CN105273725B - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element, which have good storage stability and coating property on a substrate, and can obtain a liquid crystal having well-balanced electrical characteristics, liquid crystal orientation, and heat resistance. Display components. The liquid crystal aligning agent of the present invention contains one or two or more polymers as a polymer component, and the partial structure (a-1) represented by the following formula (1) and the following Partial structure (a-2) represented by formula (2). Among them, R ¹ and R ² are hydrogen atoms, alkyl groups with 1 to 12 carbons, etc., R ³ and R ⁴ are hydrogen atoms or substituted or unsubstituted monovalent chain hydrocarbon groups with 1 to 10 carbons; X ¹ and X ² are tetravalent organic groups, and Y ¹ and Y ² are divalent organic groups.

Description

Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element

technical field

The invention relates to a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element.

Background technique

In the past, liquid crystal display elements have developed a variety of driving methods with different electrode structures, physical properties of liquid crystal molecules used, and manufacturing steps, such as known twisted nematic (Twisted Nematic, TN) type or super twisted nematic (SuperTwisted Nematic) , STN) type, vertical alignment (Vertical Alignment, VA) type, in-plane switching (In-PlaneSwitching, IPS) type, fringe field switching (Fringe Field Switching, FFS) type and other liquid crystal display elements. These liquid crystal display elements have a liquid crystal aligning film for aligning liquid crystal molecules. Polyamic acid or polyimide is generally used as a material of a liquid crystal aligning film at the point that various characteristics, such as heat resistance, mechanical strength, and affinity with a liquid crystal, are favorable. In addition, the method of forming a liquid crystal aligning film on a substrate using polyamic acid or polyimide is generally used, for example: coating a solution containing polyamic acid on a substrate, heating it, and forming an imide film on the substrate. A method of forming a polyimide film; a method of coating a solution containing a soluble polyimide on a substrate, removing the solvent from the substrate to form a polyimide film, and the like.

In addition, in recent years, large-screen and high-definition liquid crystal televisions have become the mainstay, and the demand for reducing display defects has become stricter, and a highly reliable liquid crystal display element that can withstand long-term use in harsh environments is also required. In order to satisfy the said request, various liquid crystal aligning agents have been proposed in recent years. As one of the aspects, it is attempted to contain several types of polymers in a liquid crystal aligning agent (for example, refer patent document 1 or patent document 2).

Patent Document 1 discloses not only making polyamic acid ester and polyamic acid contained in a liquid crystal aligning agent as a polymer component, but also making the weight average molecular weight of polyamic acid ester smaller than polyamic acid. It is described that the liquid crystal aligning agent described in this patent document 1 can reduce the fine unevenness|corrugation which arises in the film surface of a liquid crystal aligning film, and can improve the liquid crystal orientation and electrical characteristics of a liquid crystal display element.

Moreover, patent document 2 proposes the liquid crystal aligning agent containing a polyamic acid ester and a soluble polyimide. In the liquid crystal aligning agent described in this patent document 2, it is described that even if the imidization rate is high, no whitening phenomenon occurs when the coating film is formed, the printability and the rubbing resistance of the coating film are good, and the liquid crystal display can be improved. Liquid crystal orientation and electrical characteristics of the device.

[Prior art literature]

[Patent Document]

[Patent Document 1] International Publication No. 2011/115078

[Patent Document 2] International Publication No. 2013/147083

Contents of the invention

[Problem to be solved by the invention]

In recent years, the demand for higher definition and longer life of liquid crystal displays has been further increased, and further improvements have been demanded for basic properties such as electrical characteristics, liquid crystal orientation, and heat resistance of liquid crystal display elements. Moreover, as a liquid crystal aligning agent, storage stability and the applicability (printability) to a board|substrate are requested|required to be favorable from viewpoints, such as improvement of the convenience at the time of industrial use, and a yield.

The present invention was made in view of the above problems, and one of the objects is to provide a liquid crystal display that has good storage stability and coating properties on substrates, and that can obtain well-balanced electrical characteristics, liquid crystal orientation, and heat resistance. Liquid crystal alignment agent for components.

[Technical means to solve the problem]

The inventors of the present invention firstly related to the four kinds of polymers of polyamic acid, polyimide, polyamic acid ester and polyisoimide, the storage stability of each polymer, the thermal imidization rate and the substrate coating properties were studied. Furthermore, among these four kinds of polymers, focusing on polyisoimides with low storage stability but good thermal imidization rate and coatability, attempts were made to combine the isoimide rings of polyisoimides The structure is combined with other partial structures to improve various properties of the liquid crystal aligning agent and the liquid crystal display element. And as a result of such an attempt, the said problem was solved by the combination of an isoimide ring structure, an amic acid structure, and an amic acid ester structure, and at least some structure, and this invention was completed. Specifically, the present invention provides the following liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element.

One aspect of the present invention is to provide a liquid crystal aligning agent, which contains one or two or more polymers as a polymer component, and includes a partial structure represented by the following formula (1) in the polymer component ( a-1), and a partial structure (a-2) represented by the following formula (2).

[chemical 1]

In formula (1) and formula (2), R ¹ and R ² are independently a hydrogen atom, an alkyl group with 1 to 12 carbons, -Si(R ⁷ ) ₃ (wherein, R ⁷ is an alkyl or alkoxy A plurality of R ⁷ can be the same or different), a monovalent group with a fluorine atom, a monovalent group with a (meth)acryloyl group, or a monovalent group with a cinnamic acid structure, R ³ and R ⁴ are respectively independently a hydrogen atom or a substituted or unsubstituted monovalent chain hydrocarbon group with 1 to 10 carbons; X ¹ and X ² are independently a tetravalent organic group, and Y ¹ and Y ² are independently a divalent Organic based.

Another aspect of this invention provides the liquid crystal display element provided with the liquid crystal aligning film formed using the said liquid crystal aligning agent, and this liquid crystal aligning film.

[Effect of the invention]

According to this invention, the favorable liquid crystal aligning agent of storage stability and the applicability to a board|substrate can be obtained. Moreover, by using the said liquid crystal aligning agent, the liquid crystal display element which has electrical characteristics, liquid crystal orientation, and heat resistance well-balanced can be obtained.

