KR20070111354A - Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display - Google Patents

Abstract

A vertical type liquid crystal aligning agent is provided to ensure excellent voltage maintenance characteristics in a vertical type liquid crystal device while exhibiting good coatability on a substrate. A vertical type liquid crystal aligning agent comprises a polymer having at least one of amic acid repeating units represented by the following formula 1a and imide repeating units represented by the following formula 2, wherein Q1 in formula 1a and Q2 in formula 1b contains at least one divalent organic group represented by the following formulae 2a and 2b, and at least one divalent organic group represented by the formula of -X2-3-X2. In formulae 1a and 1b, each of P1 and P2 represents a tetravalent organic group forming a tetracarboxylic acid, and each of Q1 and Q2 represents a divalent organic group forming a diamine. In formulae 2a and 2b, X1 is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S-, methylene, C2-C6 alkylene or phenylene; R1 is a C10-20 alkyl, C4-C40 alicyclic monovalent organic group or C6-C20 fluorine-containing monovalent organic group; and R2 is a C4-C40 alicyclic divalent organic group or C5-C30 fluorine-containing divalent organic group. In the formula of -X2-3-X2, X2 independently represents methylene or a C2-C20 alkylene; and R3 is an aromatic ring-containing backbone, organosiloxane backbone, divalent organic group represented by the formula of -R-(O-C2H4)n-O-R- (wherein R is a C2-C5 alkylene and n is 1-100), a divalent organic group represented by the formula of -R-(O-C2H4)n-O-R- (wherein R is a C2-C5 alkylene, and n is 1-50), C4-C40 alicyclic ring backbone-containing divalent organic group.

Description

Vertically oriented liquid crystal aligning agent and vertically oriented liquid crystal display element TECHNICAL FIELD [Vertical ALIGNMENT TYPE LIQUID CRYSTAL ALIGNING AGENT AND VERTICAL ALIGNMENT TYPE LIQUID CRYSTAL DISPLAY}

The present invention relates to a liquid crystal display device having a vertical alignment liquid crystal alignment agent and a vertical alignment liquid crystal alignment film. More specifically, it is related with the liquid crystal display element which has a favorable printability and is excellent in various electrical characteristics, and has a vertical alignment type liquid crystal aligning agent and a vertical alignment type liquid crystal aligning film.

Currently, as a liquid crystal display element, the liquid crystal aligning film which consists of a polyamic acid, a polyamide, etc. is formed in the surface of the board | substrate with which the transparent conductive film is provided, and it is set as a board | substrate for liquid crystal display elements, and two of them are opposingly arranged, and positive (+ A so-called TN type (torsion nematic;) in which a layer of nematic liquid crystal having dielectric anisotropy is formed to form a sandwich cell, and the long axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other. Twisted Nematic) TN type liquid crystal display elements having liquid crystal cells are known.

Moreover, STN (Super Twisted Nematic) type | mold liquid crystal display element which has high contrast compared with TN type liquid crystal display element, and its visual dependence is small, and the vertically-aligned type liquid crystal display element is developed. This STN type liquid crystal display element is produced by blending a nematic liquid crystal with a chiral agent, which is an optically active substance, as a liquid crystal, and is produced when the long axis of the liquid crystal molecules is continuously twisted over 180 degrees between the substrates. It is to use the birefringence effect.

In addition, in recent years, the development of new liquid crystal display devices is also active, and among them, two electrodes for driving a liquid crystal are arranged on the substrate on one side in a cross-sectional shape to generate an electric field parallel to the substrate surface. Transverse electric field type liquid crystal display elements which control liquid crystal molecules have been proposed. This device is commonly referred to as In-plane switching (IPS type) and is known for its wide viewing angle characteristics. In addition, in recent years, the optical viewing film has been used to further improve the wide viewing angle characteristics, and thus, a large viewing angle comparable to a CRT without layer reversal and color tone change can be obtained.

As another liquid crystal display device, MVA (Multi domain Vertical Alignment) method or PVA (patterned vertical alignment) formed by aligning liquid crystal molecules having negative dielectric anisotropy perpendicular to a substrate; A vertical alignment liquid crystal display element called a Patterned Vertical Alignment) method has been proposed. The liquid crystal display elements of these MVA system and PVA system are excellent not only in viewing angle and contrast, but also in terms of a manufacturing process, such as not having to perform a rubbing process in formation of a liquid crystal aligning film.

Conventionally, as these liquid crystal aligning films, since it is excellent in heat resistance, affinity with a liquid crystal, or mechanical strength, polyamic acid or the polyimide which carried out the dehydration ring closure of this in many display modes is used for the liquid crystal display element.

Currently, the liquid crystal aligning film of a vertically-aligned liquid crystal display element is formed by apply | coating a liquid crystal aligning agent to a board | substrate as described in Unexamined-Japanese-Patent No. 2002-327058 (patent document 1), and a liquid crystal is perpendicular | vertical as a basic characteristic. Vertical orientation that can be oriented is required. In recent years, as the penetration rate of a vertically oriented liquid crystal display element expands, the demand for the improvement of the display quality and productivity which can be achieved by a vertical liquid crystal aligning film becomes higher. Although various characteristics are required for the alignment film, among them, the most important characteristics are Japanese Patent Application Laid-Open No. 2002-327058 (Patent Document 1), Japanese Patent Application Laid-Open No. 2002-162630 (Patent Document 2) and Japanese Patent Publication As described in Japanese Patent Application Laid-Open No. 2004-67589 (Patent Document 3) and Japanese Patent Application Laid-Open No. 2005-308924 (Patent Document 4), improvements for high voltage holding characteristics and good applicability to a substrate can be cited. . Generally, in order to achieve high voltage holding | maintenance characteristics, as described in Unexamined-Japanese-Patent No. 2004-163724 (patent document 5), the method of making the polyimide used for an oriented film into a high imidation ratio is known. However, since the increase in the imidation rate lowers the solubility in a solvent, the solvent range which can be used is limited, and as a result, it becomes difficult to realize favorable applicability. Thus, the improvement of the imidation ratio which can provide high voltage holding | maintenance property has a problem that it becomes a trade-off relationship, since the applicability | paintability greatly deteriorates.

