KR20100105460A - Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display device, polyamic acid, imide polymer and diamine compound - Google Patents

Abstract

PURPOSE: A liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display device, and a compound containing polyamic acid, an imidized polymer, and a diamine compound are provided to perform a long time back light irradiation without decreasing the voltage holding rate. CONSTITUTION: A liquid crystal alignment agent contains more than one polymer selected form the group consisting polyamic acid and an imidized polymer. The polyamic acid is obtained by reacting tetra carboxylic dianhydride and diamine. The diamine contains a compound A with two amino groups. The compound A includes a cyclic amine structure substituted with two hydrocarbon groups, or a phenol structure.

Description

LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNING FILM, LIQUID CRYSTAL DISPLAY DEVICE, POLYAMIC ACID, IMIDE POLYMER AND DIAMINE COMPOUND}

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. In more detail, the liquid crystal aligning agent which can form the liquid crystal aligning film which is excellent in reliability, and the fall of the voltage retention by light is few, and the excellent liquid crystal display element which has little fall of the voltage retention by light, and does not deteriorate display quality. It is about.

A liquid crystal display element can be classified into each mode shown below according to the electrode structure and the physical property of the liquid crystal molecule to be used.

A liquid crystal alignment film is formed on the surface of the substrate on which the transparent conductive film is provided to form a substrate for a liquid crystal display device, and two sheets thereof are opposed to each other to form a layer of nematic liquid crystal having positive dielectric anisotropy in the gap to form a cell having a sandwich structure. And a TN type liquid crystal display element (Patent Document 1) having a so-called TN (Twisted Nematic) type liquid crystal cell in which the long axis of the liquid crystal molecules is continuously twisted by 90 ° from one substrate to the other substrate (Patent Document 1) and the TN type liquid crystal display element. Compared with the above, STN (Super Twisted Nematic) type liquid crystal display device (Patent Document 2) and the like, which can realize a high duty ratio, are mentioned.

Further, in the same counter electrode arrangement as that of the TN type liquid crystal display element, a VA (Vertical Alignment) type display element in which a layer of a nematic liquid crystal having negative dielectric anisotropy is injected into the electrode gap, and the liquid crystal is oriented almost perpendicular to the substrate. Can be mentioned. The VA display element is high contrast and can be a display element with a large area (Patent Document 3).

On the other hand, by arranging the electrode pairs in a single comb surface, the IPS (In-Plane Switching) type liquid crystal display elements (Patent Documents 4 and 5) in which the driving direction of the liquid crystal at the time of electric field application is only the in-plane direction of the substrate, By changing the electrode structure of the IPS type, a FFS (Fringe Field Switching) type liquid crystal display element (Patent Document 6) has been developed in which the aperture ratio of the display element portion is increased to improve luminance, and each has excellent viewing angle characteristics.

In addition, an OCB (Optical Compensated Bend) type liquid crystal display device (Patent Document 7) and the like having low visual dependence and excellent high-speed response of an image screen have been developed.

As a material of the liquid crystal aligning film in these various liquid crystal display elements, resin materials, such as a polyamic acid, a polyimide, a polyamide, polyester, are known, Especially the liquid crystal aligning film containing a polyamic acid or a polyimide has heat resistance, mechanical strength, a liquid crystal It is used for many liquid crystal display elements because it is excellent in affinity with etc. (patent document 8).

In such a liquid crystal aligning agent, performance without the functional fall by light irradiation in recent years has become more demanding than before. The circumstances are as follows.

In the manufacturing process of a liquid crystal display element, what started to be used from a viewpoint of process shortening and a yield improvement is a liquid crystal dropping method, ie, an ODF (One Drop Fill) system. Unlike the conventional method of injecting a liquid crystal into an empty liquid crystal cell assembled using a thermosetting sealant in advance, the ODF method applies an ultraviolet photocurable sealant to a required location of one substrate to which a liquid crystal alignment film is applied. After dropping a liquid crystal in a required location and bonding the other board | substrate, ultraviolet light is irradiated to the whole surface, hardening a sealing agent, and manufacturing a liquid crystal cell. Ultraviolet light irradiated at this time is generally stronger than several joules (J) per cm 2. That is, in the liquid crystal display element manufacturing process, a liquid crystal aligning film is exposed to this strong ultraviolet light with a liquid crystal.

Focusing on the change in the use of the liquid crystal display device, compared to notebook computers, monitor displays, etc., which are the main uses of the conventional liquid crystal display devices, liquid crystal televisions, which have recently been widely used, are required to have a long repurchase cycle and have a long service life. Exposure to back light irradiation In addition, in liquid crystal display devices for liquid crystal projector applications, which are not only used for business purposes but also recently as home theaters, light sources such as metal halide lamps with very high irradiation intensity are used. In addition, liquid crystal display elements for mobile devices such as mobile phones and car-mounted car navigation systems are exposed to sunlight containing strong ultraviolet rays, and it is necessary to increase the brightness of the backlight in order to improve visibility.

As described above, the liquid crystal display device has been exposed to harsh environments that were not previously considered, such as high-intensity light irradiation, long-time driving, etc., due to improvements in its manufacturing process, versatility, and the like.

It is pointed out that the conventionally known liquid crystal aligning film lacks resistance to such a harsh environment.

Japanese Patent Laid-Open No. 4-153622 Japanese Patent Publication No. 60-107020 Japanese Patent Laid-Open No. 11-258605 Japanese Patent Laid-Open No. 56-91277 US Patent No. 5,928,733 Japanese Patent Laid-Open No. 2002-082357 Japanese Patent Publication No. 9-105957 Japanese Patent Laid-Open No. 62-165628 Japanese Patent Publication No. 6-222366 Japanese Patent Laid-Open No. 6-281937 Japanese Patent Publication No. 5-107544

This invention is made | formed in view of the said situation, and the objective is to provide the liquid crystal aligning agent which can form the liquid crystal aligning film excellent in reliability, with little fall of the voltage retention by light irradiation.

Another object of the present invention is to provide an excellent liquid crystal display device in which the reduction in voltage retention due to light is small and the display quality is not degraded.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are, firstly,

It is a liquid crystal aligning agent containing 1 or more types of polymers chosen from the group which consists of a polyamic acid obtained by making tetracarboxylic dianhydride and diamine react, and its imidation polymer,

The diamine,

A cyclic amine structure in which two carbon atoms adjacent to a nitrogen atom are each substituted by an oxygen atom, a sulfur atom, a carbonyl group or two hydrocarbon groups which may be interrupted by an ester bond, or

A phenol structure in which at least one carbon in the ortho position relative to the hydroxyl group is substituted by an oxygen atom, a sulfur atom, a carbonyl group or a hydrocarbon group which may be interrupted by an ester bond,

It is achieved by the said liquid crystal aligning agent containing the compound (A) which has two amino groups.

The above objects and advantages of the present invention are second,

It is achieved by the liquid crystal display element provided with the liquid crystal aligning film formed from said liquid crystal aligning agent.