Description of drawings

FIG. 1 is a schematic configuration diagram of an FFS type liquid crystal display element.

(a) and (b) of FIG. 2 are schematic plan views of the top electrode. Fig. 2(a) is a plan view of the top electrode, and Fig. 2(b) is a partially enlarged view of the top electrode.

Fig. 3 is a schematic diagram showing four systems of driving electrodes.

[explanation of the symbol]

10: Liquid crystal display element

11a, 11b: glass substrate

12: Liquid crystal alignment film

13: Top electrode

14: insulation layer

15: Bottom electrode

16: Liquid crystal layer

A, B: electrode

C1: partial

d1: line width of the electrode

d2: Distance between electrodes

Detailed ways

＜Polymer composition＞

The liquid crystal aligning agent of the present invention contains one or more polymers as polymer components, and the polymer components contain the partial structure (a-1) represented by the formula (1) and the formula (2) Partial structure (a-2) shown.

Regarding the partial structure (a-1), R ¹ and R ² of the formula (1) are a hydrogen atom, an alkyl group with 1 to 12 carbons, -Si(R ⁷ ) ₃ (wherein, R ⁷ is an alkyl group or Alkoxy group, multiple R ⁷ may be the same or different), a monovalent group with a fluorine atom, a monovalent group with a (meth)acryloyl group, or a monovalent group with a cinnamic acid structure.

Here, examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, deca Dialkyl groups and the like, these alkyl groups may be linear or branched. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and is especially preferably a methyl group or an ethyl group, from the viewpoint of vaporization by post-baking during film formation.

In the group "-Si(R ⁷ ) ₃ ", the alkyl group and alkoxy group of R ⁷ preferably have 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. In addition, a plurality of R ⁷ may be the same or different.

The monovalent group having a fluorine atom includes, for example, a fluorinated alkyl group, a fluorinated alkoxy group, a fluorinated alkyl ester group, etc., and is preferably a fluorinated alkyl group. The fluorinated alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.

Examples of the monovalent group having a (meth)acryloyl group include groups represented by "-R ⁸ -A ³ " (where R ⁸ is a divalent organic group and A ³ is a (meth)acryloyl group). Wait. Examples of divalent organic groups for R ⁸ include -CH ₂ -CH ₂ -O-*, -CH ₂ -CH ₂ -NH-*, -CH(CH ₃ )-CH ₂ -O-*, and -CH( CH ₃ )-CH ₂ -NH-* (wherein, the bonding bond with "*" is bonded to A ³ ) as a preferable specific example. In addition, "(meth)acryloyl" means including acryloyl and methacryloyl.

The monovalent group having a cinnamic acid structure is not particularly limited as long as it contains cinnamic acid or a derivative thereof as a basic skeleton. As a preferable specific example, the group represented by following formula (x-1), the group represented by following formula (x-2), etc. are mentioned, for example.

[Chem 2]

In formula (x-1) and formula (x-2), R ¹¹ and R ¹⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group with 1 to 20 carbons, or a fluoroalkyl group with 1 to 20 carbons; X ¹¹ , X ¹² and X ¹³ are each independently a single bond, an oxygen atom, a sulfur atom, *-COO- or *-OCO- (wherein, the bond with "*" is connected to R ¹¹ , R ¹² or R ¹⁴ Bonding); R ¹² and R ¹⁵ are independently 1,4-phenylene or 1,4-cyclohexylene; X ¹⁴ is a single bond, an alkanediyl group with 1 to 3 carbons, an oxygen atom, a sulfur atom Or -NH-; X ¹⁵ is an oxygen atom, *-COO- or *-OCO- (wherein, the bonding bond with "*" is bonded to R ¹⁶ ); R ¹⁶ is a divalent aromatic group, a divalent lipid Cyclic group, divalent heterocyclic group or divalent condensed cyclic group; R ¹⁷ is a single bond, *-OCO-(CH ₂ ) _h - or *-O-(CH ₂ ) _i - (wherein, with The bonding bond of "*" is bonded to R ¹⁶ , h and i are integers from 1 to 10 respectively); X ¹⁶ is *-COO- or *-OCO- (wherein, the bonding bond with "*" is bonded to R ¹⁷ Bonding); R ¹³ and R ¹⁸ are each independently a fluorine atom, a cyano group or a methyl group; a, e, and d are each independently an integer of 0 to 3, b and f are each independently an integer of 1 to 10, c and g are each independently an integer of 0-4.

As a preferred specific example of the monovalent group having a cinnamic acid structure, the group represented by the formula (x-1) can include, for example, the following formula (x-1-1) to formula (x-1-11 ) and the like respectively; the groups represented by the formula (x-2) include, for example, compounds represented by the following formula (x-2-1) to formula (x-2-3), etc. ; Other examples include groups described in JP-A-2011-133825.

[Chem 3]

In the formula, R ¹¹ and b have the same meaning as R ¹¹ and b in the formula (x-1).

[chemical 4]

In the formula, R ¹⁴ and f have the same meaning as R ¹⁴ and f in the formula (x-2).

From the viewpoint of suppressing quality degradation caused by impurities originating in R ¹ and R ² remaining in the film, R ¹ and R ² in the formula (1) are preferably a hydrogen atom or a carbon number 1 in the above-mentioned formula (1). The alkyl group having ∼5 carbon atoms is more preferably an alkyl group having 1 to 5 carbon atoms from the viewpoint of storage stability.

In addition, hereinafter, in the partial structure represented by the above-mentioned formula (1), the structure in which both R ¹ and R ² are hydrogen atoms is called "amic acid structure", and at least one of R ¹ and R ² is a hydrogen atom Other structures are also called "amic acid ester structure". In addition, the partial structure represented by the said formula (2) is also called "isoimide ring structure".

The monovalent chain hydrocarbon groups with 1 to 10 carbons in R ³ and R ⁴ may be saturated or unsaturated, specifically, alkyl groups with 1 to 10 carbons, alkyl groups with 2 to 10 carbons, etc. alkenyl, alkynyl having 2 to 10 carbons, etc. These groups may be linear or branched. R ³ and R ⁴ may have a substituent, and the substituent includes, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxyl group, a cyano group, an alkoxy group, and the like.