An object of the present invention is to provide a vertically aligned liquid crystal aligning agent which has high voltage retention characteristics and has good applicability to a substrate.

Another object of the present invention is to provide a vertically aligned liquid crystal display device having a high voltage retention characteristic having a liquid crystal alignment film formed of the liquid crystal aligning agent of the present invention.

Further objects and advantages of the invention will be apparent from the following description.

According to the present invention, the above object and advantages of the present invention, first, consists of a polymer consisting of at least one repeating unit of the imide repeating unit represented by the following formula (1a) and the acid repeating unit represented by the formula (1b), Q ¹ in Formula 1a and Q ² in Formula 1b contain at least one of the divalent organic groups represented by the following Formulas 2a and 2b, and at least one of the divalent organic groups represented by the following Formula 3a. It is achieved by the vertical alignment liquid crystal aligning agent characterized by the above-mentioned.

(Wherein

P ¹ represents a tetravalent organic group constituting tetracarboxylic acid,

Q ¹ represents a divalent organic group constituting a diamine.)

(Wherein

P ² represents a tetravalent organic group constituting tetracarboxylic acid,

Q ² represents a divalent organic group constituting a diamine.)

(Wherein

X ¹ is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S-, methylene group, an alkylene group having 2 to 6 carbon atoms or a phenylene group,

R ¹ is a monovalent organic group having an alkyl group having 10 to 20 carbon atoms, an alicyclic skeleton having 4 to 40 carbon atoms, or a monovalent organic group having a fluorine atom having 6 to 20 carbon atoms,

R ² is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms or a divalent organic group having a fluorine atom having 5 to 30 carbon atoms.)

(Wherein

X ² is a methylene group or an alkylene group having 2 to 20 carbon atoms,

R ³ is an aromatic ring-containing skeleton, an organosiloxane skeleton, a divalent organic group represented by -R- (OC ₂ H ₄ ) _n -OR- (R is an alkylene group having 2 to 5 carbon atoms, n is 1 to 100) Divalent organic group represented by -R- (OC ₃ H ₆ ) _n -OR- (R represents an alkylene group having 2 to 5 carbon atoms, n represents 1 to 50), and an alicyclic group having 4 to 40 carbon atoms. It is a divalent organic group which has a formula cyclic skeleton,

^Two or more X <^2> in a formula may respectively be same or different.)

According to the present invention, the above objects and advantages of the present invention include, secondly, P ¹ in Formula 1a and P ² in Formula 1b contain at least one of tetravalent organic groups represented by the following Formulas 4a to 4f. It is achieved by the vertical alignment liquid crystal aligning agent characterized by the above-mentioned.

(In the above formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a monovalent organic group.)

According to the present invention, the above object and advantage of the present invention is, thirdly, P ¹ in the general formula (1a) and P ² in the general formula (1b), at least one of the tetravalent organic groups represented by each of the general formulas (4e) and 4f to 4 with respect to the monovalent organic group (P ¹ + P ²⁾ is achieved by means of the vertical alignment type liquid crystal alignment which is characterized in that it contains at least 50 mol%.

According to the present invention, the above object and advantage of the present invention is that, the fourth, the divalent organic group represented by the formula (3a) contains at least one of the divalent organic groups represented by each of the formulas (5a) to (5e) It is achieved by the vertically-aligned liquid crystal aligning agent set as.

(Wherein

R ^a represents a hydrogen atom or a monovalent organic group,

R ^b is an alkylene group having 1 to 20 carbon atoms,

A plurality of R ^a and R ^b may be the same or different, respectively,

p is an integer from 1 to 99,

q is an integer from 1 to 20.)

According to the present invention, the above object and advantage of the present invention is that, in the polymer, the imide repeating unit is a total of the imide repeating unit represented by the above formula (a) and the acid repeating unit represented by the above formula (1b). It is achieved by the vertically-aligned liquid crystal aligning agent characterized by the imidation polymer which occupies 40 mol% or more.

According to the present invention, the above objects and advantages of the present invention are sixth, at least one epoxy group-containing compound selected from the group consisting of compounds containing at least two epoxy groups in the molecules represented by the formulas (6a) and (6b), respectively; It is achieved by the vertically-aligned liquid crystal aligning agent characterized by containing 1-50 weight part further with respect to 100 weight part of polymers.

(Wherein

s is an integer from 2 to 6,

t is an integer from 1 to 4,

R ^c is an s-valent organic group,

R ^d is a t-valent organic group.)

According to this invention, the said objective and advantage of this invention are 7th achieved by the vertical alignment liquid crystal display element characterized by including the vertical alignment liquid crystal aligning film formed from the said liquid crystal aligning agent of this invention.

