at arbitrary temperature of 100-300 degreeC, Preferably it is 150 degreeC-250 degreeC. This firing can be performed by a hot plate, a hot air circulating furnace, an infrared furnace, or the like.

Rayon cloth, nylon cloth, cotton cloth, etc. can be used for a rubbing process. Since the liquid-crystal aligning film for vertical alignment is hard to obtain a uniform orientation state by a rubbing process, when using as a liquid-crystal aligning agent for vertical alignment, it is preferable to use, without rubbing.

The liquid crystal cell of this invention can be manufactured by a conventional method, and the manufacturing method is not specifically limited. Generally, the sealing agent is apply | coated to the glass substrate in which the liquid crystal aligning film was formed on the at least one board | substrate, a spacer was disperse | distributed so that a fixed gap can be maintained, and then, two board | substrates are attached and the sealing agent is hardened | cured and empty. A method of manufacturing a cell, and then injecting liquid crystal from the liquid crystal inlet under vacuum and sealing the inlet to produce a liquid crystal cell; Or the liquid crystal is dripped on the board | substrate which disperse | distributed a spacer, and the method of manufacturing a liquid crystal cell by sticking two board | substrates after that, etc. can be used. As a liquid crystal, the fluorine-type liquid crystal, cyano-type liquid crystal, etc. which have a positive and negative dielectric constant anisotropy can be used according to a use.

The liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention as mentioned above can provide a large pretilt angle to a liquid crystal, and can be used for the liquid crystal aligning film of various uses.

Example

Although an Example is given to this invention concretely below, it cannot be overemphasized that this invention is limited to these Examples.

"Synthesis of the diamine of the present invention"

<Example 1>

Of diamines [9]

[Formula 13]

4-methoxyphenylmagnesium bromide [1] (0.5 M-tetrahydrofuran solution, 2.4 liter (L), 1.20 mol) and tetrahydrofuran (200 mL) were added to the nitrogen-substituted four neck flask. After cooling the reactor to 0 ° C., a tetrahydrofuran (280 g) solution of 4- (trans-4-n-pentylcyclohexyl) cyclohexanone [2] (300 g, 1.20 mol) was added dropwise. After completion | finish of dripping, it heated up to 25 degreeC gradually and stirred at 25 degreeC again for 15 hours. After completion | finish of reaction, after cooling a reaction liquid at 0 degreeC, 10% acetic acid aqueous solution (1.0 L) was dripped gradually. Thereafter, the aqueous layer was removed by a liquid separation operation, and toluene (2.4 L) was added, followed by washing with saturated brine (1.0 L), saturated aqueous sodium hydrogen carbonate solution (1.0 L) and saturated brine (1.0 L). The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. Obtained compound [3] (cis-trans isomer mixture) (430 g) was used for the next reaction in that state.

In addition, ¹ H-NMR of the obtained compound was carried out using an NMR measuring apparatus (400 MHz) in deuterated chloroform using TMS (Si (CH ₃ ) ₄ ) as a reference substance. Although the measurement result of compound [3] is shown below, it is the same also about other compounds.

Compound [3] (cis-trans isomer mixture);

A dehydrated toluene (2.5 L) mixture of compound [3] (cis-trans isomer mixture) (430 g, 1.20 mol) and p-toluenesulfonic acid monohydrate (13.1 g, 72.0 mmol) was extracted with water while refluxing. The reaction was carried out for 2 hours. After the completion of the reaction, the reaction mixture was brought to a temperature of 80 ° C, and washed with saturated aqueous sodium hydrogen carbonate solution (1.5 L) and saturated brine (1.5 L). The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained crude substance was recrystallized with the ethyl acetate / ethanol (1: 1 v / v) mixed solvent, and compound [4] (cis-trans isomer mixture) was obtained (amount 379 g, 89% yield).

Compound [4] (cis-trans isomer mixture);

A mixture of compound [4] (379 g, 1.10 mol), 5% palladium carbon (function, 19.0 g, 5 wt%), ethyl acetate, 1 liter, and ethanol (1 liter) was carried out at room temperature (25 ° C) in the presence of hydrogen. Stirred. After completion of the reaction, the reaction mixture was filtered through celite and the celite was washed with toluene (1 L). The filtrate was concentrated under a reduced pressure to obtain compound [5] (cis-trans isomer mixture) (gain 347 g, yield 91%).

Compound [5] (cis-trans isomer mixture);

Boron tribromide (1.0 M-dichloromethane solution, 1.0 L, 1.00 mol) in a 2.0 L solution of methylene chloride of Compound [5] (cis-trans isomer mixture) (347 g, 1.00 mol) at 0 ° C. Was added dropwise. After dripping, it stirred at 0 degreeC for 2 hours. After the reaction was completed, the reaction solution was added little by little in distilled water. Extraction was performed with ethyl acetate (2.0 L), and the extract was washed twice with distilled water (1.0 L). After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained crude substance was recrystallized with ethanol, and wash | cleaned with ethanol, and the compound [6] (trans isomer) was obtained (183 g of yield, 55% of yield). The cis-trans isomers of 1,4-cyclohexylene of compound [6] are each trans isomers.

Compound [6] (trans isomer);

In a mixture of compound [6] (trans isomer) (20.0 g, 61.0 mmol), potassium carbonate (25.3 g, 183 mmol), toluene (149 g), under reflux, 1-chloro-2,4-dinitro A toluene (49.0 g) solution of benzene [7] (12.4 g, 61.0 mmol) was added dropwise. After dropping, the mixture was stirred at reflux overnight. After the reaction was completed, the reaction solution was washed three times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained crude was recrystallized with 2-propanol and washed with ethanol to obtain compound [8] (trans isomer) (amount 27.4 g, yield 90%). The cis-trans isomers of 1,4-cyclohexylene of compound [8] are each trans isomers.

Compound [8] (trans isomer);

A mixture of compound [8] (trans isomer) (27.4 g, 55.0 mmol), 5% palladium carbon (2.74 g, 10 wt%), 1,4-dioxane (329 g) in the presence of hydrogen, 26 ° C., Stir for 4 hours. After the reaction was completed, the mixture was filtered through celite. The filtrate was removed under reduced pressure to obtain a crude product. This crude product was recrystallized with ethanol / ethyl acetate (1: 1 v / v) mixed solvent, and the diamine [9] (trans isomer) was obtained (22.0 g of yield, 91% of yield). The cis-trans isomers of 1,4-cyclohexylene of compound [9] are each trans isomers.