Here, the term "hydrocarbon group" in this specification includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The term "chain hydrocarbon group" refers to a hydrocarbon group that does not contain a ring structure in the main chain, but is composed of only a chain structure. Wherein, the chain structure may be linear or branched. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group including only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. However, it does not need to consist only of the structure of an alicyclic hydrocarbon, and what has a chain structure in part is also included. In addition, the term "aromatic hydrocarbon group" refers to a hydrocarbon group including an aromatic ring structure as a ring structure. However, it does not need to consist only of an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in a part thereof.

The organic groups of ^X1 and ^Y1 in the partial structure (a-1) and partial structure (a-2) include, for example: hydrocarbon groups such as chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups; A group formed by introducing functional groups such as -O-, -COO-, -CO-, -NHCO-, -S-, -NH-, -SO ₂ - between carbon bonds; the hydrogen atom in the hydrocarbon group is passed through the halogen atom, A group substituted by a hydroxyl group, a nitro group, etc.; a group having a heterocyclic ring, etc.

The partial structure (a-1) and the partial structure (a-2) may exist in the same molecule, or may exist in different molecules, respectively. The following [1] and [2] are mentioned as a preferable aspect of the liquid crystal aligning agent of this invention.

[1] An aspect including a polymer having a partial structure (a-1) and a partial structure (a-2) in one molecule (hereinafter also referred to as "polymer (P)") as a polymer component.

[2] A state including a polymer having a partial structure (a-1) (hereinafter also referred to as "polymer (Q)") and a polymer (polyisoimide) having a partial structure (a-2) Sample.

Among these aspects, the aspect which contains a polymer (P) is preferable from the viewpoint of the surface unevenness|corrugation of a coating film, or the storage stability of a liquid crystal aligning agent.

[1] Regarding aspects including polymer (P)

The polymer (P) can be synthesized according to a common method of organic chemistry. As an example, for example, the following method can be enumerated: tetracarboxylic dianhydride and diamine are reacted to synthesize polyamic acid; After imidization and polyisoimide are obtained, the obtained polyisoimide is made to react with an esterification agent.

(1) Polyamic acid and its synthesis

(tetracarboxylic dianhydride)

As tetracarboxylic dianhydride used for synthesis|combination of polyamic acid, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride etc. are mentioned, for example. As specific examples of these tetracarboxylic dianhydrides, for example, aliphatic tetracarboxylic dianhydrides include butane tetracarboxylic dianhydrides, etc.;

Examples of alicyclic tetracarboxylic dianhydride include: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5 -Dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5 -Dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane Alkane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furyl)-3 -Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, bicyclo[3.3 .0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2: 3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraone, 1,2,4,5-cyclo Hexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, etc.;

As aromatic tetracarboxylic dianhydride, pyromellitic dianhydride etc. are mentioned, for example; In addition, the tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 can be used. Moreover, the tetracarboxylic dianhydride used for synthesis|combination of a polyamic acid can use these tetracarboxylic dianhydrides individually by 1 type, or can use them in combination of 2 or more types.

From the viewpoint of liquid crystal orientation and solubility in solvents, the tetracarboxylic dianhydride used in the synthesis of polyamic acid preferably contains bicyclo[2.2.1]heptane-2,3,5,6- Tetracarboxylic 2:3,5:6-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2 ,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2 ,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, bicyclo[3.3.0]octane- Group consisting of 2,4,6,8-tetracarboxylic 2:4,6:8-dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and pyromellitic dianhydride At least one compound in the group (hereinafter also referred to as "specific tetracarboxylic dianhydride").

The use amount of the specific tetracarboxylic dianhydride is preferably 5 mol % or more, more preferably 10 mol % or more, and particularly preferably It should be 20 mol% or more. The tetracarboxylic dianhydride used for the synthesis|combination of a polyamic acid can use these compounds individually by 1 type or in combination of 2 or more types. Moreover, X1 of the said formula ( ¹ ) and ^X2 of the said formula (2) have the structure derived from the tetracarboxylic dianhydride used for the synthesis|combination of polyamic acid.

(diamine)

As diamine used for synthesis|combination of polyamic acid, aliphatic diamine, alicyclic diamine, aromatic diamine, diamino organosiloxane etc. are mentioned, for example.

As specific examples of these diamines, aliphatic diamines include, for example, m-xylylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, 1,3-bis( Aminomethyl)cyclohexane, etc.; alicyclic diamines include, for example: 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), etc.;

Examples of aromatic diamines include p-phenylenediamine, 4,4'-ethylenediphenylamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1 ,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4 ,4'-Diaminodiphenyl ether, 2-(4-aminophenyl)ethylamine, bis(4-aminophenyl)amine, N,N-bis(4-aminophenyl)methylamine, 4,4'-Diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)benzene base] hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropylidene)bisaniline, 4,4'-(m-phenylene Diisopropylidene) bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, N,N'-bis(4 -aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, dodecyloxy-2,4-diaminobenzene, tetradecyl Alkoxy-2,4-diaminobenzene, Octadecyloxy-2,5-diaminobenzene, Cholesteryloxy-3,5-diaminobenzene, Cholesteryloxy-3,5- Diaminobenzene, Cholesteryloxy-2,4-diaminobenzene, Cholesteryloxy-2,4-diaminobenzene, Cholesteryl 3,5-diaminobenzoate, 3,5- Cholesteryl diaminobenzoate, 3,5-lanostyl diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4 -aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, {4-[2-(3, 5-diaminophenoxy)-ethoxy]-phenyl}-ethanone, 3,4-diaminobenzophenone, {4-[2-(3,5-diaminophenoxy)- Ethoxy]-phenyl}-phenyl-methanone, {4-[2-(2,4-diaminophenoxy)-ethoxy]-phenyl}-p-toluoyl-methanone, 2,7-diaminofluorenone, 2,7-diaminofluorene, and 9,9-bis(4-aminophenyl)fluorene, the following formula (D-1)

[chemical 5]

In formula (D-1), X ^I and X ^II are each independently a single bond, -O-, -COO- or -OCO-, R ^I is an alkanediyl group with 1 to 3 carbon atoms, and R ^II is a single bond Or an alkanediyl group having 1 to 3 carbons, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1; wherein a and b cannot be 0 at the same time.