The liquid crystal aligning agent of this invention can form the liquid crystal aligning film which voltage retention does not fall even if it irradiates for a long time back light. The liquid crystal display element of this invention provided with the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention can display a high quality, and display performance does not deteriorate even if it drive | operates for a long time. Therefore, the liquid crystal display device of the present invention can be effectively applied to various devices, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a portable information terminal, a digital camera, a mobile phone, various It can be used suitably for display apparatuses, such as a monitor and a liquid crystal television.

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

The liquid crystal aligning agent of this invention contains 1 or more types of polymers chosen from the group which consists of a polyamic acid obtained by making tetracarboxylic dianhydride and the diamine containing a compound (A) mentioned above, and its imidation polymer. do.

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, butane tetracarboxylic dianhydride etc .;

As the alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a , 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro -3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6 -Dianhydrides, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 3,5: 6- dianhydrides, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] Undecane-3,5,8,10-tetraon and the like;

As aromatic tetracarboxylic dianhydride, not only a pyromellitic dianhydride etc. can be mentioned, respectively, but the tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2009-66252 can be used, for example.

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, it is preferable to contain alicyclic tetracarboxylic dianhydride among these, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, and 1, It is more preferable to contain 1 or more types chosen from the group which consists of 2,3, 4- cyclobutane tetracarboxylic dianhydride, It is especially preferable to contain 2,3,5- tricarboxycyclopentyl acetic dianhydride. Do.

As tetracarboxylic dianhydride used for synthesizing the polyamic acid, the group consisting of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride It is preferable to contain 10 mol% or more with respect to all the tetracarboxylic dianhydrides, More preferably, it contains 20 mol% or more, and 2,3,5-tricarboxycyclopentyl acetic dianhydride is selected from the above. And one or more selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

[Diamine]

The diamine used for the synthesis of the polyamic acid in the present invention,

A cyclic amine structure in which two carbon atoms adjacent to a nitrogen atom are each substituted by an oxygen atom, a sulfur atom, a carbonyl group or two hydrocarbon groups which may be interrupted by an ester bond, or

A phenol structure in which at least one carbon in the ortho position relative to the hydroxyl group is substituted by an oxygen atom, a sulfur atom, a carbonyl group or a hydrocarbon group which may be interrupted by an ester bond,

It includes the compound (A) which has two amino groups.

When the said compound (A) has a cyclic amine structure, as a hydrocarbon group substituted by the carbon atom adjacent to the nitrogen atom of the said cyclic amine, it is a C1-C6 alkyl group and a C6-C20 aryl group, for example. And an aralkyl group having 7 to 20 carbon atoms. However, these hydrocarbon groups may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond in the middle.

On the other hand, when the said compound (A) has a phenol structure, as a hydrocarbon group substituted by the carbon of an ortho position with respect to a hydroxyl group, a C4-C16 alkyl group is mentioned, for example. However, this alkyl group may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond in the middle.

As such a compound (A), the compound represented by following formula (A2) as a compound which has a phenol structure is mentioned, respectively, as having a cyclic amine structure, respectively.

[Formula A1]

[Formula A2]

(In formula A1, R <^I> is a hydrogen atom, a C1-C6 alkyl group, a C6-C20 aromatic group, a C7-13 aralkyl group, or a 1, 3- dioxobutyl group,

X ¹ is a single bond, a carbonyl group or * -CONH- (wherein the bond to which "*" is attached is combined with a piperidine ring),

R ^II to R ^V are each an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms, provided that the benzene ring having the aryl group and aralkyl group has a formyl group or 1 to 4 carbon atoms. May be substituted with an alkoxyl group),

X ² to X ⁵ each represent a single bond, a carbonyl group, * -CH ₂ -CO- or * -CH ₂ -CH (OH)-(wherein the bond to which "*" is attached is combined with a piperidine ring),

In formula (A2), R ^VI is an alkyl group having 4 to 16 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond in the middle, and R ^VII is a hydrogen atom or an oxygen atom, a sulfur atom, a carbonyl group in the middle Or an alkyl group having 1 to 16 carbon atoms which may be interrupted by an ester bond,

X ⁶ in the formula A1 and A2 are each an oxygen atom, * -OCO-, a group represented by the formula (X ⁶ -1)

(Formula (X ⁶ -1) of, a is an integer from 1 to 12, b is an integer of from 0 to 5)

(However, in the above description, the bond group with “*” is bonded to the piperidine ring in the formula (A1) and the benzene ring having a hydroxyl group in the formula (A2), respectively), and is a methylene group or an alkylene group having 2 to 6 carbon atoms.)

Examples of the alkyl group having 1 to 6 carbon atoms of R ^I in the general formula (A1) include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-butyl group, i-butyl group, t- Butyl group etc. are mentioned.

Examples of the aromatic group having 6 to 20 carbon atoms for R ^I include an aryl group having 6 to 12 carbon atoms and other aromatic groups. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, 3-fluorophenyl group, and 3- Chlorophenyl group, 4-chlorophenyl group, 4-i-propylphenyl group, 4-n-butylphenyl group, 3-chloro-4-methylphenyl group and the like;

As said other aromatic group, 4-pyridinyl group, 2-phenyl-4-quinolinyl group, 2- (4'-t-butylphenyl) -4-quinolinyl group, 2- (2'-thio), for example A phenyl) -4-quinolinyl group etc. are mentioned, respectively.

As a C7-13 aralkyl group of R <^I> , a benzyl group etc. are mentioned, for example.

As the combination of R ^I and X ¹ in the formula A1, the group R ¹ -X ^I integrate them - as, for example, methyl, ethyl, n- propyl, i- propyl, n- butyl, 2- Butyl group, i-butyl group, t-butyl group, formyl group, acetyl group, phenyl group, benzyl group, 1,3-dioxobutyl group, 4-pyridinylcarbonyl group, benzoyl group, 2-phenyl-4-quinoli Nyl group, 2- (4'-t-butylphenyl) -4-quinolinyl group, 2- (2'-thiophenyl) -4-quinolinyl group, formula -CONH-Ph (where Ph is a phenyl group, 3- And fluorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-i-propylphenyl group, 4-n-butylphenyl group or 3-chloro-4-methylphenyl group).

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^II to R ^V in the general formula (A1) include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-butyl group and i-butyl group. , t-butyl group and the like;

As the aryl group having 6 to 12 carbon atoms (the benzene ring which the aryl group may have may be substituted with a formyl group or an alkoxyl group having 1 to 4 carbon atoms), for example, a phenyl group, 4-formylphenyl group, 3,4,5 -Trimethoxyphenyl group;

Examples of the aralkyl group having 7 to 13 carbon atoms (however, the benzene ring of the aralkyl group may be substituted with a formyl group or an alkoxyl group having 1 to 4 carbon atoms) include, for example, benzyl groups.