Diamine [9] (trans isomer);

<Example 2>

Of diamines [15]

[Formula 14]

4- (trans-4-n-pentylcyclohexyl) bromobenzene [10] (50.0 g, 162 mmol), 4-methoxyphenylboronic acid [11] (36.9 g, 243 mmol), toluene (1.4 L), a mixed solution of ethanol (0.16 L) and an aqueous sodium carbonate solution (sodium carbonate (44.6 g, 0.42 mol) / distilled water 0.6 L) was degassed by nitrogen gas. Pd (PPh ₃ ) ₄ (0.934 g, 0.808 mmol) was added to this solution under a nitrogen atmosphere, and the mixture was stirred at 90 ° C for 6 hours. After completion of the reaction, the organic layer was separated and washed twice with distilled water (0.5 L). After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained crude material was recrystallized with the ethyl acetate / hexane (1: 1 v / v) mixed solvent, and wash | cleaned with hexane, and the compound [12] (trans isomer) was obtained (40.0 g of yield, 73% of yield). The cis-trans isomer of 1,4-cyclohexylene of compound [12] is a trans isomer.

Compound [12] (trans isomer);

Boron tribromide (120 mL, 1.0 M-dichloromethane solution, 120 mmol) in a dichloromethane (500 mL) solution of compound [12] (trans isomer) (40.0 g, 120 mmol) at 0 ° C. under nitrogen substitution. It dripped. After dripping, it stirred at 0 degreeC for 2 hours. After the reaction was completed, the reaction solution was added little by little in distilled water (500 mL). Extraction was performed with ethyl acetate (500 mL), and the extract was washed twice with distilled water (300 mL). After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained crude substance was recrystallized with the ethyl acetate / hexane (1: 1 v / v) mixed solvent, and wash | cleaned with hexane, and the compound [13] (trans isomer) was obtained (29.5 g of yield, 77% of yield). The cis-trans isomer of 1,4-cyclohexylene of compound [13] is a trans isomer.

Compound [13] (trans isomer);

1-chloro-2,4-dinitro under reflux in a mixture of compound [13] (trans isomer) (15.3 g, 47.5 mmol), potassium carbonate (19.7 g, 140 mmol) and toluene (69.0 g) A toluene (35.0 g) solution of benzene [7] (9.62 g, 48.0 mmol) was added dropwise. After dripping, it stirred at reflux for 5 hours. After the reaction was completed, the reaction solution was washed twice with distilled water. After drying the organic layer with magnesium sulfate, the solvent was removed under reduced pressure. The obtained crude substance was wash | cleaned with 2-propanol, and the compound [14] (trans isomer) was obtained (21.0 g of yields, 90% of yields). The cis-trans isomer of 1,4-cyclohexylene of compound [14] is a trans isomer.

Compound [14] (trans isomer);

A mixture of compound [14] (trans isomer) (21.0 g, 430 mol), 5% -palladium carbon (2.1 g, 10 wt%) and 1,4-dioxane (240 g) was refluxed under a hydrogen atmosphere. After stirring for 32 hours, the mixture was stirred at 25 ° C. for 72 hours. After the reaction was completed, the mixture was filtered through celite. The filtrate was removed under reduced pressure to obtain a crude product. The crude product was recrystallized twice with toluene to obtain diamine [15] (trans isomer) (amount 9.42 g, yield 51%). The cis-trans isomer of 1,4-cyclohexylene of compound [15] is a trans isomer.

Diamine [15] (trans isomer);

<Example 3>

Synthesis of diamines [18]

[Formula 15]

In the same synthesis method as in Example <1>, diamine [18] (trans isomer) was obtained through compound [17] (trans isomer) using compound [16].

The cis-trans isomers of 1,4-cyclohexylene of compound [17] and diamine [18] are each trans isomers.

Compound [17] (trans isomer);

Diamine [18] (trans isomer);

Synthesis Example 1

Of diamines [23]

[Formula 16]

4-bromo-4 '-(n-pentyl) biphenyl [19] (25.0 g, 82.4 mmol) and tetrakis (triphenylphosphine) palladium (0) 4.76 g, 4.12 mmol) was added, and 4-methoxyphenylmagnesium bromide [1] (0.5 M-tetrahydrofuran solution, 280 mL, 140 mmol) was added thereto, followed by heating to reflux. . After completion of the reaction, the mixture was cooled to room temperature to precipitate a solid, and then the reaction solution was poured into ethyl acetate (200 g) / 1M hydrochloric acid (280 ml) and filtered. The obtained solid was washed with water, washed with ethyl acetate and dried to obtain an off-white solid compound [20] (gain 26.8 g, yield 98%).

Compound [20];

Boron tribromide (1.0 M-dichloromethane solution, 75.7 mL, 75.7 mmol) was added dropwise into a dehydrated dichloromethane (300 g) solution of compound [20] (25.0 g, 75.7 mmol) at 0 ° C under nitrogen substitution. . After dripping, it stirred and stirred at 0 degreeC for 2 hours, and after completion | finish of reaction, the reaction liquid was added little by little in distilled water. It extracted with 2.5 L of ethyl acetate warmed to 60 degreeC, and the organic layer was wash | cleaned twice with 300 ml of distilled water. The organic layer was dried over magnesium sulfate and concentrated until the solvent became about 500 ml. The precipitated solid was filtered, washed with ethyl acetate and dried to obtain an iso-colour solid compound [21] (gain 19.1 g, yield 80%).

Compound [21];

1-chloro-2,4-dinitrobenzene [7] under reflux in a mixture of compound [21] (10.0 g, 31.6 mmol), potassium carbonate (13.10 g, 31.6 mmol) and toluene (46 g). Toluene (31 g) solution of (6.40 g, 31.6 mmol) was added dropwise. After dripping, reaction was performed at reflux for 17 hours. After completion of the reaction, ethyl acetate (2.5 L) and distilled water (200 g) were added to the reaction solution, and the aqueous layer was removed by liquid separation. Thereafter, the organic layer was washed three times with distilled water (200 mL). The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. Ethyl acetate (50 g) was added to the obtained crude product, and the resulting mixture was washed with ultrasonic waves, and then filtered and dried to obtain a white solid mixture [22] (gain 12.1 g, yield 79%).

[Compound 22];

A mixture of compound [22] (11.0 g, 22.8 mmol), 5% palladium carbon (1.1 g, 10 wt%) and 1,4-dioxane (165 g) was stirred at 65 ° C in the presence of hydrogen. After completion | finish of reaction, after filtrating with Celite, the filtrate was removed under reduced pressure and the crude material was obtained. Dioxane (50 g) was added to this crude product, which was then dispersed and washed with an ultrasonic device, followed by filtration and drying to obtain a diamine [23] as a pale white solid (yield 7.8 g, yield 81%). .