Indicated compounds, etc., in addition,

Examples include: 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-Diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminobiphenyl Methane-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-bis Aminodiphenylethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, and 4,4'-diaminodiphenylether-3,3 Carboxyl group-containing diamines such as '-dicarboxylic acid:

2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6 -Diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, the following formula (d-1) ~ formula (d-3)

[chemical 6]

Nitrogen-containing heterocyclic diamines such as compounds represented respectively: the following formula (d-4) to formula (d-7)

[chemical 7]

The compounds represented respectively, etc.;

Examples of diaminoorganosiloxane include: 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, 3,3'-[1,4-phenylenebis(dimethylsilane) Diyl)] bis(1-propaneamine), etc.; In addition, diamines described in JP-A-2010-97188 can be used.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _d -" in the formula (D-1) is preferably an alkanediyl group with 1 to 3 carbon atoms, *-O-, *- COO- or *-OC ₂ H ₄ -O- (wherein, the bond with "*" is bonded to a diaminophenyl group). The group "-C _c H _2c+1 " is preferably linear. The two amino groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position with respect to other groups.

Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-5), respectively.

[chemical 8]

Moreover, Y1 of said formula ( ¹ ) and ^Y2 of said formula (2) are structural units derived from the diamine used for the synthesis|combination of polyamic acid. Diamine These compounds can be used individually by 1 type or in combination of 2 or more types.

·Synthesis of polyamic acid

The ratio of tetracarboxylic dianhydride and diamine used in the synthesis reaction of polyamic acid is preferably such that the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 2 equivalents, more preferably It is set to the ratio of 0.3 equivalent - 1.2 equivalent.

When synthesizing a polyamic acid, it is also possible to synthesize|combine the terminal modification type polymer using a suitable molecular weight modifier together with tetracarboxylic dianhydride and diamine as mentioned above. The applicability (printability) of a liquid crystal aligning agent can be further improved without impairing the effect of this invention by making it into the said terminal modification type polymer.

Examples of molecular weight regulators include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; phenyl isocyanate, isocyanate, and Monoisocyanate compounds such as naphthyl cyanate, etc. It is preferable that the usage ratio of a molecular weight modifier shall be 20 weight part or less with respect to the total 100 weight part of tetracarboxylic dianhydride and diamine used, and it is more preferable to set it as 10 weight part or less.

The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, more preferably 0°C to 100°C. In addition, the reaction time is preferably 0.1 hour to 24 hours, more preferably 0.5 hour to 12 hours.

Examples of the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Among these organic solvents, it is preferable to use at least one selected from the group consisting of aprotic polar solvents and phenolic solvents (organic solvents of the first group), or to use an organic solvent selected from the first group A mixture of one or more of these and one or more of them selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (organic solvents of the second group). In the latter case, the proportion of the organic solvent in the second group is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the organic solvent in the first group and the organic solvent in the second group. % or less, especially preferably 30% by weight or less.

It is particularly preferred to use N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethyl One or more solvents selected from the group consisting of urea, hexamethylphosphoric triamide, m-cresol, xylenol, and halogenated phenol, or preferably one or more of these solvents are used within the stated ratio range Mixture with other organic solvents.

It is preferable that the usage-amount (a) of an organic solvent is the quantity which makes the total amount (b) of tetracarboxylic dianhydride and a diamine into 0.1 weight% - 50 weight% with respect to the total amount (a+b) of a reaction solution.

The reaction solution which melt|dissolved polyamic acid was obtained in this way. The reaction solution may be directly supplied to the reaction with the dehydration condensing agent, or the polyamic acid contained in the reaction solution may be separated and then supplied to the reaction with the dehydration condensing agent, or the separated polyamic acid may be purified and then Provided for reaction with dehydrating condensing agent. The isolation and purification of polyamic acid can be performed according to a well-known method.

(2) Isoimidation of polyamic acid

Then, the polyamic acid synthesized as above is isoimidated and polyisoimide is set. The polyisoimide obtained here may be a complete isoimide obtained by dehydrating and condensing the entire amic acid structure of the polyamic acid as its precursor, or may be a part of the amic acid structure A partial isoimide formed by dehydration condensation. The former is preferred.

The isoimidation of polyamic acid can be performed by the method which preferably adds a dehydration condensation agent and a catalyst as needed to the solution which polyamic acid was disperse|distributed or dissolved in the organic solvent.

As a dehydration condensation agent used for isoimidation, trifluoroacetic anhydride, N,N'- dicyclohexylcarbodiimide, thionyl chloride, etc. are mentioned. Although the usage ratio of a dehydration condensing agent depends also on the desired ratio of isoimidization, it is preferable to set it as 0.01 mol - 20 mol with respect to 1 mol of the amic acid structure which a polyamic acid has.

As the catalyst, for example, tertiary amines such as triethylamine, pyridine, and picoline can be used. It is preferable that the usage ratio of a catalyst shall be 0.01 mol - 10 mol with respect to 1 mol of the dehydration condensation agent used.

Examples of the organic solvent used in the isoimidation reaction include compounds exemplified as the organic solvent used in the synthesis of polyamic acid. The reaction temperature of isoimidation is preferably -20°C to 150°C, more preferably 0°C to 100°C. The reaction time is preferably 1 hour to 120 hours, more preferably 2 hours to 50 hours.

A polyisoimide-containing reaction solution is obtained in the manner described. The reaction solution may be directly used for the reaction with the esterification agent, or the polyisoimide contained in the reaction solution may be separated and then provided for the reaction with the esterification agent, or the separated polyisoimide may be used for the reaction with the esterification agent. The amine is purified and then supplied to the reaction with an esterifying agent. Isolation and purification of polyisoimide can be performed according to a known method.