As the combination of R ^II and X ² , R ^III and X ³ , R ^IV and X ^4, and R ^V and X ⁵ in the formula (A1), groups incorporating these groups R ^II -X ^2- , R ^III -X ^3- , As R ^IV -X ⁴ -or R ^V -X ^5- , respectively, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-butyl group, i-butyl group, t- Butyl group, phenyl group, benzyl group, benzoyl group, 4-formylbenzoyl group, 2-hydroxy-2-phenylethyl group, 2-oxo-2- (3,4,5-trimethoxyphenyl) ethyl group Can be.

As a C2-C6 alkylene group of X <^6> in the said General formula A1, a 1, 3- propylene group, a 1, 6- hexylene group, etc. are mentioned, for example. As X <^6> , an oxygen atom or * -OCO- (however, the bond which attached "*" couple | bonds with a piperidine ring) is preferable.

Two amino groups bonded to the benzene ring of the formula A1 is preferably in the 2,4-position or 3,5-position relative to the group X ^6.

As the compound represented by the formula (A1), particularly preferably, R ^I in the formula (A1) is a hydrogen atom or a methyl group, R ^II to R ^V are all methyl groups, and X ¹ to X ⁵ are all single bonds, ie It is a compound represented by following formula (A1-1).

[Formula A1-1]

(In Formula A1-1, R ^I is a hydrogen atom or a methyl group, X ⁶ is the same as in Formula (A1).)

Two amino groups in the above formulas A1-1 is preferably in the 2,4-position or 3,5-position relative to the group X ^6. As the compound represented by the general formula (A1), the compounds represented by the following general formulas (A1-1-1) to (A1-1-4) are most preferred.

[Formula A1-1-1]

[Formula A1-1-2]

[Formula A1-1-3]

[Formula A1-1-4]

Such a compound represented by the above formula (A1) can be easily synthesized by combining organic chemistry.

For example, in the formula (A1), a compound in which X ⁶ is * -OCO- (wherein the bond to which "*" is attached is combined with a piperidine ring) is a compound represented by the following formula (P-1): dinitrobenzoic acid After reacting with chloride, it can be synthesized by converting the nitro group to an amino group with a suitable reducing system such as hydrazine and palladium carbon.

[Formula P-1]

(In Formula P-1, R ^I to R ^V and X ¹ to X ⁵ each have the same meaning as in Formula A1.)

Further, in the above formula A1, X ⁶ is an oxygen atom, and after reacting the compound represented by the above formula (P-1) with dinitrochlorobenzene in the presence of a suitable base such as potassium t-butoxide, a suitable reducing system, For example, it can synthesize | combine by converting a nitro group into an amino group by hydrazine and palladium carbon.

As an alkyl group having 4 to 16 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond in the middle of R ^VI and R ^VII in the formula A2, each having 4 carbon atoms which may be interrupted by a sulfur atom in the middle It is preferable that it is an alkyl group of 16, for example, a t-butyl group, a 1-methyl pentadecyl group, an octyl thiomethyl group, etc. are mentioned, Among these, a t-butyl group is especially preferable. As the position on the benzene ring of the group R ^VII, is in the 5-position or 6-position is preferred when a hydroxyl group at the 1-position, R ^VI groups into a second position.

Examples of X ⁶ in the formula A2, preferably a group represented by the formula (X ⁶ -1), and in the formula (X ⁶ -1), and a is 2, it is particularly preferred b is 1, group.

Particularly preferred as the compound represented by the formula (A2) is a compound in which both R ^VI and R ^VII in the formula (A2) are t-butyl groups, that is, the compound represented by the following formula (A2-1).

[Formula A2-1]

In Formula A2-1, X ⁶ has the same meaning as in Formula A2.

Two amino groups in the above formulas A2-1 is preferably in the 3,5 position relative to the group X ^6. Most preferred as the compound represented by the formula (A2) is a compound represented by the following formula (A2-1-1).

[Formula A2-1-1]

Such compounds represented by the formula (A2) can be easily synthesized by combining organic chemistry.

For example, the group X ⁶ in the formula A2 groups of the formula (X ⁶ -1), (single, b is 1, Im) the compound is 4-hydroxy-substituted with the desired group R ^VI and R ^VII The benzoic acid is sequentially reacted with thionyl chloride and (poly) methylenediol having the desired methylene chain length a to obtain an alcohol compound which is an intermediate, and the intermediate is reacted with dinitrobenzoic acid chloride, followed by a suitable reducing system such as hydrazine. And it can synthesize | combine by converting nitro group into an amino group by palladium carbon.

As a diamine used for the synthesis | combination of a polyamic acid in this invention, only a compound (A) may be used, or a compound (A) and another diamine may be used together.

As other diamine which can be used here, an aliphatic diamine, an alicyclic diamine, an aromatic diamine (however, except the compound represented by each of the said Formula A1 and A2 is the same below), diamino organosiloxane, etc. are mentioned, for example. Can be.

As these specific examples, As an aliphatic diamine, For example, 1, 1-methacrylylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc .;

As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc .;

As aromatic diamine, for example, p-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl sulfide, 1,5- diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy Phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m- Phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 -Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3 , 6-diaminocarbazole, N-phenyl -3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4- Bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy-2,4-diaminobenzene, tetradecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2, 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecaneoxy-2,5- Diaminobenzene,

Pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, chole Stenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3 , 5-diaminobenzoic acid cholesterol, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane , 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate , 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1 , 1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-hep Ylcyclohexyl) cyclohexane and the compound represented by the following general formula (D-1);

[Formula D-1]

(In Formula D-1, X ^I is an alkyl group having 1 to 3 carbon atoms, * -O-, * -COO- or * -OCO-, provided that a bond with "*" is bonded to a diaminophenyl group.) , x is 0 or 1, y is an integer from 0 to 2, z is an integer from 1 to 20)

Examples of the diaminoorganosiloxanes include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and diamines described in Japanese Patent Application No. 2009-66252 can be used. .

X ^I in the general formula (D-1) is preferably an alkyl group having 1 to 3 carbon atoms, * -O- or * -COO-, provided that the bond to which "*" is attached is combined with a diaminophenyl group. Group C _z H _{2z + 1} - Specific examples of, for example, methyl, ethyl, n- propyl, n- butyl, n- pentyl, n- hexyl, n- heptyl, n- octyl, n -Nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. are mentioned. Two amino groups in the diaminophenyl group are preferably at the 2,4-position or 3,5-position relative to the other group.

As a specific example of the compound represented by the said General formula (D-1), the compound etc. which are respectively represented by following General formula (D-1-1) -D-1-4 are mentioned, for example.

[Formula D-1-1]

[Formula D-1-2]

[Formula D-1-3]

[Formula D-1-4]

In the above formula (D-1), x and y are preferably not 0 at the same time.

These other diamine can be used individually or in combination of 2 or more types.

It is preferable that the diamine used for the synthesis | combination of the polyamic acid in this invention contains a compound (A) 0.1 mol% or more with respect to all diamine, It is more preferable that 0.1-80 mol% is included, It is 1-50 mol% It is particularly preferable to include.