The vertical liquid crystal aligning film formed by the liquid crystal aligning agent of this invention is a preferable liquid crystal aligning film which is excellent in the vertical alignment property, has voltage retention characteristics, and has favorable applicability to a board | substrate.

The liquid crystal display element of this invention can be used effectively for various apparatuses, For example, it can be used suitably as display apparatuses, such as a table calculator, a wristwatch, a table clock, a mobile telephone, a counting plate, a word processor, a personal computer, and a liquid crystal television. .

Best Mode for Carrying Out the Invention

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

The vertically-aligned liquid crystal aligning agent (henceforth "the liquid crystal aligning agent of this invention") in this invention consists of a polymer containing a dark acid repeating unit and / or an imide repeating unit as mentioned above. The polymer containing a dark acid repeating unit among the said repeating units (henceforth a "polyamic acid polymer") is obtained, for example by making tetracarboxylic dianhydride and a diamine compound react in an organic solvent. In addition, the polymer containing an imide repeating unit (henceforth an "imidization polymer") is obtained by dehydrating and ring-closing the dark acid part of a polyamic-acid polymer. The polymer containing the dark acid repeating unit and / or the imide repeating unit used in the present invention may be a combination of a polyamic acid polymer and an imidized polymer, or may be a polymer containing a dark acid repeating unit and an imide repeating unit in one polymer. good. Hereinafter, the manufacturing method of the polyamic acid polymer and imidation polymer which can be used for this invention is demonstrated.

Tetracarboxylic dianhydride

As tetracarboxylic dianhydride which can be used for the polyamic-acid polymer and / or polyimide polymer which comprise the liquid crystal aligning agent in this invention, a butane tetracarboxylic dianhydride, the following general formula (IV-1 ⁰ )

(IV-1⁰)

(IV-1 ⁰ )

(R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom or a monovalent organic group.)

Cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4, 4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,4-tricarboxycyclopentylacetic dianhydride, bicyclo [2,2,1] heptane -2,3,5,6-tetracarboxylic dianhydride, 3,5,6-tricarboxynobornane-2-acetic dianhydride, tetracyclo [4,4,0,12,5,17,10] dode Kane-3,4,8,9-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, formula (IV-6 ⁰ )

(IV-6⁰)

(IV-6 ⁰ )

(Wherein R ⁹ is a hydrogen atom or a monovalent organic group)

Dicarboxylic acid dianhydride represented by: 5- (2,5-dioxotetrahydrophthal) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo [2,2,2] -Octo-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2,2,2] -octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, Aliphatic and alicyclic tetracarboxylic dianhydrides such as compounds represented by 1) and (2);

(Herein, R ¹⁰ and R ¹² represent a divalent organic group having an aromatic ring, R ¹¹ and R ¹³ represent a hydrogen atom or an alkyl group, and a plurality of R ¹¹ and R ¹³ may be the same or different, respectively.)

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3', 4,4'-dimethyl Diphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3 , 4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy Diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) Phenylphosphine oxide dianhydride, ethylene glycol bis (Anhai) Low trimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (an Hydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), Aromatic tetracarboxylic dianhydrides, such as the compound represented by (3)-(6), are mentioned. These are used individually by 1 type or in combination of 2 or more types.

Examples of the cyclobutane tetracarboxylic dianhydride represented by the general formula (IV-1 ⁰ ) include 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cycloview Teintetracarboxylic dianhydride, 1,3-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride Water and 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride are mentioned.

Examples of the dicarboxylic acid dianhydride represented by the formula (IV-6 ^0), for example, 1,3,3a, 4,5,9b- hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl Yl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetra Hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7 -Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5, 9b-hexahydro-7-ethyl-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-da Ion, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furan ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione is mentioned.

Among these, cyclobutane tetracarboxylic dianhydride represented by the general formula (IV-1 ⁰ ), such as 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 1,2-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, 1,3-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-tetra methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride; Bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride; 1,2,3,4-cyclopentanetetracarboxylic dianhydride; 1,2,4,5-cyclohexanetetracarboxylic dianhydride; Tetracarboxylic dianhydride represented by the above formula (IV-6 ⁰ ), such as 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-5-methyl-5 (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro-2 , 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl- 5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexa Hydro-7-ethyl-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, 1 , 3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] -furan-1,3-dione; It is preferable to contain 50 mol% or more of at least 1 sort (s) of tetracarboxylic dianhydride chosen from 2,3,5- tricarboxy cyclopentyl acetic dianhydride with respect to all tetracarboxylic dianhydride, and 70 mol from a viewpoint of a characteristic improvement. % Or more is more preferable.

[Diamine Compound]

The group represented by each of said Formula (2a), (2b) and (3a) which each of Q <^1> and Q <^2> in the repeating unit represented by the said Formula (1a) and (1b) represents is a group derived from diamine, and removes two amino groups from diamine. Corresponds to the residue.