(3) Esterification of polyisoimide

Next, the polyisoimide obtained by the said synthesis reaction is made to react with an esterification agent. As the esterifying agent used here, alcohols, epoxy compounds, etc. are mentioned, for example. As specific examples of these esterification agents, alcohols include, for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, trifluoromethanol, 2,2,2-trifluoroethanol, 2- (Meth)acryloyloxyethanol, 1-(meth)acryloyloxy-2-propanol, 2-(meth)acrylamide ethanol, 1-(meth)acrylamide-2-propanol, etc. Epoxy compounds include, for example: a compound having a group represented by the formula (x-1) and an epoxy group, a compound having a group represented by the formula (x-2) and an epoxy group, etc. . Among them, alcohols can be preferably used as the esterification agent.

It is preferable to carry out the reaction of polyisoimide and an esterification agent in an organic solvent. The reaction temperature at this time may be appropriately set depending on the type of esterification agent, and for example, in the case of alcohols, it is preferably -20°C to 200°C, more preferably 0°C to 120°C. In addition, the reaction time is preferably 0.1 hour to 24 hours, more preferably 0.5 hour to 12 hours.

The organic solvent used in the reaction includes the compounds exemplified as the organic solvent used in the synthesis of polyamic acid. Specifically, N,N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc. It is preferable that the usage-amount of an organic solvent shall be the quantity which makes polyisoimide 0.1 weight% - 50 weight% with respect to the total amount of a reaction solution.

The usage ratio of an esterification agent can be adjusted suitably according to the content ratio of the amic acid ester structure and the isoimide ring structure in the polymer (P) contained in a liquid crystal aligning agent. The partial structure (a-1 ) to the partial structure (a-2) is preferably 1/99 to 99/1 as the molar ratio of the partial structure (a-1)/partial structure (a-2). More preferably, it is 3/97 to 97/3, and especially preferably, it is 5/95 to 95/5. Therefore, what is necessary is just to select the usage-amount of an esterification agent so that the content ratio of the partial structure (a-1) and partial structure (a-2) in a polymer (P) may become the said range. Specifically, it is preferable that the usage ratio of the esterification agent which reacts with polyisoimide is 0.02 mol - 1.99 with respect to the total 1 mol of the tetracarboxylic dianhydride used for the synthesis|combination of polyisoimide. As a mole, it is more preferable to set it as 0.06 mol - 1.94 mol, and it is especially preferable to set it as 0.1 mol - 1.9 mol.

A reaction solution containing polymer (P) is obtained in the manner described. The reaction solution can be directly provided to the preparation of liquid crystal aligning agent, or the polymer (P) contained in the reaction solution can be separated and then provided to the preparation of liquid crystal aligning agent, or the separated polymer (P) can be purified Then it is provided to the preparation of liquid crystal aligning agent. Isolation and purification of the polymer (P) can be performed according to known methods.

＜Polyamic acid＞

The liquid crystal aligning agent of this invention may contain only the said polymer (P) as a polymer component, but may contain both a polymer (P) and a polyamic acid from viewpoints, such as cost. The polyamic acid contained in the liquid crystal aligning agent of this invention can be obtained by making tetracarboxylic dianhydride and diamine react, for example. In addition, the description of the above-mentioned polymer (P) can be applied to the specific examples of the tetracarboxylic dianhydride and diamine used for the synthesis|combination of a polyamic acid, and reaction conditions.

In terms of improving the electrical characteristics of the liquid crystal display element, the polyamic acid used together with the polymer (P) preferably has a structure represented by the following formula (3-1), the following formula The structure represented by (3-2) (excluding those contained in the amide bond formed by the reaction of the anhydride group of the tetracarboxylic dianhydride with the amino group of the diamine) and the nitrogen-containing heterocycle At least one structure (hereinafter also referred to as a specific structure (x)) in the formed group.

[chemical 9]

In formula (3-1), R ⁵ is a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbons, or an alkoxy group with 1 to 10 carbons, and r is an integer of 1 or 2; there are multiple R ⁵ In the case of , multiple R ⁵ can be the same or different; "*" means a bond; in formula (3-2), R ⁶ is a hydrogen atom or an alkyl group with 1 to 6 carbons; "*" means a bond key.

In the above-mentioned formula (3-1), the alkyl group having 1 to 10 carbon atoms of R ⁵ can be exemplified: methyl group, ethyl group, propyl group, butyl group, etc., and these alkyl groups can be linear or can be Branched. In addition, the alkoxy group having 1 to 10 carbons includes a group in which an alkyl group having 1 to 10 carbons is bonded to an oxygen atom, specifically, a methoxy group, an ethoxy group, a propoxy group, etc. Wait. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example. r is preferably 1.

R ⁶ in the formula (3-2) is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, in terms of improving the electrical characteristics of the liquid crystal display element.

Examples of the nitrogen-containing heterocycle include piperidine ring, pyrrolidine ring, pyridine ring, pyrazine ring, piperazine ring, pyrimidine ring, homopiperazine ring, and the like. Among these nitrogen-containing heterocyclic rings, a piperidine ring or a piperazine ring is preferable, and a piperidine ring is more preferable in terms of a high effect of alleviating accumulated residual charges.

The polyamic acid which has a specific structure (x) can be obtained by using the diamine which has a specific structure (x) at the time of synthesizing a polyamic acid. Specifically, the polyamic acid which has the structure represented by the said formula (3-1) can be obtained by making at least a part of the diamine used for synthesis|combination of a polyamic acid into the said carboxyl group-containing diamine. In addition, by using bis(4-aminophenyl)amine, N,N-bis(4-aminophenyl)methylamine, a compound represented by the above formula (d-4), etc., it is possible to obtain the compound having the above formula (3-2) The polyamic acid of the structure shown. Moreover, the polyamic acid which has a nitrogen-containing heterocycle can be obtained by using the said nitrogen-containing heterocyclic diamine.

When synthesizing polyamic acid, the usage ratio of the monomer having the specific structure (x) is preferably 1 mol % to 30 mol %, more preferably 2 mol %, based on the total amount of monomers used in the synthesis. ~20 mol%.