Diamine [23];

"Synthesis of the polyamic acid or polyimide of the present invention"

Abbreviation and structure of the compound used by the following example and a comparative example

(Tetracarboxylic dianhydride)

BODA: Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

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

[Formula 17]

(Diamine)

p-PDA: p-phenylenediamine

DBA: 3,5-diamino benzoic acid

DAA: N, N-diallyl-2,4-diaminoaniline

PBCH5DAB: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene

BPCH5DAB: 1,3-diamino-4- {4- [4- (trans-4-n-pentylcyclohexyl) phenyl] phenoxy} benzene

PBCH7DAB: 1,3-diamino-4- {4- [trans-4- (trans-4-n-heptylcyclohexyl) cyclohexyl] phenoxy} benzene

m-PBCH5DABEs: 3,5-diamino- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenyl} benzoate

PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

PBP5DAB: 1,3-diamino-4-[(4-n-pentylphenyl) phenoxy] benzene

(Remarks)

PBCH5DAB is a diamine [9] synthesized in the same manner as in Example 1.

BPCH5DAB is a diamine [15] synthesized in the same manner as in Example 2.

PBCH7DAB is a diamine [18] synthesized in the same manner as in Example 3.

m-PBCH5DABEs were synthesized in accordance with the examples of JP-A-2004-67589 using compound [6] synthesized in the same manner as in Example 1.

PCH7DAB was synthesize | combined according to the Example of Unexamined-Japanese-Patent No. 9-278724.

PBP5DAB is a diamine [23] synthesized in the same manner as in Synthesis Example 1.

[Formula 18]

[Formula 19]

[Formula 20]

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

The measuring method used by the following example is shown below.

[Molecular Weight]

In this Example, the molecular weight of the polyimide was measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex, a column (KD-803, KD-805) manufactured by Shodex, as follows. It was.

Column temperature: 50 ℃

Eluent: N, N-dimethylformamide (as additive, lithium bromide monohydrate (LiBrH ₂ O) is 30.0 mmol / L, phosphoric acid and anhydrous crystals (o-phosphate) is 30.0 mmol / L, tetrahydrofuran 10.0 ml / l)

Flow rate: 1.00 ml / min

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) by Tosoh Corporation and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) by Polymer Laboratories.

[Imidization rate]

In the present Example, the imidation ratio of the polyimide was measured as follows.

About 20.0 mg of polyimide powder was put into an NMR sample tube, and about 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS (Si (CH ₃ ) ₄ ) mixture) was added thereto, followed by the application of ultrasonic waves to complete the process. Dissolved. This solution was measured for proton NMR at 500 MHz in an NMR measuring apparatus.

The imidation ratio determines the proton derived from the structure which does not change before and after imidization as a reference proton, and uses the peak integration value of this proton and the proton peak integration value derived from the NH group of the amic acid which appears in 10.0 ppm vicinity. It calculated | required by the following formula.

·x/y) × 100Imidation ratio (%) = (1-

X / y) × 100

는 폴리아믹산 (이미드화율이 0 ％) 인 경우에 있어서의 아믹산의 NH 기 프로톤 1 개에 대한 기준 프로톤의 개수 비율이다.In the above formula, x is the proton peak integration value derived from the NH group of amic acid, y is the peak integration value of a reference proton,

Is the number ratio of the reference protons to one NH group proton of amic acid in the case of polyamic acid (imidation ratio is 0%).

<Example 4>

BOB (5.07 g, 20.3 mmol), p-PDA (2.48 g, 22.9 mmol) and PBCH5DAB (1.76 g, 4.05 mmol) as side chain diamines were mixed in NMP (22.0 g) and reacted at 40 ° C. for 5 hours. CBDA (1.22 g, 6.22 mmol) and NMP (20.0g) were added after making it react, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic-acid solution (30.0g), and it diluted to 6 mass%, acetic anhydride (4.63g) and pyridine (3.59g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (442 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (A). The imidation ratio of this polyimide was 45%, the number average molecular weight was 15,300 and the weight average molecular weight was 36,200.

Example 5

BODA (4.88 g, 19.5 mmol), p-PDA (2.39 g, 22.1 mmol) and BPCH5DAB (1.67 g, 3.90 mmol) as side chain diamines were mixed in NMP (22.0 g) and reacted at 40 DEG C for 5 hours. CBDA (1.16g, 5.92 mmol) and NMP (18.0g) were added after making it react, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic-acid solution (35.0g), and it diluted to 6 mass%, acetic anhydride (4.67g) and pyridine (3.62g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (443 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (B). The imidation ratio of this polyimide was 40%, the number average molecular weight was 13,200 and the weight average molecular weight was 38,400.

<Example 6>

BOB (8.25 g, 33.0 mmol), p-PDA (3.33 g, 30.8 mmol) and side chain diamine were mixed with PBCH5DAB (5.74 g, 13.2 mmol) in NMP (38.0 g) and reacted at 40 ° C for 5 hours. CBDA (2.10g, 10.7 mmol) and NMP (40.0g) were added after making it react, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

After adding NMP to this polyamic-acid solution (20.0g) and diluting to 6 mass%, acetic anhydride (2.32g) and pyridine (1.80g) were added as imidation catalyst, and it was made to react at 90 degreeC for 3.5 hours. This reaction solution was poured into methanol (278 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (C). The imidation ratio of this polyimide was 60%, the number average molecular weight was 15,800 and the weight average molecular weight was 50,900.

<Example 7>

BOB (4.13 g, 16.5 mmol), p-PDA (2.01 g, 18.6 mmol), and PBCH7DAB (1.53 g, 3.31 mmol) as side chain diamines were mixed in NMP (20.0 g) and reacted at 40 ° C. for 5 hours. CBDA (0.97g, 4.95 mmol) and NMP (14.6g) were added after making it react, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic-acid solution (20.0g), and it diluted to 6 mass%, acetic anhydride (2.59g) and pyridine (2.01g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (250 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (D). The imidation ratio of this polyimide was 52%, the number average molecular weight was 14,600 and the weight average molecular weight was 36,300.

<Example 8>

BOB (6.44 g, 25.7 mmol), p-PDA (2.60 g, 24.0 mmol), and PBCH7DAB (4.77 g, 10.3 mmol) as side chain diamines were mixed in NMP (30.0 g) and reacted at 40 ° C. for 5 hours. After making it CBDA (1.64g, 8.35 mmol) and NMP (31.2g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (20.0g) and diluting to 6 mass%, acetic anhydride (2.31g) and pyridine (1.80g) were added as imidation catalyst, and it was made to react at 90 degreeC for 3.5 hours. This reaction solution was poured into methanol (290 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (E). The imidation ratio of this polyimide was 59%, the number average molecular weight was 16,400 and the weight average molecular weight was 48,600.