[Synthesis of Polyamic Acid]

The polyamic acid in this invention can be obtained by making tetracarboxylic dianhydride and the diamine containing compound (A) mentioned above react.

The use ratio of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of the polyamic acid is preferably a ratio in which the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents relative to 1 equivalent of the amino group of the diamine. Preferably it is the ratio which becomes 0.3 to 1.2 equivalent.

Synthesis reaction of the polyamic acid is preferably in an organic solvent, preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours under the temperature conditions of -20 ℃ to 150 ℃, more preferably 0 to 100 ℃ Is done during.

Examples of the organic solvent that can be used in the synthesis of the polyamic acid include aprotic polar solvents, phenols and derivatives thereof, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like. Examples of the aprotic polar solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone and tetramethylurea. And hexamethylphosphortriamide may be mentioned. As said phenol derivative, m-cresol, xylenol, a halogenated phenol, etc. are mentioned, for example. As said alcohol, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4- butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc. are mentioned, for example. Acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are mentioned as said ketone. Ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, and diethyl malonate are mentioned as said ester. Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, and ethylene glycol ethyl ether. Acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran Can be. Examples of the halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, and o-dichlorobenzene. As said hydrocarbon, hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether is mentioned, for example.

Among these organic solvents, at least one selected from the group consisting of aprotic polar solvents and phenols and derivatives thereof (first group of organic solvents), or at least one type and alcohols selected from the first group of organic solvents, Preference is given to using at least one mixture selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight or less, based on the total of the organic solvent of the first group and the organic solvent of the second group. It is more preferable that it is 30 weight% or less.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained.

This reaction solution may be used as it is for the production of a liquid crystal aligning agent, may be used for the production of a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or after the isolated polyamic acid is purified to prepare a liquid crystal aligning agent. Can also be used for

When the polyamic acid is dehydrated and closed to form an imidized polymer, the reaction solution may be used as it is for dehydration and ring closure, or after isolating the polyamic acid contained in the reaction solution and then used for dehydration and ring closure. The acid may be purified and then used for the dehydration ring closure reaction.

Isolation of a polyamic acid can be performed by pouring the said reaction solution in a large quantity of poor solvents, obtaining a precipitate, and drying this precipitate under reduced pressure, or distilling off the organic solvent in a reaction solution by evaporation under reduced pressure. In addition, a method of dissolving the polyamic acid again in an organic solvent, followed by precipitation with a poor solvent, or washing the solution in which the polyamic acid is dissolved in the organic solvent again, and then distilling off the organic solvent in the solution under reduced pressure using an evaporator. Polyamic acid can be refine | purified by the method of performing once or several times.

<Imidated Polymer>

The imidation polymer in this invention can be obtained by imidating by dehydrating and ring-closing polyamic acid as mentioned above.

As tetracarboxylic dianhydride used for the synthesis | combination of the said imidation polymer, the compound similar to tetracarboxylic dianhydride used for the synthesis | combination of the polyamic acid mentioned above is mentioned. The kind of preferable tetracarboxylic dianhydride and its preferable use ratio are also the same as that of polyamic acid.

As a diamine used for synthesizing the imidation polymer in this invention, the same diamine as the diamine used for the synthesis | combination of said polyamic acid is mentioned. That is, the diamine used for the synthesis | combination of the imidation polymer in this invention contains the compound (A) as mentioned above, Only a compound (A) may be used and a compound (A) and another diamine may be used together. . Preferred types of other diamines and preferred use ratios of each diamine are also the same as in the case of polyamic acid.

The imidized polymer in this invention may be the complete imide which dehydrated and closed all the amic acid structures which the polyamic acid which is a raw material has, and only a part of amic acid structure is dehydrated and closed, and an amic acid structure and an imide ring structure coexist. The partial imide may be sufficient. It is preferable that the imidation ratio in this invention is 20% or more, It is more preferable that it is 30 to 90%, It is especially preferable that it is 40 to 80%. This imidation ratio shows the ratio which the number of the imide ring structures to the sum total of the number of the amic acid structures and the number of imide ring structures of an imidation polymer occupies as a percentage. At this time, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating it as necessary. It is done by the method.

Preferably the reaction temperature in the method of heating the polyamic acid of said (i) is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall. The reaction time is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours.

On the other hand, as a dehydrating agent, acid anhydrides, such as an acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used as a dehydrating agent in the method of adding a dehydrating agent and a dehydration ring-closure catalyst in the solution of said polyamic acid of said (ii). Although the usage-amount of a dehydrating agent changes with a desired imidation ratio, it is preferable to set it as 0.01-20 mol with respect to 1 mol of the amic-acid structure of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to this. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. The imidation ratio can be increased as the usage-amount of the above-mentioned dehydrating agent and dehydrating ring closure agent increases. As an organic solvent used for dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

The imidation polymer obtained by the said method (i) may be used for manufacture of a liquid crystal aligning agent as it is, or may be used for manufacture of a liquid crystal aligning agent after refine | purifying the imidation polymer obtained. On the other hand, in the said method (ii), the reaction solution containing an imidation polymer is obtained. This reaction solution may be used as it is for the production of a liquid crystal aligning agent, or may be used for the production of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closure catalyst from the reaction solution. It may be used, or may be used for the production of a liquid crystal aligning agent after purifying the isolated imidized polymer. In order to remove a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, methods, such as solvent substitution, can be applied, for example. Isolation and purification of the imidized polymer can be performed by performing the same operation as described above as the isolation and purification method of the polyamic acid.

Terminal Modified Polymer

The polyamic acid and its imidized polymer in the liquid crystal aligning agent of the present invention may each be a terminal-modified polymer having a controlled molecular weight. By using the polymer of the terminal modification type, the coating characteristic of a liquid crystal aligning agent, etc. can be further improved, without impairing the effect of this invention. Such terminal-modified polymer can be carried out by adding a molecular weight regulator to the polymerization reaction system when synthesizing the polyamic acid. As a molecular weight modifier, an acid anhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example.

As said acid anhydride, maleic anhydride, a phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n- tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. are mentioned, for example. have. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n- Eicosylamine, etc. are mentioned. As said monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid.

Solution viscosity

It is preferable that the polyamic acid obtained by the above and its imidation polymer have a solution viscosity of 20-800 mPa * s, when these are respectively made into the solution of 10 weight% of concentration, and have a solution viscosity of 30-500 mPa * s. It is more preferable to have.

The solution viscosity (mPa.s) of the polymer is a polymer having a concentration of 10% by weight using the good solvent of the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is the value measured at 25 degreeC using the E-type rotational viscometer with respect to a solution.

<Other additives>

Although the liquid crystal aligning film of this invention contains as an essential component 1 or more types of polymers chosen from the group which consists of the polyamic acid and imidation polymer as mentioned above, you may contain other components as needed. Examples of such other components include other polymers, compounds having one or more epoxy groups in the molecule (hereinafter referred to as "epoxy compound"), functional silane compounds, and the like.