In addition, when a coating film is formed on a substrate using a liquid crystal aligning agent containing a polymer (P) and a polyamic acid, it is presumed that the polymer (P) is unevenly distributed in the coating film due to the difference in polarity of each polymer. The upper layer, the polyamic acid is partial to the lower layer. In the blend system of the above-mentioned multiple polymers, since the phase separation of the polymers is not good, there is a concern that the surface roughness of the coating film will decrease, but the liquid crystal containing the polymer (P) and the polyamic acid Alignment agent to obtain a liquid crystal alignment film with good surface unevenness.

When using the liquid crystal aligning agent of the present invention for photo-alignment, part or all of the polymer (P) blended in the liquid crystal aligning agent and optionally blended polyamic acid can be polymerized to have a photo-alignment structure. things. Here, the photo-alignment structure is a concept including both the photo-alignment group and the decomposition-type photo-alignment part. Specifically, the photo-alignment structure can be a structure derived from various compounds that exhibit liquid crystal orientation through photoisomerization, photodimerization, photolysis, etc., for example, include: Azobenzene-containing group containing cinnamic acid or its derivatives as basic skeleton, group having cinnamic acid structure containing cinnamic acid or its derivatives as basic skeleton, chalcone-containing group containing chalcone or its derivatives as basic skeleton group, a benzophenone-containing group containing benzophenone or its derivatives as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, a polyimide or Its derivatives are polyimide-containing structures as the basic skeleton, etc.

As the polymer having a photo-alignment structure contained in the liquid crystal aligning agent of the present invention, a polymer having a group containing a cinnamic acid structure and a polymer containing a decomposable photo-alignment part can be preferably used. The polymer having a group containing a cinnamic acid structure includes, for example: a polymer in which at least one of R and ^R of the formula ( ¹ ) described in the polymer (P) is a monovalent group having a cinnamic acid structure, Polyamic acid and the like having a cinnamic acid structure on the side chain. In addition, among the polymers containing the decomposition-type photo-alignment portion, polymers having a cyclobutane skeleton or a bicyclo[2.2.2]octene skeleton can be preferably used. Polymers having these skeletons can be obtained by setting a part or all of the tetracarboxylic dianhydride used in the synthesis as, for example, cyclobutane tetracarboxylic dianhydride or bicyclo[2.2.2]oct-7-ene-2,3, 5,6-tetracarboxylic dianhydride.

When imparting liquid crystal orientation ability to the coating film by the photo-alignment method, it is preferable to set the usage ratio of the polymer having a photo-alignment structure to 50% by weight relative to the total amount of polymer components contained in the liquid crystal aligning agent. % or more, more preferably 60% by weight or more, particularly preferably 70% by weight or more.

The polymer (P) and polyamic acid in the present invention preferably have a solution viscosity of 15 mPa·s to 1500 mPa·s, more preferably 20 mPa·s to 1200mPa·s solution viscosity. In addition, the solution viscosity (mPa·s) of the polymer is for a concentration of 15% by weight prepared using a good solvent for the polymer (such as γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The polymer solution is a value measured at 25° C. using an E-type rotational viscometer.

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer (P) and polyamic acid in the present invention measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) is preferably 1,000 to 500,000, more preferably 2,000 ~300,000. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, more preferably 10 or less. Favorable orientation and stability of a liquid crystal display element can be ensured by being in the said molecular weight range.

In the liquid crystal aligning agent containing a polymer (P) and a polyamic acid, it is preferable that the content ratio of a polymer (P) and a polyamic acid is 1/99-99 by weight ratio of a polymer (P)/polyamic acid /1. More preferably, it is 5/95 to 97/3, and especially preferably, it is 10/90 to 95/5.

Moreover, the liquid crystal aligning agent of the aspect of [1] may further contain at least 1 sort(s) of polymer chosen from the group which consists of a polyamic acid ester and a polyisoimide. When these polymers are contained, from the viewpoint of cost and the like, the compounding ratio of the polymers (when two or more are contained) is 100 parts by weight of the total amount of the polymer (P) and polyamic acid The total amount thereof) is preferably 30 parts by weight or less, more preferably 20 parts by weight or less.

[2] Regarding the aspects including polymer (Q) and polyisoimide

Polyamic acid and polyamic acid ester are contained as a polymer (Q). Here, the polyamic acid in this specification refers to the polymer containing the partial structure (amic acid structure) in which ^R1 and ^R2 in the said formula (1) are both hydrogen atoms. In addition, polyamic acid ester is a polymer which has a partial structure (amic acid ester structure) in which at least one of R ¹ and R ² in the formula (1) is a hydrogen atom. In addition, the polyamic acid ester may have only an amic acid ester structure, and may be a partial esterified product in which an amic acid structure and an amic acid ester structure coexist.

Polymer (Q) and polyisoimide can be synthesize|combined according to the normal method of organic chemistry. For example, polyamic acid and polyisoimide can be obtained by the method demonstrated above. In addition, regarding polyamic acid ester, for example, the following methods can be used to obtain: [I] a method of reacting polyamic acid with an esterification agent; [II] a method of reacting polyisoimide with an esterification agent; [III] A method of reacting tetracarboxylic acid diester with diamine; [IV] A method of reacting tetracarboxylic acid diester dihalide with diamine; and [V] making tetracarboxylic dianhydride, diamine And the method of reacting the esterification agent in an organic solvent, etc.

Here, examples of the esterifying agent used in the method [I] and the method [II] include the compounds exemplified in the synthesis of the polymer (P) and the like. Among these methods, the reaction of method [I] is preferably performed in the presence of a catalyst. On the other hand, method [II] is preferable in that the reaction proceeds sufficiently even in the absence of a catalyst. The tetracarboxylic-acid diester used by method [III] can be obtained by the method of making tetracarboxylic dianhydride and alcohols react and opening a ring, the method of esterifying tetracarboxylic acid, etc. Moreover, the tetracarboxylic-acid diester dihalide used by method [IV] can be obtained by making the tetracarboxylic-acid diester obtained in this way react with an appropriate halogenating agent, such as thionyl chloride. The diamine used by the method [III] and the method [IV] includes the compound etc. which were illustrated as the diamine used for synthesis|combination of a polyamic acid. Method [V] can be used preferably when obtaining a silane type polyamic acid ester. In this case, as the esterification agent, for example, silylamide-based silanes such as bis(trimethylsilyl)acetamide, bis(trimethylsilyl)trifluoroacetamide, and bis(trimethylsilyl)urea can be used. base agent.