Comparative Example 1

BODA (5.07 g, 20.3 mmol), p-PDA (2.48 g, 22.9 mmol), m-PBCH5DABEs (1.87 g, 4.04 mmol) as side chain diamines were mixed in NMP (22.0 g) and 5 at 40 ° C. After making it react for time, CBDA (1.00g, 5.10 mmol) and NMP (20.0g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic-acid solution (30.0g), and it diluted to 6 mass%, acetic anhydride (4.28g) and pyridine (3.32g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (408 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (F). The imidation ratio of this polyimide was 45%, the number average molecular weight was 14,900 and the weight average molecular weight was 38,800.

Comparative Example 2

BODA (5.03 g, 20.1 mmol), p-PDA (2.03 g, 18.8 mmol) and m-PBCH5DABEs (3.73 g, 8.06 mmol) as side chain diamines were mixed in NMP (23.0 g) and 5 at 40 ° C. After making it react for time, CBDA (1.28g, 6.53 mmol) and NMP (24.5g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic-acid solution (20.0g), and it diluted to 6 mass%, acetic anhydride (2.28g) and pyridine (1.82g) were added as imidation catalyst, and it reacted at 90 degreeC for 3.5 hours. This reaction solution was poured into methanol (280 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (G). The imidation ratio of this polyimide was 60%, the number average molecular weight was 15,600 and the amount average molecular weight was 42,800.

Comparative Example 3

BODA (4.13 g, 16.5 mmol), p-PDA (2.02 g, 18.7 mmol) and PBP5DAB (1.39 g, 3.29 mmol) as side chain diamines were mixed in NMP (19.0 g) and reacted at 40 ° C. for 5 hours. CBDA (0.86 g, 4.39 mmol) and NMP (14.6 g) were added after making it react, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic-acid solution (20.0g), and it diluted to 6 mass%, acetic anhydride (2.60g) and pyridine (2.02g) were added as imidation catalyst, and it was made to react at 80 degreeC for 2.5 hours. This reaction solution was poured into methanol (250 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (H). The imidation ratio of this polyimide is 45%, the number average molecular weight is 14800 and the amount average molecular weight is 36,300.

<Solubility Test of Polyimide> (Comparison of Butyl Cellosolve Mixing Allowance)

Using the polyimide powder obtained in Examples 4-8 and Comparative Examples 1-3, the butyl cellosolve mixing tolerance with respect to the polyimide solution was performed in the following procedure.

NMP (8.70g) was added to the polyimide powder (1.30g), and it stirred at 80 degreeC for 40 hours, and it was set as the polyimide solution of 13 mass% of resin concentration. This polyimide solution (1.00g) was isolate | separated into a sample tube, the magnetic stirrer was put, and BCS was dripped by the pipette, stirring at 25 degreeC. The point of time when the haze generated immediately after the dropping of the BCS was not extinguished even after a few seconds was visually confirmed to be the end point. In addition, 1 drop of BCS was about 0.004 g at this time. The BCS mixing amount at the end point was determined by confirming the mass of the entire sample tube before and after BCS mixing.

As a result of the said test, the end point when the polyimide of Example 4 is used is 1.33 g of BCS, and the end point when the polyimide of Example 5 is used is the end point when B08 is 1.08 g and the polyimide of Example 6 is used. When the BCS is 1.43 g and the polyimide of Example 7 is used, the BIS is 1.26 g and the longitudinal islands when the polyimide of Example 8 is used are 1.38 g of BCS and the polyimide of Comparative Example 1 is used. As for the end point, when BCS used 0.11g and the polyimide of Comparative Example 2, the end point when BCS used 0.08g and the polyimide of Comparative Example 3 was 0.76g.

The results of Examples 4 to 8 and Comparative Examples 1 to 3 were summarized in Table 1C-.

According to the above result, it was confirmed that the polyimide using the diamine of this invention has much larger mixing tolerance of butyl cellosolve than the polyimide using the comparative diamine.

"Preparation and evaluation of the liquid-crystal aligning agent of this invention"

Example 9

p-PDA (1.46 g, 13.5 mmol) and PBCH5DAB (0.65 g, 1.50 mmol) as side chain diamines are mixed in NMP (20.0 g), CBDA (2.85 g, 14.5 mmol) and NMP (24.7 g) Was added and reacted at 25 degreeC for 5 hours, and the polyamic-acid solution was obtained. The liquid-crystal aligning agent (1) was obtained by adding NMP (24.0g) and BCS (16.0g) to the obtained polyamic-acid solution (40.0g), and stirring for 1 hour. Abnormalities such as haze and precipitation were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was dissolved uniformly.

The liquid-crystal aligning agent (1) obtained above was spin-coated to the glass substrate in which the ITO electrode was formed, and it dried for 5 minutes on an 80 degreeC hotplate, and baked at 230 degreeC hot-air circulation type oven for 1 hour, and was 100 nm in thickness. A polyimide membrane was produced.

The board | substrate with which the liquid crystal aligning film was formed by rubbing this polyimide film surface on the conditions of the roll rotation speed 1000rpm, the roll advancing speed 50mm / sec, and the press amount 0.3mm using the rubbing apparatus of 120 mm of roll diameters, and a liquid crystal aligning film. Got.

Two board | substrates with this liquid crystal aligning film were prepared, the 50-micrometer spacer was sandwiched between the liquid crystal aligning film surfaces inside, and it was combined so that the rubbing direction might be reversed, and the surrounding was bonded by the sealing compound, and the empty cell was produced. . Liquid crystal MLC-2003 (made by Merck Japan) was injected into this empty cell by the pressure reduction injection method, the injection hole was sealed, and the nematic liquid crystal cell of antiparallel orientation was obtained.

The pretilt angle of the liquid crystal cell manufactured by the above was measured at room temperature using the tilt measuring apparatus (Model PAS-301 made from ELSICON). As a result, the pretilt angle was 81.8 degrees and it was 84.2 degrees after heat-processing a liquid crystal cell at 120 degreeC for 1 hour.