 Such other polymers can be used to improve solution properties and electrical properties. These other polymers are polymers other than the polyamic acid obtained by making tetracarboxylic dianhydride and the diamine containing a compound (A) react, and its imidation polymer, For example, tetracarboxylic dianhydride and a compound (A) Polyamic acid obtained by reacting a diamine containing no, an imidized polymer of the polyamic acid, polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative And poly (meth) acrylates.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl Ether, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N '-Tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-digly Cydyl-cyclohexylamine etc. are mentioned as a preferable thing.

The compounding ratio of these epoxy compounds becomes like this. Preferably it is 40 weight part or less, More preferably, it is 0.1-30 weight part with respect to 100 weight part of polymers in total.

As said functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimeth Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl-3 , 6-diazanonyl acetate, 9-trimethoxysilyl-3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, 9-tet Methoxysilyl-3,6-methyl diazanonanate, 9-triethoxysilyl-3,6-methyl diazanonanate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyl Triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2 -Glycidoxy ethyl trimethoxy silane, 2-glycidoxy ethyl triethoxy silane, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxy silane, etc. are mentioned.

The blending ratio of these functional silane compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight with respect to 100 parts by weight in total of the polymer.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of the present invention is preferably composed by dissolving one or more polymers selected from the group consisting of polyamic acid and imidized polymers thereof as described above and other additives optionally blended as necessary in an organic solvent. .

As an organic solvent which can be used for the liquid crystal aligning agent of this invention, for example, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N -Dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Isobutyl ketone, and the like can be mentioned isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate. These may be used independently, or may mix and use 2 or more types.

Solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies in the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention is selected suitably in consideration of viscosity, volatility, etc., Preferably it is 1 To 10% by weight. That is, the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate as mentioned later, Preferably, the coating film used as a liquid crystal aligning film is formed by heating, However, when solid content concentration is less than 1 weight%, the film thickness of this coating film is too small. When a good liquid crystal aligning film cannot be obtained, and solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes large too much and a favorable liquid crystal aligning film cannot be obtained, the viscosity of a liquid crystal aligning agent increases, and coating property falls. .

The range of especially preferable solid content concentration changes with the method used when apply | coating a liquid crystal aligning agent to a board | substrate. For example, the range of 1.5 to 4.5 weight% of solid content concentration is especially preferable by the spinner method. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is in the range of 12 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s.

The temperature at the time of manufacturing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10 degreeC-50 degreeC, More preferably, it is 20 degreeC-30 degreeC.

<Liquid crystal display element>

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention as mentioned above.

The liquid crystal display element of this invention can be manufactured by the process of the following (1)-(3), for example. The process (1) differs in the heating substrate after apply | coating a use board | substrate, the preferable coating method of a liquid crystal aligning agent, and a liquid crystal aligning agent depending on a desired operation mode. Steps (2) and (3) are common to each operation mode.

(1) First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, and then a coating film is formed on a board | substrate by heating a coating surface.

(1-1) When manufacturing a TN type, STN type, or VA type liquid crystal display element, two board | substrates with which the patterned transparent conductive film is provided are made into a pair, and the liquid crystal of this invention on each transparent conductive film formation surface. An aligning agent is apply | coated preferably by the offset printing method, the spin coating method, or the inkjet printing method, respectively, and then a coating film is formed by heating each application surface. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; Transparent substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, poly (alicyclic olefin) and the like can be used. Examples of the transparent conductive film provided on one side of the substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd.) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ). In order to obtain a patterned transparent conductive film, for example, a method of forming a transparent conductive film without a pattern and then forming a pattern by photo-etching or a mask having a desired pattern when forming a transparent conductive film is used. This can be done by the method. At the time of coating of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, and the like are previously applied to the surface on which the coating film should be formed on the substrate surface. Pretreatment can also be performed.

After application of the liquid crystal aligning agent, preliminary heating (pre-baking) is preferably performed for the purpose of preventing the liquid dripping of the applied alignment agent. Preliminary baking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. The preliminary baking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, the solvent is completely removed, and a firing (post-baking) step is performed for the purpose of thermally imidizing the amic acid structure present in the polymer as necessary. This firing (post-baking) temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 µm, more preferably 0.005 to 0.5 µm.

(1-2) On the other hand, when manufacturing an IPS type | mold liquid crystal display element, this invention is carried out on the electrically conductive film formation surface of the board | substrate with which the transparent conductive film patterned by the comb-tooth shape is provided, and the one side of the opposing board | substrate with which the conductive film is not provided. The liquid crystal aligning agent of preferably is apply | coated by an offset printing method, a spinner method, or the inkjet printing method, respectively, and then a coating film is formed by heating each application surface.

About the material of the board | substrate and a transparent conductive film used at this time, the patterning method of a transparent conductive film, the pretreatment of a board | substrate, and the heating method after apply | coating a liquid crystal aligning agent, it is the same as said (1-1).

The preferable film thickness of the coating film formed is the same as said (1-1).

(2) When the liquid crystal display element manufactured by the method of this invention is a VA type liquid crystal display element, the coating film formed as mentioned above can be used as a liquid crystal aligning film as it is, but the rubbing process mentioned later according to the objective was performed. You can also use it later.

On the other hand, when manufacturing liquid crystal display elements other than VA type, a rubbing process is given to the coating film formed as mentioned above, and it is set as a liquid crystal aligning film.

The rubbing treatment can be performed by rubbing in a predetermined direction with a roll wound with a cloth containing fibers such as nylon, rayon, cotton and the like on the coating film surface formed as described above. Thereby, the orientation ability of liquid crystal molecules is provided to a coating film, and it becomes a liquid crystal aligning film.

Moreover, about the liquid crystal aligning film formed as mentioned above, for example, in patent document 9 (Unexamined-Japanese-Patent No. 6-222366) and patent document 10 (Japanese Unexamined-Japanese-Patent No. 6-281937). A process of changing the pretilt angle of a partial region of the liquid crystal aligning film by irradiating a part of the liquid crystal aligning film as described, and Patent Document 11 (Japanese Patent Laid-Open No. 5-107544) A liquid crystal display obtained by forming a resist film on a part of the surface of the liquid crystal alignment film as described above, then performing a rubbing treatment in a direction different from the previously performed rubbing treatment, and then removing the resist film so that the liquid crystal alignment film has a different liquid crystal alignment ability for each region. It is possible to improve the viewing characteristics of the device.

(3) The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as above-mentioned, and arrange | positioning a liquid crystal between two board | substrates which oppose. Here, when the rubbing process is performed with respect to a coating film, two board | substrates are mutually arrange | positioned so that the rubbing direction in each coating film may mutually become a predetermined angle, for example, orthogonal or antiparallel.