The polymer (Q) and polyisoimide in the present invention preferably have a solution viscosity of 15 mPa·s to 1500 mPa·s, more preferably 20 mPa·s when they are made into a solution with a concentration of 15% by weight. s ~ 1200mPa·s solution viscosity. In addition, the solution viscosity (mPa·s) of the polymers is for the concentration of 15% by weight prepared using good solvents for these polymers (such as γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The polymer solution is a value measured at 25° C. using an E-type rotational viscometer.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polymer (Q) and polyisoimide in this invention becomes like this. Preferably it is 1,000-500,000, More preferably, it is 2,000-500,000. 300,000. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, more preferably 10 or less.

In the liquid crystal aligning agent containing a polymer (Q) and a polyisoimide, it is preferable that the content ratio of a polymer (Q) and a polyisoimide is equal to polyisoimide from a viewpoint of fully obtaining the effect of this invention The weight ratio of imide/polymer (Q) shall be 1/99-99/1. More preferably, it is 10/90 to 90/10, and especially preferably, it is 15/85 to 85/15.

＜Other ingredients＞

The liquid crystal aligning agent of this invention may further contain other components other than the said polymer as needed. The other components include, for example, polymers (P), polymers (Q) and other polymers other than polyisoimides, compounds having at least one epoxy group in their molecules (hereinafter referred to as "epoxy group-containing compounds") Compounds"), functional silane compounds, etc.

[Other polymers]

The other polymers can be used to improve solution properties or electrical properties. The other polymers include, for example, polyimide, polyester, polyamide, polyorganosiloxane, cellulose derivatives, polyacetal, polystyrene derivatives, poly(styrene-phenylbutadiene imide) derivatives, poly(meth)acrylates, etc.

When adding the other polymer to the liquid crystal aligning agent, the compounding ratio of the other polymer is preferably 30 parts by weight or less, more preferably It is 0.1 weight part - 20 weight part, and it is especially preferable to set it as 0.1 weight part - 10 weight part.

[Epoxy group-containing compound]

The compound containing an epoxy group can be used for improving the adhesiveness of the liquid crystal aligning film and the board|substrate surface. Here, the epoxy group-containing compound, for example, may include the following compounds as preferred: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl ether Diol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-amino Methylcyclohexane, N,N-diglycidyl-cyclohexylamine, epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598, and the like.

When adding these epoxy group-containing compounds to a liquid crystal aligning agent, it is preferable that the compounding ratio of the said epoxy group containing compound is 40 with respect to the total 100 weight part of polymers contained in a liquid crystal aligning agent. It is less than or equal to parts by weight, more preferably 0.1 to 30 parts by weight.

[Functional silane compound]

The functional silane compound can be used to improve the printability of the liquid crystal aligning agent. Examples of such functional silane compounds include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane Silane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazo Nonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-Benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidyloxymethyltrimethoxysilane, glycidyloxymethyltriethoxy base silane, etc.

When adding a functional silane compound to a liquid crystal aligning agent, the compounding ratio of the said functional silane compound is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight with respect to a total of 100 parts by weight of the polymer. parts by weight.

In addition, the following compounds can also be added to the liquid crystal aligning agent: metal chelate compounds such as diisopropoxyethyl acetoacetate and tris(acetylacetonate)aluminum; hardening accelerators such as phenols and silanols ;Nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, fluorine-containing surfactants and other surfactants; phenolic antioxidants, amine antioxidants and other antioxidants ; Ethylene glycol diacrylate, 1,6-hexanediol diacrylate and other multifunctional (meth)acrylates, etc.

<Solvent>

It is preferable to prepare the liquid crystal aligning agent of this invention as the liquid composition which disperse|distributed or melt|dissolved the said polymer and other components used as needed in an appropriate solvent.

Examples of solvents used include: N-methyl-2-pyrrolidone, γ-butyrolactone, γ-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-isopropyl 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 acetic acid Esters, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, etc. These solvents may be used alone or in combination of two or more.

The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) can be appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1% by weight to 10% by weight. That is, the liquid crystal aligning agent of this invention forms the coating film which becomes a liquid crystal aligning film or the coating film which becomes a liquid crystal aligning film by coating on the board|substrate surface as mentioned later, and preferably heating. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a favorable liquid crystal aligning film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large and it is difficult to obtain a good liquid crystal aligning film. In addition, the viscosity of the liquid crystal aligning agent increases to reduce the applicability. tendency.

The range of the especially preferable solid content density|concentration differs with the use of a liquid crystal aligning agent, or the method used when apply|coating a liquid crystal aligning agent on a board|substrate. For example, for a liquid crystal aligning agent for a liquid crystal unit, when utilizing a spinner method to apply on a substrate, the solid content concentration (the total weight of all components other than the solvent in the liquid crystal aligning agent in the total weight of the liquid crystal aligning agent The proportion in which it occupies) is particularly preferably in the range of 1.5% by weight to 4.5% by weight. When using the printing method, it is particularly preferable to set the solid content concentration in a range of 3% by weight to 9% by weight, whereby the solution viscosity is in a range of 12mPa·s to 50mPa·s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration in a range of 1% by weight to 5% by weight, whereby the solution viscosity is in a range of 3 mPa·s to 15 mPa·s. The temperature at the time of preparing 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. Moreover, about the liquid crystal aligning agent for phase difference films, it is preferable that the solid content concentration of a liquid crystal aligning agent is 0.2 weight% - 10% from a viewpoint of making the applicability of a liquid crystal aligning agent and the film thickness of the coating film formed moderate. The range of weight % is more preferably the range of 3 weight% - 10 weight%.

＜Liquid crystal display element and retardation film＞

A liquid crystal aligning film can be manufactured by using the liquid crystal aligning agent of this invention demonstrated above. Moreover, the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention can be suitably applied to the liquid crystal aligning film for liquid crystal display elements (for liquid crystal cells), and the liquid crystal aligning film for retardation films. Hereinafter, the liquid crystal display element and retardation film of this invention are demonstrated.