In the above formula (2a), as the alkyl group having 10 to 20 carbon atoms represented by R ¹ , for example, n-decyl group, n-dodecyl group, n-pentadecyl group, n-hexadecyl group, n-octadecyl group, n- Eicosyl group etc. are mentioned. Examples of the monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms include alicyclic skeletons derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, and cyclodecane; Bridged alicyclic skeletons such as norbornene and adamantane; And monovalent organic groups having a steroid skeleton such as cholesterol and cholestanol. The monovalent organic group having the alicyclic skeleton may be a group substituted with a halogen atom, preferably a fluorine atom. Moreover, as monovalent organic group which has a C6-C20 fluorine atom, C6-C20 linear alkyl groups, such as n-hexyl group, n-octyl group, n-decyl group; Alicyclic hydrocarbon groups having 6 to 20 carbon atoms such as a cyclohexyl group and a cyclooctyl group; The group which substituted one part or all hydrogen atoms in organic groups, such as a C6-C20 aromatic hydrocarbon group, such as a phenyl group and a biphenyl group, with the fluorine atom or the fluoroalkyl group is mentioned. In addition, in the formula (2a), the group represented by X ¹ is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S-, methylene group, carbon number It is an alkylene group or phenylene group of 2-6, The group represented by -O-, -CO-, -COO-, -OCO- is especially preferable among these.

Specific examples of the diamine having a group represented by the formula (2a) include dodecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, and octa. Decaneoxy-2, 4- diamino benzene and the compound represented by following General formula (7)-(21) are mentioned as a preferable thing.

Next, in the above formula (2a), examples of the divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms represented by R ² include cycloalane, cyclopentane, cyclohexane, cyclodecane and the like. Alicyclic skeleton derived from kane; Bridged alicyclic skeletons such as norbornene and adamantane; And divalent organic groups having a steroid skeleton such as cholesterol and cholestanol. The divalent organic group having the alicyclic skeleton may be a group substituted with a halogen atom, preferably a fluorine atom.

As a specific example of the diamine which has group represented by the said General formula (2b), the compound represented by following General formula (22)-(26) is mentioned as a preferable thing.

In the polyamic acid polymer and / or polyimide polymer of the present invention, the ratio of the divalent organic group represented by each of the general formulas (2a) and (2b) is preferably 7 moles with respect to the total amount of diamine in terms of vertical alignment. It is% or more, More preferably, it is 10 mol% or more.

Next, as said bivalent organic group which has an aromatic ring containing skeleton represented by R <^3> in the said General formula (3a), a phenylene group, a biphenylene group, a naphthylene group, a methylene diphenylene group, an oxydiphenylene group is mentioned, for example. have. Arbitrary hydrogen of the aromatic ring in these aromatic ring containing skeletons may be substituted by halogen or a C1-C5 alkyl group. As a divalent organic group which has organosiloxane frame | skeleton, a tetramethyl disiloxane group etc. are mentioned, for example. Examples of the divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms include alicyclic skeletons derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, and cyclodecane; And divalent organic groups having a bridged alicyclic skeleton such as norbornene and adamantane. The divalent organic group having the alicyclic skeleton may be a group substituted with a halogen atom, preferably a fluorine atom.

Specific examples of the diamine having a group represented by the formula (3a) include 1,4-bis (aminomethyl) -bicyclo [2,2,1] heptane, 1,4-bis (aminopropyl) -bicyclo [2, 2,1] heptane, isophoronediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminopropyl) cyclohexane , Metaxylenediamine, paraxylenediamine, 3,3 '-(hexamethyltrisiloxane-1,3-diyl) bis (propylamine), a compound represented by the following formulas (27) and (28) Etc. are mentioned as a preferable thing.

(Wherein n is an integer of 1 to 100).

 In the polyamic acid polymer and / or polyimide polymer of the present invention, the ratio of the divalent organic group represented by the above formula (3a) is preferably 2% or more based on the total amount of diamine from the viewpoint of improving the solubility of the polymer. More preferably, it is 5% or more.

In the synthesis of the polyamic acid polymer and / or polyimide polymer used in the present invention, other diamine compounds can be used in combination to the extent that the effects of the present invention are not impaired. Examples of other diamine compounds include p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-ethyl-1,4-phenylenediamine, 2,5-dimethyl-1,4 -Phenylenediamine, 2,5-diethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, m-phenylenediamine, 4 , 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 2,2'-di Methyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diamino Biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-di (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-di Ethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobar Phenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylinde, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethyl Phosphorus, 3,4'-diaminodiphenylether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [ 4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) propane , 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene , 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7- Diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4 '-Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybar Phenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenylene Isopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoro methylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2 ' -Bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 4- (4-n-heptylcyclohexyl Aromatic diamines such as phenoxy-2,4-diaminobenzene;

1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, etc. Aliphatic diamines;

2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5 , 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 2,4-diamino-6-isopropoxy -1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine , 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2 , 4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole , 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis ( In a molecule, such as 4-aminophenyl) phenylamine Diamines having two primary amino groups and nitrogen atoms other than this primary amino group;

The compound etc. which are represented by following General formula (29) and (30) are mentioned. These diamine compounds can be used individually or in combination of 2 or more types.

(In formula, y is an integer of 2-12, z is an integer of 1-5.)

Among them, p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-ethyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenedia Min, 2,5-diethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-diethyl-4 , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 3,3'- Di (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-diaminodiphenylether, 4,4'-diaminobenzophenone, 2,2-bis (4-aminophenyl ) Propane, 2, 2-bis (4-aminophenyl) hexafluoro propane, 2, 6- diamino pyridine, 3, 4- diamino pyridine, etc. are mentioned as a preferable example.