In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a method known in the art. First, two substrates are disposed to face each other so as to face each liquid crystal alignment film, and the peripheral portions of the two substrates are bonded together using a sealant, and the cell partitioned by the substrate surface and the sealant. After the injection filling of the liquid crystal within the interval, the liquid crystal cell can be produced by sealing the injection hole.

The second method is called a one drop fill (ODF) method. An ultraviolet photocurable sealing material is apply | coated to the predetermined place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, for example, after dropping a liquid crystal on the liquid crystal aligning film surface, the other board | substrate is bonded so that a liquid crystal aligning film may oppose. Then, a liquid crystal cell can be manufactured by irradiating ultraviolet light to the whole surface of a board | substrate, and hardening a sealing agent.

In any case, the liquid crystal cell produced as described above is preferably heated to a temperature at which the used liquid crystal takes an isotropic phase, and then gradually cooled to room temperature to remove the flow orientation during liquid crystal filling.

Moreover, the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell.

Here, as a sealing agent, the epoxy resin etc. which contain the hardening agent and the aluminum oxide sphere as a spacer can be used, for example.

As said liquid crystal, a nematic liquid crystal, a smectic liquid crystal, etc. can be used, for example, A nematic liquid crystal is preferable among these. In the case of a VA type liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy is preferable, and for example, a dicyano benzene liquid crystal, a pyridazine liquid crystal, a Schiff base liquid crystal, a cfamily clock liquid crystal, a biphenyl liquid crystal And phenylcyclohexane-based liquid crystals are used. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy is preferable, for example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a non A phenylcyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. are used. To these liquid crystals, For example, cholesteric liquid crystals, such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate; Chiral agent sold as brand names C-15 and CB-15 (made by Merck); Ferroelectric liquid crystals such as p-disiloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and used.

As a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which sandwiched the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching polyvinyl alcohol, and between the cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned.

[Example]

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples. The solution viscosity of the polymer in the Example and the comparative example and the imidation ratio of the imidation polymer were evaluated by the following method.

[Solution Viscosity of Polymer]

The solution viscosity (mPa * s) of a polymer was measured at 25 degreeC using the E-type rotational viscometer about the polymer solution indicated by each synthesis example.

[Imidation Rate of Imidized Polymer]

The solution containing the imidized polymer was poured into pure water, and the obtained precipitate was dried under reduced pressure at room temperature sufficiently, dissolved in deuterated dimethyl sulfoxide, and determined from ¹ H-NMR spectrum measured at room temperature using tetramethylsilane as a reference substance. The imidation ratio was calculated | required by following formula (1).

&Quot; (1) &quot;

Imidation ratio (%) = (1-A ¹ / A ² × α) × 100

(In Formula 1, A ¹ is the area of the peak derived from the proton of the NH group appearing near 10 ppm of chemical shift, A ² is the area of the peak derived from other protons, and α is the precursor of the imidized polymer. Number of other protons to one proton of NH group in polyamic acid)

Synthesis Example of Compound (A)

Synthesis Example 1

According to Scheme 1 below, compound (A1-1-1) was synthesized.

(1) Synthesis of Compound (A1-1-1a)

In a 500 mL three-necked flask equipped with a dropping funnel, a nitrogen introduction tube and a thermometer, 16 g of 2,2,6,6-tetramethyl-4-piperidinol and 250 mL of pyridine were added and ice-cooled. The solution which melt | dissolved 23 g of 3, 5- dinitro benzoyl chlorides in 100 mL of tetrahydrofuran was dripped at this solution over 30 minutes under ice cooling, and it stirred as it is at room temperature for 3 hours. Thereafter, 1 L of ethyl acetate was added to the reaction mixture, followed by separating and washing with 500 mL of water. Subsequently, the organic layer was dried over magnesium sulfate, concentrated and dried, and then recrystallized with ethanol to obtain 28 g of pale yellow crystals of compound (A1-1-1a).

(2) Synthesis of Compound (A1-1-1)

To a 500 mL three-necked flask equipped with a reflux tube, nitrogen introduction tube and thermometer were added 28 g of the compound (A1-1-1a) obtained above, 0.5 g of 5 wt% palladium carbon, 290 mL of ethanol and 20 mL of hydrazine monohydrate. After stirring at room temperature for 1 hour, the reaction was further performed at 70 ° C. for 1 hour with stirring. After the completion of the reaction, palladium carbon was removed from the reaction mixture by filtration, and 1.6 L of ethyl acetate was added thereto, followed by separating and washing with 800 mL of water. The organic layer was dried over magnesium sulfate, and then the solvent was removed under reduced pressure and the dried product was recrystallized from a mixed solvent of ethyl acetate and hexane to obtain 16 g of white crystals of compound (A1-1-1).

Synthesis Example 2

Compound (A1-1-2) was synthesized according to the following Scheme 2.

(1) Synthesis of Compound (A1-1-2a)

In a 500 mL three-necked flask equipped with a dropping funnel, nitrogen introduction tube and thermometer, 17 g of 1,2,2,6,6-pentamethyl-4-piperidinol and 16.6 mL of triethylamine were added to 100 mL of tetrahydrofuran. The dissolved solution was added and ice-cooled. The solution which melt | dissolved 23 g of 3, 5- dinitro benzoyl chlorides in 100 mL of tetrahydrofuran was dripped at this solution under ice cooling over 30 minutes, and it heated up to room temperature, and also reacted under stirring for 3 hours. After the completion of the reaction, 300 mL of ethyl acetate was added to the reaction mixture, and the organic layer was washed sequentially with 1 mol / L aqueous sodium hydroxide solution and water. Subsequently, the organic layer was dried over magnesium sulfate, and the solid obtained by removing the solvent under reduced pressure was recrystallized from a mixed solvent consisting of ethanol and tetrahydrofuran (ethanol: tetrahydrofuran = 50: 50 (weight ratio)) to thereby give a compound (A1- 29 g of pale yellow crystals of 1-2a) were obtained.

(2) Synthesis of Compound (A1-1-2)

Into a 500 mL three-necked flask equipped with a reflux tube, nitrogen introduction tube, and thermometer, 28 g of the compound (A1-1-2a) obtained above, 1.9 g of 5 wt% palladium carbon, 290 mL of ethanol, and 20 mL of hydrazine monohydrate were added. After stirring at room temperature for 1 hour, the reaction was further performed at 70 ° C. for 1 hour with stirring. After the completion of the reaction, the reaction mixture was filtered to remove palladium carbon, and then the organic layer obtained by adding 1.6 L of ethyl acetate was washed with 800 mL of water. After drying this organic layer with magnesium sulfate, the solid obtained by removing a solvent under reduced pressure was recrystallized from the mixed solvent which consists of ethyl acetate and hexane (ethyl acetate: hexane = 50: 50 (weight ratio)), and a compound (A1-1-2) 17 g of white crystals were obtained.

Synthesis Example 3

Compound (A2-1-1) was synthesized according to the following Schemes 3 (1) and 3 (2).