Moreover, when the liquid crystal cell manufactured similarly to the above except the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

<Example 10>

p-PDA (1.39 g, 12.8 mmol) and PBCH7DAB (0.66 g, 1.43 mmol) as side chain diamines are mixed in NMP (19.2 g), CBDA (2.71 g, 13.8 mmol) and NMP (23.5 g) Was added and reacted at 25 degreeC for 5 hours, and the polyamic-acid solution was obtained. The liquid-crystal aligning agent (2) was obtained by adding NMP (23.8g) and BCS (16.0g) to the obtained polyamic-acid solution (40.0g), and stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the liquid-crystal aligning agent (2) obtained above, the nematic liquid crystal cell of antiparallel orientation was produced like Example 9, and the pretilt angle was measured. As a result, the pretilt angle was 83.4 degrees and after heat-processing a liquid crystal cell for 1 hour at 120 degreeC, it was 85.1 degrees.

Moreover, when the liquid crystal cell manufactured similarly to the above except the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

<Comparative Example 4>

p-PDA (1.56 g, 14.4 mmol) and PCH7DAB (0.61 g, 1.60 mmol) as side chain diamines were mixed in NMP (22.0 g), CBDA (3.04 g, 15.5 mmol) and NMP (24.9 g) Was added and reacted at 25 degreeC for 5 hours, and the polyamic-acid solution was obtained. The liquid-crystal aligning agent (3) was obtained by adding NMP (24.0g) and BCS (16.0g) to the obtained polyamic-acid solution (40.0g), and stirring for 1 hour. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the liquid-crystal aligning agent (3) obtained above, the nematic liquid crystal cell of antiparallel orientation was produced like Example 9, and the pretilt angle was measured. As a result, the pretilt angle was 22.2 degrees and it was 22.8 degrees after heat-processing a liquid crystal cell at 120 degreeC for 1 hour.

Moreover, when the liquid crystal cell manufactured similarly to the above except the rubbing process was observed with the polarization microscope, it was confirmed that the orientation of a liquid crystal is nonuniform and is not orientated vertically.

The results of Example 9, Example 10 and comparison 4 are summarized in Table 2.

According to the above result, it was confirmed that the polyamic acid using the diamine of this invention can express a large pretilt angle with the introduction amount less than the polyamic acid using the comparative diamine.

<Example 11>

NMP (28.8g) was added to the polyimide powder (A) obtained in Example 4, and (4.00g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (2.68g) and BCS (29.3g) were added to this solution, and the liquid-crystal aligning agent (4) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

The liquid-crystal aligning agent (4) obtained above was spin-coated to the glass substrate in which the ITO electrode was formed, and it dried for 5 minutes on an 80 degreeC hotplate, and baked at 210 degreeC hot-air circulation type oven for 1 hour, and has a film thickness of 100 nm. Polyimide membrane was prepared.

The board | substrate with this liquid crystal aligning film was rubbed with a rayon cloth on condition of a roll rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.3 mm using the rubbing device of 120 mm of roll diameters, and the liquid crystal aligning film was formed. A substrate was obtained.

After preparing two board | substrates with this liquid crystal aligning film, spread | dispersing a 6 micrometers bead spacer on the one liquid crystal aligning film surface, a sealing compound is printed from it, and another board | substrate has a liquid crystal aligning film surface inside. The adhesive was cured so that the rubbing direction was reversed, and then the sealing agent was cured to prepare an empty cell. Liquid crystal MLC-6608 (made by Merck Japan) was injected into this empty cell by the pressure reduction injection method, the injection hole was sealed, and the nematic liquid crystal cell of antiparallel orientation was obtained.

The pretilt angle of the liquid crystal cell manufactured by the above was measured at room temperature using the tilt measuring apparatus (Model PAS-301 made from ELSICON). As a result, the pretilt angle was 47.1 degrees and it was 54.8 degrees after heat-processing a liquid crystal cell at 120 degreeC for 1 hour.

Moreover, when the liquid crystal cell manufactured similarly to the above except the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

<Example 12>

NMP (26.3g) was added to the polyimide powder (B) obtained in Example 5, and (4.00g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (6.40g) and BCS (30.0g) were added to this solution, and the liquid-crystal aligning agent (5) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

The process similar to Example 11 was performed using the liquid-crystal aligning agent (5) obtained above, and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by operation similar to Example 11, it was 15.3 degrees after heat processing at 54.6 degrees and 120 degreeC for 1 hour at room temperature.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

Example 13

NMP (22.0g) was added to the polyimide powder (C) obtained in Example 6, and (3.00g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (2.50g) and BCS (22.5g) were added to this solution, and the liquid-crystal aligning agent (6) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

The process similar to Example 11 was performed using the liquid-crystal aligning agent (6) obtained above, and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, it was 86.2 degrees after heat processing at 84.3 degrees and 120 degreeC for 1 hour at room temperature. Moreover, when the liquid crystal cell after heat processing at room temperature and 1 hour was observed with the polarization microscope, the liquid crystal was orientated uniformly, and also the heat treatment was uniformly aligned.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

<Example 14>

PBCH5DAB (3.0 g, 6.90 mmol) is mixed in NMP (22.0 g) as BODA (4.32 g, 17.3 mmol), p-PDA (1.74 g, 16.1 mmol), and side chain diamine, and it is 5 hours at 40 degreeC. After reacting, CBDA (1.01 g, 5.15 mmol) and NMP (18.0 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic-acid solution (30.0g), and it diluted to 6 mass%, acetic anhydride (3.75g) and pyridine (2.90g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (400 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (I). The imidation ratio of this polyimide was 45%, the number average molecular weight was 15,900 and the weight average molecular weight was 40,800.

NMP (28.8g) was added to this polyimide powder (I) (4.00g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (2.69g) and BCS (29.0g) were added to this solution, and the liquid-crystal aligning agent (7) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

The same process as Example 11 was performed using the liquid-crystal aligning agent (7) obtained above, and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, it was 87.3 degrees after heat processing at 85.6 degrees and 120 degreeC for 1 hour at room temperature. Moreover, when the liquid crystal cell after heat processing at room temperature and 1 hour was observed with the polarization microscope, the liquid crystal was orientated uniformly, and also the heat treatment was orientated uniformly.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

<Example 15>

PBCH5DAB (2.04 g, 4.69 mmol) was mixed in NMP (23.0 g) as BODA (4.41 g, 17.6 mmol), DBA (2.86 g, 18.8 mmol) and side chain diamine, and reacted at 80 degreeC for 5 hours. Thereafter, CBDA (1.01 g, 5.15 mmol) and NMP (18.0 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution.

NMP was added to this polyamic-acid solution (30.0g), and it diluted to 6 mass%, acetic anhydride (3.79g) and pyridine (2.94g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (408 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (J). The imidation ratio of this polyimide was 40%, the number average molecular weight was 17,300 and the weight average molecular weight was 46,800.