[Synthesis of Polyamic Acid]

The use ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction is preferably a ratio in which the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2.0 equivalents to 1 equivalent of the amino group of the diamine, more preferably 0.8. To 1.2 equivalents. The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under a temperature condition of -20 ° C to 150 ° C, more preferably 0 to 100 ° C.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized. Examples of the organic solvent include 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethyl urea and hexamethylphosphotriamide; Phenol solvents, such as m-cresol, a xylenol, a phenol, and a halogenated phenol, can be illustrated. In addition, it is preferable that the usage-amount of (alpha) of an organic solvent is an amount which becomes 0.1 to 30 weight% with respect to the total amount ((beta)) of tetracarboxylic dianhydride and a diamine compound, with respect to the total amount ((alpha) + (beta)) of a reaction solution.

In addition, the said organic solvent can use together the alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon etc. which are poor solvents of polyamic acid in the range which does not precipitate polyamic acid produced. Specific examples of such poor solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4- Butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl Methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, 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, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether , Diethylene glycol Ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, Dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene Etc. can be mentioned.

As described above, a reaction solution formed by dissolving polyamic acid is obtained. The reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the polyamic acid can be obtained by drying the precipitate under reduced pressure. Moreover, polyamic acid can be refine | purified by carrying out the process which dissolves this polyamic acid again in an organic solvent, and then precipitates with a poor solvent once or several times.

[Synthesis of imidized polymer]

The imidation polymer which comprises the liquid crystal aligning agent of this invention can be synthesize | combined by dehydrating and ring-closing the said polyamic acid. The imidized polymer used in the present invention may be partially dehydrated and closed in an imidization ratio of less than 100%. The "imidation ratio" here is the value which showed the ratio of the repeating unit which has an imide ring or an isoimide ring in all the repeating units of a polymer as a percentage. 40% or more is preferable and, as for the imidation ratio of the polyamic acid polymer and / or imidation polymer used for this invention, 70% or more is more preferable from a voltage retention characteristic. The dehydration ring closure of polyamic acid may be carried out by (i) heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating phenyl ring catalyst, and heating it as necessary. , A method of condensation and synthesis is used.

The reaction temperature in the method of heating the polyamic acid of said (i) becomes like this. Preferably it 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.

On the other hand, in the method of adding the dehydrating agent and the dehydrating ring catalyst in the solution of the polyamic acid of the above (ii), acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride and the like can be used as the dehydrating agent. 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 repeating units of polyamic acid. As the dehydration cyclic ring catalyst, tertiary amines such as pyridine, collidine and triethylamine can be used, for example. However, it is not limited to these. 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 made higher, so that the usage-amount of the said dehydrating agent and dehydration ring closure agent is large. On the other hand, as an organic solvent used for dehydration ring-closure reaction, the thing similar to the organic catalyst illustrated as what is used for the synthesis | combination of polyamic acid is mentioned. And the reaction temperature of a dehydration ring-closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. Moreover, the imidation polymer can be refine | purified by performing the same operation as the purification method of polyamic acid about the reaction solution obtained in this way.

[Terminal Modified Polymer]

The polyamic acid / imidized polymer of the present invention may be a terminal modified form having a molecular weight controlled. By using this terminal modified polymer, the coating property of a liquid crystal aligning agent, etc. can be improved, without the effect of this invention being impaired. Such a terminal-modified polymer can be synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound and the like to the reaction system when synthesizing the polyamic acid. Here, examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and the like. Can be mentioned. As the monoamine compound, for example, 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-eico Silamine etc. are mentioned. Moreover, as a monoisocyanate compound, a phenyl isocyanate, a naphthyl isocyanate, etc. are mentioned, for example.

Algebraic Viscosity of Polymers

The polyamic acid and / or imidized polymer obtained as described above has a logarithmic viscosity (η _ln ) of preferably 0.05 to 10 dl / g, more preferably 0.05 to 5 dl / g.

The value of the logarithmic viscosity (η _ln ) in the present invention uses N-methyl-2-pyrrolidone as a solvent, and the viscosity is measured at 30 ° C with respect to a solution having a concentration of 0.5 g / 100 ml. obtained by (i).

(i)

(i)

[Imidation Rate of Polymer]

As for the imidation polymer obtained by making it above, it is preferable that the imidation ratio is 50-100% from a viewpoint of the improvement of a voltage retention characteristic, It is more preferable that it is 65-100%, Furthermore, it is 75-100% desirable.

Already been values of the imidization ratio of the imidized polymer of the present invention, and then dried under reduced pressure the already encoded in the polymer 60 ℃, dissolved in deuterated dimethyl sulfoxide, ¹ H- at room temperature to a tetramethyl silane as the reference substance NMR was measured and calculated | required by the formula represented by following formula (ii).

Imidation ratio (%) = (1-A1 / A2 × α) × 100. … (ii)

A1: peak area (10 ppm) derived from proton of NH group

A2: peak area (7-8 ppm) derived from proton derived from aromatic ring

(alpha): The number ratio of the proton derived from an aromatic ring with respect to one proton of NH group in the precursor (polyamic acid) of a polymer.

[Vertical Alignment Type Liquid Crystal Alignment Agent]

In order to obtain the liquid crystal aligning agent of this invention, the said polyamic acid polymer and / or this imidation polymer are preferably melt | dissolved in an organic solvent, and are comprised. Moreover, the temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0 degreeC-200 degreeC, More preferably, it is 20 degreeC-60 degreeC.