(1) Synthesis of Compound (A2-1-1b)

In a 500 mL three-necked flask equipped with a dropping funnel, nitrogen introduction tube and thermometer, 13 g of 3,5-di-t-butyl-4-hydroxybenzoic acid and 20 mL of thionyl chloride, 0.6 mL of N, N-dimethylformamide Was added and the reaction was carried out at 80 ° C. for 1 hour while stirring. After completion of the reaction, thionyl chloride was distilled off from the reaction mixture under reduced pressure, and then 100 mL of dichloromethane was added to the residue to obtain an organic layer. The organic layer was washed with distilled water, dried over magnesium sulfate, and the solid obtained by removing the solvent under reduced pressure was dissolved in 40 mL of tetrahydrofuran to give a solution.

Apart from the above, 27.7 mL of ethylene glycol, 7.67 mL of triethylamine, and 40 mL of tetrahydrofuran were added to a 500 mL three-necked flask equipped with a dropping funnel, a nitrogen inlet tube, and a thermometer, and uniformly mixed to prepare a solution. A tetrahydrofuran solution containing the reaction product of the above-mentioned 3,5-di-t-butyl-4-hydroxybenzoic acid and thionyl chloride was added dropwise thereto, and the reaction was carried out at 0 ° C. under stirring for 1 hour. After the completion of the reaction, 300 mL of ethyl acetate was added to the reaction mixture, the organic layer was washed with water, dried over magnesium sulfate, and concentrated to obtain a crystalline solid. This solid was recovered by filtration extraction and washed with hexane to obtain 10 g of compound (A2-1-1a).

In a 500 mL three-necked flask equipped with a dropping funnel, a nitrogen introduction tube and a thermometer, 9.2 g of the compound (A2-1-1a) obtained above and 5.23 mL of triethylamine were dissolved in 50 mL of tetrahydrofuran, and 3 A solution obtained by dissolving 7.6 g of, 5-dinitrobenzoyl chloride in 50 mL of tetrahydrofuran was added dropwise, followed by reaction at room temperature under stirring for 1 hour. After the completion of the reaction, 200 mL of ethyl acetate was added to the reaction mixture, the organic layer was washed with water, dried over magnesium sulfate, and the solvent was removed under reduced pressure to recrystallize the solid obtained from ethanol to determine the compound (A2-1-1b). 12 g were obtained.

(2) Synthesis of Compound (A2-1-1)

Into a 500 mL three-necked flask equipped with a reflux tube, a nitrogen introduction tube and a thermometer, 12 g of the compound (A2-1-1b) obtained above, 0.6 g of 5 wt% palladium carbon, 70 mL of ethanol and 70 mL of tetrahydrofuran were charged. And mixed. 6 mL of hydrazine monohydrate was added dropwise thereto, stirred at room temperature for 1 hour, and further reacted at 70 ° C for 2 hours with stirring. After completion of the reaction, palladium carbon was removed from the reaction mixture by filtration, and then 200 mL of ethyl acetate was added to wash the organic layer obtained with 200 mL of water. The organic layer was concentrated and 10 g of a white solid of Compound (A2-1-1) was obtained by removing the solvent under reduced pressure from the distillate obtained by purification by column chromatography (filler: silica gel, developing solvent: chloroform). .

Synthesis Example of Polymer

Synthesis Example 4

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 15 g (0.05 mol) of compound (A1-1-1) obtained in Synthesis Example 1 as diamine, 38 g (0.35 mole) of p-phenylenediamine and 52 g (0.10 mole) of 3,5-diaminobenzoic acid-3-cholestanyl are dissolved in 800 g of N-methyl-2-pyrrolidone, and The reaction was carried out for 6 hours to obtain a polyamic acid solution. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of N-methyl- 2-pyrrolidone, and measuring as a solution of 10 weight% of polyamic-acid concentration was 60 mPa * s.

Subsequently, 1,800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 39 g of pyridine and 50 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was substituted with fresh N-methyl-2-pyrrolidone (pyridine and acetic anhydride used for the dehydration ring closure reaction in this operation were removed to the outside of the system, which is the same below). A solution containing about 15% by weight of imidized polymer (PI-1) was obtained. A small amount of the solution of the imidized polymer was fractionated, and the solution viscosity measured as a solution having an imidized polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 87 mPa · s.

Synthesis Example 5

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 15 g (0.05 mol) of compound (A1-1-2) obtained in Synthesis Example 2 as diamine, 46 g (0.3 mol) of 3,5-diaminobenzoic acid, 39 g (0.075 mol) of 3,5-diaminobenzoic acid-3-cholestanyl and 37 g (0.075) of cholestanyloxy-2,4-diaminobenzene Mole) was dissolved in 800 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a polyamic acid solution. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of N-methyl- 2-pyrrolidone, and measured as a solution of 10 weight% of polyamic-acid concentration was 50 mPa * s.

Subsequently, 1,800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 39 g of pyridine and 50 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing 15% by weight of imidized polymer (PI-2) having an imidization ratio of about 60%. A small amount of the solution of the imidized polymer was aliquoted, and the solution viscosity measured as a solution having an imidized polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 70 mPa · s.

Synthesis Example 6

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 21 g (0.05 mol) of compound (A2-1-1) obtained in Synthesis Example 3 as diamine, 46 g (0.3 mol) of 3,5-diaminobenzoic acid, 39 g (0.075 mol) of 3,5-diaminobenzoic acid-3-cholestanyl and 37 g (0.075 of cholestanyloxy-2,4-diaminobenzene) Mole) was dissolved in 800 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain a polyamic acid solution. A small amount of the obtained polyamic acid solution was fractionated, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 52 mPa · s.

Subsequently, 1,800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 39 g of pyridine and 50 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing 15% by weight of an imidization polymer (PI-3) having an imidization ratio of about 50%. A small amount of the solution of the imidized polymer was collected, and the solution viscosity measured as a solution having an imidized polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 72 mPa · s.

<Comparative Synthesis Example of Polymer>

Comparative Synthesis Example 1

Except for using 43 g (0.40 mol) of p-phenylenediamine and 52 g (0.10 mol) of 3,5-diaminobenzoic acid-3-cholestanyl as diamine, the imidation ratio was about A solution containing 15% by weight of 50% imidized polymer (PI-4) was obtained. A small amount of the solution of the imidized polymer was fractionated, and the solution viscosity measured as a solution having an imidized polymer concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 68 mPa · s.

<Production and Evaluation of Liquid Crystal Alignment Agent>

Example 1

[Production of Liquid Crystal Alignment Agent]

N-methyl-2-pyrrolidone and butyl cellosolve were added to a solution containing the imidized polymer (PI-1) obtained in Synthesis Example 4, and the solvent composition was N-methyl-2-pyrrolidone: A butyl cellosolve = 65:35 (weight ratio) and solid content concentration were used as the solution of 4 weight%, and this liquid-crystal aligning agent was manufactured by filtering by the filter of 1 micrometer of pore diameters.