NMP (26.3g) was added to this polyimide powder (J) (4.00g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (6.40g) and BCS (30.0g) were added to this solution, and the liquid-crystal aligning agent (8) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

The same process as Example 11 was performed using the liquid-crystal aligning agent (8) obtained above, and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, it was 88.6 degrees after heat processing at 87.2 degrees and 120 degreeC for 1 hour at room temperature. Moreover, when the liquid crystal cell after heat processing at room temperature and 1 hour was observed with the polarization microscope, the liquid crystal was orientated uniformly, and also the heat treatment was orientated uniformly.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

<Example 16>

PBCH5DAB (5.74 g, 13.2 mmol) was mixed in NMP (45.0 g) as BODA (8.26 g, 33.0 mmol), DBA (4.69 g, 30.8 mmol), and a side chain diamine, and reacted at 80 degreeC for 5 hours. Thereafter, CBDA (2.10 g, 10.7 mmol) and NMP (38.0 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic-acid solution (20.0g), and it diluted to 6 mass%, acetic anhydride (2.16g) and pyridine (1.67g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (247 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (K). The imidation ratio of this polyimide was 45%, the number average molecular weight was 19,100 and the weight average molecular weight was 50,800.

NMP (16.0g) was added to this polyimide powder (K) (3.30g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (8.20g) and BCS (27.5g) were added to this solution, and the liquid-crystal aligning agent (9) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

The process similar to Example 11 was performed using the liquid-crystal aligning agent (9) obtained above, and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, it was 89.0 degrees after heat processing at 88.5 degrees and 120 degreeC for 1 hour at room temperature. Moreover, when the liquid crystal cell after heat processing at room temperature and 1 hour was observed with the polarization microscope, the liquid crystal was orientated uniformly, and also the heat treatment was orientated uniformly.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

<Example 17>

NMP was added to the polyamic acid solution (20.0 g) obtained in Example 16 and diluted to 6 mass%, acetic anhydride (4.31 g) and pyridine (3.34 g) were added as an imidation catalyst, and it reacted at 90 degreeC for 3.5 hours. I was. This reaction solution was poured into methanol (260 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (L). The imidation ratio of this polyimide was 80%, the number average molecular weight was 15,200 and the weight average molecular weight was 45,500.

NMP (16.1g) was added to this polyimide powder (L) (3.30g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (8.24g) and BCS (27.6g) were added to this solution, and the liquid-crystal aligning agent (10) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the liquid-crystal aligning agent (10) obtained above, the same process as Example 11 was performed, and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, it was 88.3 ° after heat treatment at 87.7 ° and 120 ° C. for 1 hour at room temperature. Moreover, when the liquid crystal cell after heat processing at room temperature and 1 hour was observed with the polarization microscope, the liquid crystal was orientated uniformly, and also the heat treatment was orientated uniformly.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

Example 18

NMP was added to the polyamic acid solution (20.0 g) obtained in Example 16, and diluted to 6 mass%, acetic anhydride (4.31 g) and triethylamine (1.52 g) were added as an imidation catalyst, and 4 was added at 100 degreeC. The reaction was time. Oxalic acid (1.90 g) was added to this reaction solution, and the mixture was neutralized. Then, the precipitate was added to methanol (253 ml) and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (M). The imidation ratio of this polyimide was 98%, the number average molecular weight was 19,200 and the weight average molecular weight was 61,500.

NMP (15.6g) is added to this polyimide powder (M) (3.2g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (12.6g) and BCS (21.2g) were added to this solution, and the liquid-crystal aligning agent (11) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

The same process as Example 11 was performed using the liquid-crystal aligning agent (11) obtained above, and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, it was 88.2 ° after heat treatment at 87.5 ° and 120 ° C. for 1 hour at room temperature. Moreover, when the liquid crystal cell after heat processing at room temperature and 1 hour was observed with the polarization microscope, the liquid crystal was orientated uniformly, and also the heat treatment was orientated uniformly.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

Example 19

DBA (1.05 g, 6.90 mmol), DAA (1.87 g, 9.20 mmol), PBCH5DAB (3.0 g, 6.90 mmol) were mixed in NMP (20.0 g) as side chain diamine, and CBDA (4.47 g, 22.8 m) Mol) and NMP (21.5g) were added, and it reacted at 25 degreeC for 10 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic-acid solution (20.0g), and it diluted to 6 mass%, acetic anhydride (4.51g) and pyridine (3.50g) were added as imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (261 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (N). The imidation ratio of this polyimide was 98%, the number average molecular weight was 16,800, and the weight average molecular weight was 47,900.

NMP (20.5g) was added to this polyimide powder (N) (3.10g), and it stirred for 20 hours and made it melt | dissolve at 50 degreeC. NMP (13.2g) and BCS (24.5g) were added to this solution, and the liquid-crystal aligning agent (12) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the liquid-crystal aligning agent (12) obtained above, the same process as in Example 11 was performed to obtain a nematic liquid crystal cell having an antiparallel orientation subjected to a rubbing treatment. When the pretilt angle of this liquid crystal cell was measured by operation similar to Example 11, it was 87.5 degrees after heat processing at 86.7 degrees and 120 degreeC for 1 hour at room temperature. Moreover, when the liquid crystal cell after heat processing at room temperature and 1 hour was observed with the polarization microscope, the liquid crystal was orientated uniformly, and also the heat treatment was orientated uniformly.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

Example 20

NMP (14.3g) was added to the polyimide powder (D) obtained in Example 7, (2.14g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (3.16g) and BCS (16.1g) were added to this solution, and the liquid-crystal aligning agent (13) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

The process similar to Example 11 was performed using the liquid-crystal aligning agent (13) obtained above, and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. The pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, and it was 77.7 ° after heat treatment at 76.5 ° and 120 ° C. for 1 hour at room temperature.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

Example 21

NMP (21.8g) was added to the polyimide powder (E) obtained in Example 8, and (3.00g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (2.51g) and BCS (22.5g) were added to this solution, and the liquid-crystal aligning agent (14) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the liquid-crystal aligning agent (14) obtained above, the same process as Example 11 was performed, and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, it was 87.8 ° after heat treatment at 86.5 ° and 120 ° C. for 1 hour at room temperature. Moreover, when the liquid crystal cell after heat processing at room temperature and 1 hour was observed with the polarization microscope, the liquid crystal was orientated uniformly, and also the heat treatment was orientated uniformly.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

<Example 22>

BOB (8.34 g, 33.3 mmol), DBA (4.74 g, 31.2 mmol) and PBCH7DAB (6.15 g, 13.3 mmol) were mixed in NMP (45.5 g) as side chain diamine, and made to react at 80 degreeC for 5 hours. After that, CBDA (2.12 g, 10.8 mmol) and NMP (38.0 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic-acid solution (20.0g), and it diluted to 6 mass%, acetic anhydride (4.30g) and pyridine (3.30g) were added as imidation catalyst, and it reacted at 90 degreeC for 3.5 hours. This reaction solution was poured into methanol (300 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (O). The imidation ratio of this polyimide was 80%, the number average molecular weight was 16,100 and the weight average molecular weight was 48,900.