As an organic solvent which comprises the liquid crystal aligning agent of this invention, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N-di Methylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol Colmethyl 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 Tyl ether acetate etc. are mentioned. Among these, as a preferable solvent composition, it is a composition obtained by combining the said solvent, and is a composition in which a polymer does not precipitate in an alignment agent and the surface tension of an alignment agent falls in the range of 30-40 mN / m.

Although solid content concentration in the liquid crystal aligning agent of this invention is selected in consideration of viscosity, volatility, etc., Preferably it exists in the range of 1 to 10 weight%. That is, although the liquid crystal aligning agent of this invention is apply | coated to the board | substrate surface, and the resin film used as a liquid crystal aligning film is formed, when solid content concentration is less than 1 weight%, the film thickness of this resin film becomes too small and a favorable liquid crystal aligning film can be obtained. If the solid content concentration exceeds 10% by weight, the film thickness of the resin film becomes too large to obtain a good liquid crystal aligning film, and the viscosity of the liquid crystal aligning agent increases, resulting in inferior coating properties. On the other hand, 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% 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 4 to 10% by weight, and thereby the solution viscosity is in the range of 10 to 50 mPa · s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 2 to 5% by weight, and thereby the solution viscosity is in the range of 5 to 15 mPa · s.

The liquid crystal aligning agent of this invention may contain the epoxy group containing compound represented by following formula (6a) and 6b in the range which does not impair the desired physical property.

Formula 6a

Formula 6b

(Wherein

s is an integer from 2 to 6,

t is an integer from 1 to 4,

R ^c is an s-valent organic group,

R ^d is a t-valent organic group.)

Examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol diglycidyl. , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerine diglycidyl ether, 2 , 2-dibromoneopentylglycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetra Glycidyl-p-phenylenediamine, N, N, N ', N'-tetraglycidyl-m-xylenediamine, N, N, N', N'-tetraglycidyl-2, 2'-dimethyl-4,4'-diaminobiphenyl, 2,2-bis [4- (N, N-diglycidyl-4-aminophenoxy) phenyl] propane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 1,3-bis (N, N-di Lycidylaminomethyl) cyclohexane, 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,3-bis (N, N-diglycidylaminomethyl) benzene, N , N, N ', N'- tetraglycidyl-m-xylenediamine, etc. are mentioned. As content of such an epoxy group containing compound, Preferably it is 1-50 weight part with respect to 100 weight part of polymers, More preferably, it contains 5-45 weight part.

Moreover, the functional silane containing compound may be contained in the liquid crystal aligning agent of this invention from a viewpoint of improving the adhesiveness to the surface of a board | substrate within the range which does not impair a desired physical property. Examples of such functional silane-containing compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropylethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxy Silylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7- Triazadecane, 9-trimethoxysilyl-3,6-diazonyl acetate, 9-triethoxysilyl-3,6 Diazononyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- Phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N- diglycidyl) aminopropyltrimethoxysilane, etc. are mentioned.

[Manufacture of Display Element Using Liquid Crystal Alignment Agent]

The liquid crystal display element using the vertically-aligned liquid crystal aligning agent of this invention can be manufactured, for example by the following method.

(1) The liquid crystal aligning agent of this invention is apply | coated to the one surface of the board | substrate with which the patterned transparent conductive film is provided by methods, such as a roll coater method, a spinner method, the printing method, the ink manufacturing method, and then a coating surface is heated. This forms a coating film. Here, as a board | substrate, For example, glass, such as floating glass and a soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, or the like can be used. Examples of the transparent conductive film provided on one side of the substrate include an NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG, USA), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), and the like. It is available. The photoetching method and the method using a preliminary mask are used for patterning these transparent conductive films. In application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a surface of a board | substrate and a resin film more favorable, it is also possible to apply previously a functional silane containing compound, a functional titanium containing compound, etc. in advance. The heating temperature after apply | coating a liquid crystal aligning agent becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. On the other hand, the liquid crystal aligning agent of this invention forms the resin film used as an oriented film by removing an organic solvent after application | coating, but when imidation is not fully advanced yet, further heating advances dehydration ring closure, and the imidized resin film You can do The film thickness of the resin film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(2) As described above, two substrates having a vertical liquid crystal alignment film were formed, and two substrates were arranged to face each other through a gap (cell gap), and the peripheral portions of the two substrates were bonded together using a sealing agent, and the substrate Liquid crystal is injected and filled into the cell gap partitioned by the surface and the sealing agent, and the injection hole is sealed to form a liquid crystal cell. And a liquid crystal display element is obtained by arrange | positioning a polarizing plate in the outer surface of a liquid crystal cell, ie, the transparent substrate side which comprises a liquid crystal cell.

As the sealing agent, for example, an epoxy resin or the like containing an aluminum oxide sphere as a curing agent and a spacer can be used.

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Especially, a nematic type liquid crystal is preferable, For example, a Schiff base type liquid crystal, a subfamily clock liquid crystal, a biphenyl type liquid crystal, a phenyl cyclohexane type liquid crystal, an ester type liquid crystal, a terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal Pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cuban-based liquid crystals, and the like. In addition, these liquid crystals are commercially available as cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, and cholesteryl carbonate, and commercially available products such as trade names "C-15" and "CB-15" (manufactured by Merck). A chiral agent can be added and used. In addition, ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

Moreover, as a polarizing plate which can be bonded to the outer surface of a liquid crystal cell, the polarizing plate which made the polarizing film called H film which absorbed iodine absorbed with the cellulose acetate protective film, extending | stretching polyvinyl alcohol, and the polarizing plate which consists of H films themselves are mentioned. Can be.