[Production of Liquid Crystal Cell]

The liquid crystal aligning agent prepared above was apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode containing an ITO membrane using a liquid crystal aligning film printing machine (made by Nippon Shashin Insatsu Co., Ltd.), and is preliminarily reserved for 1 minute on an 80 degreeC hotplate. After baking, the film (liquid crystal aligning film) of an average film thickness of 800 Pa was formed by post-baking for 10 minutes on the 200 degreeC hotplate. This operation was repeated and the pair (2 sheets) of board | substrates which have a liquid crystal aligning film on the transparent conductive film was obtained.

Subsequently, after apply | coating the epoxy resin adhesive containing the aluminum oxide sphere of 3.5 micrometers in diameter to each outer edge part which has a pair of said liquid crystal aligning film, the liquid crystal aligning film surface was overlapped so that it might face and pressed, and the adhesive was hardened. Next, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection hole, the liquid crystal cell of a vertical alignment type was manufactured by sealing a liquid crystal injection hole with an acryl-type photocuring adhesive.

[Evaluation of Liquid Crystal Cells]

(1) Evaluation of voltage retention

The voltage retention rate of this liquid crystal cell was 98% when the voltage of 1 V was applied to 70 degreeC for 30 second with respect to the said liquid crystal cell, and the voltage retention after application | release cancellation was measured at 1 V and 70 degreeC by frame period 167 m second. .

(2) evaluation of light resistance

The liquid crystal cell was placed at a distance of 5 cm under a 100-watt white fluorescent lamp and irradiated with light for 500 hours, and the voltage retention was measured again in the same manner as above. The voltage retention after light irradiation for 500 hours was 94%. It was good.

(3) Evaluation of liquid crystal alignment

The liquid crystal display element was manufactured by bonding two polarizing plates up and down of a liquid crystal cell so that the polarization direction may orthogonally cross in the same manner to the above. When it observed with the naked eye about this liquid crystal display element, there was no light leakage when voltage was not applied and liquid crystal orientation (vertical orientation) was favorable.

Examples 2 and 3 and Comparative Example 1

In the said Example 1, the liquid crystal aligning agent was manufactured like Example 1 except having used the solution containing the imidation polymer shown in Table 1 instead of the solution containing the imidation polymer (PI-1), respectively. And the liquid crystal cell and the liquid crystal display element were manufactured and evaluated.

The evaluation results are shown in Table 1.

Claims (9)

At least one polymer selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine and its imidized polymer,
The diamine,
A cyclic amine structure in which two carbon atoms adjacent to a nitrogen atom are each substituted by an oxygen atom, a sulfur atom, a carbonyl group or two hydrocarbon groups which may be interrupted by an ester bond, or
A phenol structure in which at least one carbon in the ortho position relative to the hydroxyl group is substituted by an oxygen atom, a sulfur atom, a carbonyl group or a hydrocarbon group which may be interrupted by an ester bond,
2 amino groups
The compound (A) which has a liquid crystal aligning agent characterized by the above-mentioned. The liquid crystal aligning agent of Claim 1 whose said compound (A) is a compound represented by following General formula A1 or A2.
<Formula A1>

<Formula A2>

(In formula A1, R <^I> is a hydrogen atom, a C1-C6 alkyl group, a C6-C20 aromatic group, a C7-13 aralkyl group, or a 1, 3- dioxobutyl group,
X ¹ is a single bond, a carbonyl group or * -CONH- (wherein the bond to which "*" is attached is combined with a piperidine ring),
R ^II to R ^V are each an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms, provided that the benzene ring having the aryl group and aralkyl group is a formyl group or 1 to 4 carbon atoms. It may be substituted with an alkoxyl group of,
X ² to X ⁵ each represent a single bond, a carbonyl group, * -CH ₂ -CO- or * -CH ₂ -CH (OH)-(wherein the bond to which "*" is attached is combined with a piperidine ring),
In formula (A2), R ^VI is an alkyl group having 4 to 16 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond in the middle, and R ^VII is a hydrogen atom or an oxygen atom, a sulfur atom, a carbonyl group in the middle Or an alkyl group having 1 to 16 carbon atoms which may be interrupted by an ester bond,
X ⁶ in the formulas A1 and A2 are each an oxygen atom, * -OCO-, a group represented by the following formula (X ⁶ -1)

(Formula (X ⁶ -1) of, a is an integer from 1 to 12, b is an integer of from 0 to 5)
(However, in the above description, the bond group with “*” is bonded to the piperidine ring in the formula (A1) and the benzene ring having a hydroxyl group in the formula (A2), respectively), and is a methylene group or an alkylene group having 2 to 6 carbon atoms.) The liquid crystal aligning agent of claim 2, wherein the compound represented by Formula A1 is a compound represented by Formula A1-1, and the compound represented by Formula A2 is a compound represented by Formula A2-1.
<Formula A1-1>

<Formula A2-1>

R ^I in the formula A1-1 is a hydrogen atom or a methyl group,
X ⁶ in Formulas A1-1 and A2-1 have the same meaning as X ⁶ in Formula A1 or A2, respectively) The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the tetracarboxylic dianhydride includes 2,3,5-tricarboxycyclopentylacetic dianhydride. It formed from the liquid crystal aligning agent in any one of Claims 1-3, The liquid crystal aligning film characterized by the above-mentioned. The liquid crystal aligning film of Claim 5 is provided, The liquid crystal display element characterized by the above-mentioned. A cyclic amine structure in which two carbon atoms adjacent to a nitrogen atom are each substituted by an oxygen atom, a sulfur atom, a carbonyl group or two hydrocarbon groups which may be interrupted by an ester bond, or
A phenol structure in which at least one carbon in the ortho position relative to the hydroxyl group is substituted by an oxygen atom, a sulfur atom, a carbonyl group or a hydrocarbon group which may be interrupted by an ester bond,
Diamine containing the compound (A) which has two amino groups, and
Polyamic acid obtained by making tetracarboxylic dianhydride react. A cyclic amine structure in which two carbon atoms adjacent to a nitrogen atom are each substituted by an oxygen atom, a sulfur atom, a carbonyl group or two hydrocarbon groups which may be interrupted by an ester bond, or
A phenol structure in which at least one carbon in the ortho position relative to the hydroxyl group is substituted by an oxygen atom, a sulfur atom, a carbonyl group or a hydrocarbon group which may be interrupted by an ester bond,
Diamine containing the compound (A) which has two amino groups, and
The imidation polymer formed by dehydrating and ring-closing the polyamic acid obtained by making tetracarboxylic dianhydride react. A cyclic amine structure in which two carbon atoms adjacent to a nitrogen atom are each substituted by an oxygen atom, a sulfur atom, a carbonyl group or two hydrocarbon groups which may be interrupted by an ester bond, or
A phenol structure in which at least one carbon in the ortho position relative to the hydroxyl group is substituted by an oxygen atom, a sulfur atom, a carbonyl group or a hydrocarbon group which may be interrupted by an ester bond,
Compound (A) having two amino groups.