NMP (16.5g) was added to this polyimide powder (O) (3.29g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (8.25g) and BCS (27.5g) were added to this solution, and the liquid-crystal aligning agent (15) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the liquid-crystal aligning agent (15) obtained above, the same process as Example 11 was performed, and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, it was 89.1 ° after heat treatment at 88.3 ° and 120 ° C. for 1 hour at room temperature. Moreover, when the liquid crystal cell after heat processing at room temperature and 1 hour was observed with the polarization microscope, the liquid crystal was orientated uniformly, and also the heat treatment was orientated uniformly.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

Comparative Example 5

NMP (21.1g) was added to the polyimide powder (F) obtained by the comparative example 1, (3.15g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. When NMP (1.95g) and BCS (26.3g) were added to this solution, and it stirred for 1 hour, precipitation of the resin component occurred and the liquid-crystal aligning agent was not able to be obtained. Therefore, the liquid crystal cell could not be manufactured.

Comparative Example 6

NMP (24.4g) was added to the polyimide powder (F) obtained by the comparative example 1, and (3.65g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. When NMP (5.35g) and BCS (27.4g) were added to this solution, and it stirred for 1 hour, precipitation of the resin component occurred and the liquid-crystal aligning agent was not able to be obtained. Therefore, the liquid crystal cell could not be manufactured.

Comparative Example 7

NMP (20.7g) was added to the polyimide powder (F) obtained by the comparative example 1, and (3.10g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (27.0g) and BCS (11.2g) were added to this solution, and the liquid-crystal aligning agent (16) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the liquid-crystal aligning agent (16) obtained above, spin-coating to the glass substrate in which the ITO electrode was formed, and drying for 5 minutes on a 80 degreeC hotplate, baking for 1 hour in 210 degreeC hot-air circulation type oven, and film thickness A polyimide film of 100 nm was prepared. When the coating film surface was confirmed, many pinholes were observed. Using the board | substrate with which this liquid crystal aligning film was formed, the same process as Example 11 was performed and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, it was 80.1 degrees after heat processing at 76.4 degrees and 120 degreeC for 1 hour at room temperature. However, a large deviation of the pretilt angle was observed in the liquid crystal cell plane. Moreover, when these liquid crystal cells after heat processing at room temperature and 1 hour were observed with the polarization microscope, the orientation defect of the liquid crystal was observed along the pinhole.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was orientated vertically, and the light leakage part was observed locally along the pinhole.

<Comparative Example 8>

BODA (16.9 g, 67.5 mmol), p-PDA (6.80 g, 62.9 mmol), and PCH7DAB (10.3 g, 27.1 mmol) as side chain diamines were mixed in NMP (100.1 g) and 5 hours at 40 ° C. After reacting, CBDA (4.10 g, 20.9 mmol) and NMP (52.2 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution. After adding NMP to the obtained polyamic-acid solution (130.3g) and diluting to 6 mass%, acetic anhydride (15.6g) and pyridine (12.1g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (1600 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (P). The imidation ratio of this polyimide was 54%, the number average molecular weight was 18,300 and the weight average molecular weight was 45,300.

NMP (23.5g) was added to this polyimide powder (P) (3.20g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (2.63g) and BCS (24.0g) were added to this solution, and the liquid-crystal aligning agent (17) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

The same process as Example 11 was performed using the liquid-crystal aligning agent (17) obtained above, and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, it was 81.5 ° after heat treatment at 78.7 ° and 120 ° C. for 1 hour at room temperature. Moreover, when the liquid crystal cell after heat-processing at room temperature and 1 hour was observed with the polarization microscope, the liquid crystal was orientated uniformly, Example 14 Moreover, the light leakage by the inclination of the liquid crystal compared with Example 21 was observed.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.

Comparative Example 9

PCH7DAB (15.2 g, 39.9 mmol) is mixed in NMP (100.3 g) as BODA (15.0 g, 60.0 mmol), p-PDA (4.30 g, 39.8 mmol) and side chain diamine, and it is 5 hours at 40 degreeC. After reacting, CBDA (3.80 g, 19.4 mmol) and NMP (53.2 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution. After adding NMP to the obtained polyamic-acid solution (130.3g) and diluting to 6 mass%, acetic anhydride (13.9g) and pyridine (10.8g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (1600 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (Q). The imidation ratio of this polyimide was 55%, the number average molecular weight was 17,500 and the weight average molecular weight was 42,700.

NMP (23.1g) was added to this polyimide powder (Q) (3.15g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (2.65g) and BCS (23.6g) were added to this solution, and the liquid-crystal aligning agent (18) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the liquid-crystal aligning agent (18) obtained above, spin-coating to the glass substrate in which the ITO electrode was formed, and drying for 5 minutes on a 80 degreeC hotplate, baking for 1 hour in 210 degreeC hot-air circulation type oven, and film thickness 100 nm polyimide membrane was manufactured. When the coating film surface was confirmed, the pinhole was observed. Using the board | substrate with which this liquid crystal aligning film was formed, the same process as Example 11 was performed and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, it was 88.7 ° after heat treatment at 87.7 ° and 120 ° C. for 1 hour at room temperature. However, the variation of the pretilt angle was observed in the liquid crystal cell plane. Moreover, when these liquid crystal cells after heat processing at room temperature and 1 hour were observed with the polarization microscope, the orientation defect of the liquid crystal was observed along the pinhole.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was orientated vertically, and the light leakage part was observed locally along the pinhole.

Comparative Example 10

NMP (20.4g) was added to the polyimide powder (H) obtained by the comparative example 3, and (3.05g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (1.89g) and BCS (25.5g) were added to this solution, and the liquid-crystal aligning agent (19) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the liquid-crystal aligning agent 19 obtained above, spin-coating to the glass substrate in which the ITO electrode was formed, and drying for 5 minutes on a 80 degreeC hotplate, baking for 1 hour in 210 degreeC hot-air circulation type oven, and film thickness 100 nm polyimide membrane was manufactured. When the coating film surface was confirmed, many pinholes were observed. Using the board | substrate with which this liquid crystal aligning film was formed, the same process as Example 11 was performed and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by operation similar to Example 11, it was 8.60 degrees after heat processing at 11.2 degreeC and 120 degreeC for 1 hour at room temperature. However, a large deviation of the pretilt angle was observed in the liquid crystal cell plane. Moreover, when these liquid crystal cells after heat processing at room temperature and 1 hour were observed with the polarization microscope, the orientation defect of the liquid crystal was observed along the pinhole.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was orientated vertically, and the light leakage part was observed locally along the pinhole.