Example

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.

In addition, various measurements of the Example and the comparative example were performed by the following method.

(1) vertical orientation evaluation

Light leakage or the like when the vertically aligned liquid crystal display device produced by the above method is visually observed from the vertical direction with respect to the liquid crystal display device when no voltage is applied and when an alternating voltage of 8V (peak-peak) is applied under cross nicol. When there was no display defect and it became white display, it said "good".

(2) Measurement of voltage retention

After applying a voltage of 5 V to a liquid crystal display element at 60 degreeC by the application time of 60 microseconds and the span of 16.7 microseconds, the voltage retention after 16.7 milliseconds after application | release cancellation was measured.

(3) Solubility Evaluation of Polymer

Γ-butyrolactone: N-methyl-2-pyrrolidone: butyl cellosolve = 40 with a viscosity of 15 to 25 mPasec (solid content concentration of 6.0 wt% to 8.0 wt%) and solvent composition as the total amount of solvent : When prepared to be (60-A): A (weight ratio), the presence or absence of suspension was observed visually, and even if content A of the butyl cellosolve which is an empty solvent was 30 or more, it was called "good". .

(4) printability evaluation

After coating and baking by the printing method using the said preparation solution about the thing favorable in "the solubility evaluation of a polymer" of said (4), the coating film was observed visually. With respect to the coating film, those having no leakage or coating nonuniformity were referred to as "good".

Synthesis Examples 1 to 25, Comparative Synthesis Examples 1 to 6

N-methyl-2-pyrrolidone was added to the compositions shown in Tables 1 and 2 in the order of diamine and tetracarboxylic dianhydride (indicated as `` acid anhydride '' in the table) to give a solid content of 20% by weight. As a solution, it was made to react at 60 degreeC for 4 hours, and the polyamic acid polymer was obtained. The obtained polyamic acid polymer was added with the number of moles of times the pyridine and acetic anhydride shown in Table 1 with respect to the total amount of the polyamic acid polymer, and then heated to 110 ° C. to perform a dehydration ring closure reaction for 4 hours. The obtained solution was reprecipitated with diethyl ether, and then recovered and dried under reduced pressure to give the logarithmic viscosity shown in Tables 1 and 2, (A-1) to (A-25), which are imidization polymers, and (a-1) to (a-6) were obtained.

In Table 1 and Table 2, about a diamine compound and an acid anhydride, the number in parentheses shows a content rate, and the meaning of the symbol in a table | surface is as follows.

<Diamine Compound>

D-1: diamine represented by the above formula (10)

D-2: diamine represented by the general formula (11)

D-3: diamine represented by the above formula (14)

D-4: diamine represented by the above formula (20)

D-5: 1,4-bis (aminomethyl) -bicyclo [2.2.1] heptane

D-6: 1,3-bis (aminomethyl) cyclohexane

D-7: metaxylenediamine

D-8: 3,3 '-(tetramethyldisiloxane-1,3-diyl) bis (propylamine)

D-9: diamine represented by the general formula (28) (average molecular weight 1,000)

D-10: p-phenylenediamine

D-11: 4,4'-diaminodiphenylmethane

D-12: 4,4'-diaminodiphenyl ether

D-13: 2,2'-dimethyl-4,4'-diaminobiphenyl

<Tetracarboxylic dianhydride>

T-1: 1,2,4,5-cyclohexanetetracarboxylic dianhydride

T-2: 2,3,5-tricarboxycyclopentyl acetic dianhydride

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

T-4: 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] Furan-1,3-dione

T-5: pyromellitic dianhydride

Example 1

The imidized polymer (A-1) obtained in the synthesis example 1 was dissolved in (gamma) -butyrolactone / N-methyl- 2-pyrrolidone / butyl cellosolve mixed solution (weight ratio 40/30/30), 20 weight part of polyethyleneglycol diglycidyl ether (molecular weight: about 400; additive A) was melt | dissolved with respect to 100 weight part of polymers, and it was set as the solution of 6 weight% of solid content concentration. When the solution was visually observed, it was confirmed that good solubility was obtained from the result that a clear and clear solution was obtained. Subsequently, after filtering using the filter of 0.2 micrometer of pore diameters to prepare the composition for film formation of this invention, when printability evaluation was performed, it was confirmed that leakage and coating nonuniformity were not seen in a coating film, and it had favorable printability. .

Next, the film forming composition of the present invention was prepared in the same manner as above except that the solid content concentration was 4%.

Next, the film-forming composition was coated with a spinner on a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm, and dried at 200 ° C. for 60 minutes to form a film having a dry film thickness of 0.08 μm. Formed.

Next, after apply | coating the epoxy resin adhesive in which the aluminum oxide sphere of diameter 3.5 micrometers was mixed in each outer edge which has the liquid crystal aligning film of the said liquid crystal aligning film coating board | substrate of a pair of transparent electrode / transparent electrode board | substrate, the liquid crystal aligning film surface They were stacked so as to face each other, and the adhesive was cured. Subsequently, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between board | substrates from a liquid crystal injection hole, the liquid crystal injection hole was sealed with the acryl-type photocuring adhesive agent, and the liquid crystal display element was produced. It was favorable when vertical orientation evaluation was performed about the obtained liquid crystal display element. Moreover, when voltage retention was measured, it was 99% or more, and showed favorable voltage retention characteristic. The results are summarized in Table 3.

Examples 2 to 67, Comparative Examples 1 to 11

According to the formulations shown in Tables 3 and 4 below, as in Example 1, a film-forming composition having a solid content concentration of 6% was prepared to evaluate solubility and printability. In addition, the composition for film formation of 4% of solid content concentration was similarly prepared, and the liquid crystal display element was produced. And vertical orientation evaluation and voltage retention were performed. The results are shown in Tables 3, 4, and 5 together.

In Table 3, Table 4, and Table 5, in an additive, the number in parentheses shows a content rate, and the meaning of the symbol in a table | surface is as follows.

<Additive>

Additive A: Polyethylene glycol diglycidyl ether (molecular weight about 400)

Additive B: 1,6-hexanediol diglycidyl ether

Additive C: N, N, N ', N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl

Additive D: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

Additive E: 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane

Additive F: N, N, N ', N'-tetraglycidyl-m-xylenediamine

The vertical liquid crystal aligning film formed by the liquid crystal aligning agent of this invention is a preferable liquid crystal aligning film which is excellent in the vertical alignment property, has high voltage retention characteristic, and has favorable applicability to a board | substrate.

The liquid crystal display element of this invention can be used effectively for various apparatuses, For example, it can be used suitably as display apparatuses, such as a table calculator, a wristwatch, a table clock, a mobile telephone, a counting plate, a word processor, a personal computer, and a liquid crystal television. .

Claims (7)

A polymer composed of a repeating unit of at least one of an acid repeating unit represented by Formula 1a and an imide repeating unit represented by Formula 1b, wherein Q ¹ in Formula 1a and Q ² in Formula 1b are represented by Formula 2a And at least one of the divalent organic groups represented by each of 2b and at least one of the divalent organic groups represented by the following general formula (3a). Formula 1a

(Wherein P ¹ represents a tetravalent organic group constituting tetracarboxylic acid, Q ¹ represents a divalent organic group constituting a diamine.) Formula 1b

(Wherein P ² represents a tetravalent organic group constituting tetracarboxylic acid, Q ² represents a divalent organic group constituting a diamine.) Formula 2a

Formula 2b

(Wherein X ¹ is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S-, methylene group, an alkylene group having 2 to 6 carbon atoms or a phenylene group, R ¹ is a monovalent organic group having an alkyl group having 10 to 20 carbon atoms, an alicyclic skeleton having 4 to 40 carbon atoms, or a monovalent organic group having a fluorine atom having 6 to 20 carbon atoms, R ² is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms or a divalent organic group having a fluorine atom having 5 to 30 carbon atoms.) Formula 3a

(Wherein X ² is a methylene group or an alkylene group having 2 to 20 carbon atoms, R ³ is an aromatic ring-containing skeleton, an organosiloxane skeleton, a divalent organic group represented by -R- (OC ₂ H ₄ ) _n -OR- (R is an alkylene group having 2 to 5 carbon atoms, n is 1 to 100) Divalent organic group represented by -R- (OC ₃ H ₆ ) _n -OR- (R represents an alkylene group having 2 to 5 carbon atoms, n represents 1 to 50), and an alicyclic group having 4 to 40 carbon atoms. It is a divalent organic group which has a formula cyclic skeleton, ^Two or more X <^2> in a formula may respectively be same or different.) The method of claim 1, P ¹ in the general formula (1a) and P ² in the general formula (1b) contain at least one kind of tetravalent organic groups represented by each of the following general formulas (4a) to (4f). Formula 4a

Formula 4b

Formula 4c

Formula 4d

Formula 4e

Formula 4f

(In the above formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a monovalent organic group.) The method of claim 2, 50 mol% or more of P ¹ in Formula 1a and P ² in Formula 1b represent at least one of the tetravalent organic groups represented by each of Formulas 4e and 4f with respect to the total tetravalent organic groups (P ¹ + P ² ). The vertically-aligned liquid crystal aligning agent to contain. The method according to any one of claims 1 to 3, The vertically-aligned liquid crystal aligning agent in which the divalent organic group represented by the said General formula (3a) contains at least 1 sort (s) of the divalent organic group represented by each of following General formulas 5a-5e. Formula 5a

Formula 5b

Formula 5c

Chemical Formula 5d

Formula 5e

(Wherein R ^a represents a hydrogen atom or a monovalent organic group, R ^b is an alkylene group having 1 to 20 carbon atoms, A plurality of R ^a and R ^b may be the same or different, respectively, p is an integer from 1 to 99, q is an integer from 1 to 20.) The method of claim 1, Vertically-aligned liquid crystal aligning agent whose said polymer is an imidization polymer in which the said imide repeating unit occupies 40 mol% or more with respect to the sum total of the dark acid repeating unit represented by the said Formula (1a), and the imide repeating unit represented by the said Formula (1b). . The method of claim 1, Further containing 1 to 50 parts by weight of at least one epoxy group-containing compound selected from the group consisting of compounds containing at least two epoxy groups in the molecules represented by the formulas (6a) and (6b), respectively, relative to 100 parts by weight of the polymer Vertically-aligned liquid crystal aligning agent. Formula 6a

Formula 6b

(Wherein s is an integer from 2 to 6, t is an integer from 1 to 4, R ^c is an s-valent organic group, R ^d is a t-valent organic group.) The vertical alignment liquid crystal display element provided with the vertical alignment liquid crystal aligning film formed from the vertical alignment liquid crystal aligning agent of any one of Claims 1-6.