Comparative Example 11

NMP (10.4g) was added to the polyimide powder (H) obtained by the comparative example 3, and (1.56g), and it stirred for 40 hours and made it melt | dissolve at 80 degreeC. NMP (2.30g) and BCS (11.7g) were added to this solution, and the liquid-crystal aligning agent (20) was obtained by stirring for 1 hour. Abnormalities, such as turbidity and precipitation, were not observed by this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the liquid-crystal aligning agent (20) obtained above, spin-coating to the glass substrate in which the ITO electrode was formed, and drying for 5 minutes on a 80 degreeC hotplate, baking for 1 hour in 210 degreeC hot-air circulation type oven, and film thickness 100 nm polyimide membrane was manufactured. When the coating film surface was confirmed, many pinholes were observed. Using the board | substrate with which this liquid crystal aligning film was formed, the same process as Example 11 was performed and the nematic liquid crystal cell of the antiparallel orientation which carried out the rubbing process was obtained. When the pretilt angle of this liquid crystal cell was measured by the same operation as in Example 11, it was 8.50 ° after heat treatment at 10.9 ° and 120 ° C. for 1 hour at room temperature. However, a large deviation of the pretilt angle was observed in the plane of the liquid crystal cell. Moreover, when these liquid crystal cells after heat processing at room temperature and 1 hour were observed with the polarization microscope, the orientation defect of the liquid crystal was observed along the pinhole.

Moreover, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, it was confirmed that the liquid crystal was orientated vertically, and the light leakage part was observed locally along the pinhole.

In addition, when the liquid crystal cell manufactured similarly to Example 11 except for the rubbing process was observed with the polarization microscope, the liquid crystal was not vertically aligned and the light leakage part was observed locally.

<Printability Test>

Printing was performed using the liquid-crystal aligning agent obtained in Examples 11-22 and Comparative Examples 7-11. As a printing press, a simple press (S15 type) manufactured by Nippon Photo Printing Co., Ltd. was used. Printing is performed on a cleaned chromium vapor deposition substrate with a printing area of 8 × 8 cm, phosphorus 0.2 mm, 5 substrates to be discarded after use, time 90 seconds from printing to predrying, preliminary drying temperature of 70 ° C., 5 minutes. Was carried out.

Pinhole identification was visually observed under a sodium lamp.

Film thickness nonuniformity and edge linearity were confirmed using an optical microscope.

The result of Examples 11-22 and Comparative Examples 7-11 was put together in Table 3 and Table 4.

From the result of Examples 11-22 and Comparative Examples 7-11, the polyimide using the diamine of this invention was able to express a high pretilt angle with the introduction amount less than the polyimide using the diamine of comparative. In particular, from the comparison between Example 14 and Comparative Example 8, in Comparative Example 8, light leakage due to inclination of the liquid crystal was observed when the rubbing treatment was performed, compared with Example 14 using the diamine of the present invention. That is, the polyimide using the diamine of this invention can express high pretilt angle, even if it carries out a rubbing process. Although the polyimide using the diamine of this invention has a high imidation ratio, even if it increased the mixing tolerance of the butyl cellosolve which is a poor solvent, precipitation of resin was not observed. As a result, it was confirmed that the liquid-crystal aligning agent obtained using the diamine of this invention can form a uniform thin film by a normal coating means.

* 1: Use ratio of side chain diamine in all the diamine used for the synthesis | combination of a polymer.

* 2: Mass of the BCS mixing end point.

* 3: Use ratio of the side chain diamine in all the diamine used for the synthesis | combination of a polymer.

* 4: Use ratio of side chain diamine in all the diamine used for the synthesis | combination of a polymer.

* 5: Use ratio of BCS to the whole solvent in a liquid-crystal aligning agent.

* 6: Evaluation is impossible by precipitation of the resin component.

* 7: Poor orientation due to pin hole.

* 8: There is light leakage.

When used as a raw material of the polymer constituting the liquid crystal alignment film, the diamine of the present invention has the effect of increasing the pretilt angle of the liquid crystal, and can align the liquid crystal vertically even at a small use ratio, Even when a lot of poor solvents are used, precipitation does not occur easily. Thereby, since the liquid-crystal aligning agent of this invention can form a uniform thin film by a conventional coating means, and can manufacture the liquid crystal aligning film which gives a large pretilt angle to a liquid crystal, TN element, STN element, TFT liquid crystal Element, and furthermore, it is useful for a vertical alignment liquid crystal display element.

In addition, the JP Patent application 2007-077846, the claim, and all the content of the abstract for which it applied on March 23, 2007 are referred here, and it takes in as an indication of the specification of this invention.

Claims (10)

Diamine represented by following formula (1). [Formula 1]

(In formula (1), R <_1> is phenylene or cyclohexylene, R <_2> is a C3-C12 alkyl group, a C3-C12 fluoroalkyl group, a C3-C12 alkoxy group, or C3-C12. Fluoroalkoxy group) The method of claim 1, In formula (1), diamine whose R <_1> is ₁ , 4- phenylene or ₁ , 4- cyclohexylene. The method according to claim 1 or 2, Diamine represented by following formula (2-1). [Formula 2]

(In Formula (2-1), n is an integer of 2-11, and the cis-trans isomer of 1, 4- cyclohexylene is a trans isomer, respectively.) The method according to claim 1 or 2, Diamine represented by following formula (2-2). [Formula 3]

(In formula (2-2), n is an integer of 2-11, and the cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer.) The polyamic acid obtained by making the diamine component containing the diamine of any one of Claims 1-4, and tetracarboxylic dianhydride react, or the polyimide obtained by dehydrating and ring-closing the polyamic acid. The method of claim 5, wherein The polyamic acid or polyimide whose 10 mol% or more in a diamine component is the diamine in any one of Claims 1-4. The liquid-crystal aligning agent containing at least 1 sort (s) of compound in the polyamic acid and polyimide of Claim 5 or 6. The method of claim 7, wherein The liquid-crystal aligning agent containing the organic solvent which contains 5-60 mass% of poor solvents. The liquid crystal aligning film obtained using the liquid-crystal aligning agent of Claim 7 or 8. The liquid crystal display element which has a liquid crystal aligning film of Claim 9.