[LCD display element]

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited, for example, it can be applied to TN type, STN type, VA type (including Vertical Alignment-Multidomain Vertical Alignment (Vertical Alignment-Multidomain Vertical Alignment, VA-MVA) type, vertical Alignment-Patterned Vertical Alignment (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type, etc.), IPS type, FFS type, Optically Compensatory Bend (Optically Compensatory Bend, OCB) type and other operating modes. The liquid crystal display element of this invention can be manufactured by the process including following (1-1)-(1-3), for example. Step (1-1) uses different substrates according to the desired mode of operation. Step (1-2) and step (1-3) are common in each operation mode.

[Step (1-1): Formation of coating film]

First, the liquid crystal aligning agent of this invention is apply|coated on a board|substrate, and a coating film is formed on a board|substrate by heating an application surface next.

(1-1A) In the case of manufacturing, for example, a TN-type, STN-type or VA-type liquid crystal display element, at first, two substrates provided with a patterned transparent conductive film are used as a pair, and each transparent conductive film is used as a pair. It is preferable to coat the liquid crystal aligning agent of this invention separately by the offset printing method, the spin coater method, the roll coater method, or the inkjet printing method on a film formation surface. For the substrate, glass such as float glass and soda glass can be used; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly(alicyclic olefin) can be used. transparent substrate. The transparent conductive film provided on one side of the substrate can use Nesser (NESA) film (registered trademark of PPG Corporation of the United States) containing tin oxide (SnO ₂ ), or NESA film containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). ITO film, etc. In order to obtain a patterned transparent conductive film, for example, the following methods can be used: a method of forming a pattern by photoetching after forming a transparent conductive film without a pattern; a method of using a mask having a desired pattern when forming a transparent conductive film, etc. . When coating the liquid crystal aligning agent, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, it is also possible to apply a functional silane compound or a functional titanium compound to the surface of the substrate surface where the coating film is formed. etc. preprocessing.

After apply|coating a liquid crystal aligning agent, it is preferable to implement preheating (prebaking) for the purpose, such as preventing the sagging of the applied liquid crystal aligning agent. The prebaking temperature is preferably 30°C to 200°C, more preferably 40°C to 150°C, particularly preferably 40°C to 100°C. The prebaking time is preferably 0.25 minutes to 10 minutes, more preferably 0.5 minutes to 5 minutes. Then, a calcination (post-baking) step is implemented for the purpose of completely removing the solvent and optionally thermally imidizing the amic acid structure present in the polymer. The firing temperature (post-baking temperature) at this time is preferably 80°C to 300°C, more preferably 120°C to 250°C. The post-baking time is preferably 5 minutes to 200 minutes, more preferably 10 minutes to 100 minutes. The film thickness of the film formed in this manner is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

(1-1B) In the case of manufacturing an IPS-type or FFS-type liquid crystal display element, the liquid crystal of the present invention is coated on the electrode-forming surface of the substrate provided with electrodes and on the side of the counter substrate not provided with electrodes. The alignment agent heats each coated surface to form a coating film, and the electrodes include a comb-shaped transparent conductive film or metal film. The material of the substrate and transparent conductive film used at this time, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or metal film, the pretreatment of the substrate, and the preferred film thickness of the formed coating film Same as (1-1A) above. As the metal film, for example, a film containing metal such as chromium can be used.

In any case of the above (1-1A) and (1-1B), after coating the liquid crystal aligning agent on the substrate, the organic solvent is removed to form a liquid crystal aligning film or a coating film that becomes a liquid crystal aligning film . At this time, by further heating after the coating film is formed, the polyamic acid ester and polyimide formulated in the liquid crystal aligning agent of the present invention, and the polyamic acid formulated if necessary, undergo a dehydration ring-closing reaction, thereby A further imidized coating film was produced.

[Step (1-2): Orientation processing]

When manufacturing a TN type, STN type, IPS type, or FFS type liquid crystal display element, the process (orientation process) which provides liquid crystal orientation ability to the coating film formed in the said process (1) is implemented. Thereby, the orientation ability of a liquid crystal molecule is given to a coating film, and it becomes a liquid crystal aligning film. The orientation treatment can include rubbing treatment, photo-orientation treatment, etc., the rubbing treatment utilizes a roller wound with cloth such as nylon, rayon, cotton, etc., to wipe the coating film in a certain direction; The film is irradiated with light. On the other hand, in the case of producing a vertical alignment type liquid crystal display element, the coating film formed in the step (1) may be used as a liquid crystal alignment film as it is, or may be subjected to orientation treatment on the coating film.

The light irradiation in the photo-alignment treatment can be performed by the following methods: [1] a method of irradiating the coating film after the post-baking step; [2] irradiating the coating film after the pre-baking step and before the post-baking step. a method of irradiating; [3] a method of irradiating the coating film during heating of the coating film in at least one of the pre-baking step and the post-baking step, and the like.

The light irradiated to the coating film may be polarized or non-polarized. As light, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. In the case of polarized light, linearly polarized light or partially polarized light may be used. In addition, when the light used is linearly polarized or partially polarized, it may be irradiated from a direction perpendicular to the substrate surface, may be irradiated from an oblique direction, or may be combined. In the case of irradiating non-polarized light, the irradiating direction is an oblique direction.

As the light source used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. Ultraviolet rays in a preferable wavelength region can be obtained by a method using a light source together with, for example, a filter, a diffraction grating, and the like. The amount of light irradiation is preferably 100 J/m ² to 50,000 J/m ² , more preferably 300 J/m ² to 20,000 J/m ² . In addition, in order to improve the reactivity, the coating film may be irradiated with light while heating the coating film. The temperature at the time of heating is usually 30°C to 250°C, preferably 40°C to 200°C, more preferably 50°C to 150°C.

In addition, the liquid crystal aligning film after the rubbing treatment may be further subjected to the following treatment so that the liquid crystal aligning film has different liquid crystal aligning capabilities in each region: by irradiating a part of the liquid crystal aligning film with light, the liquid crystal aligning film in a part of the region A process of changing the pretilt angle; or a process of removing the resist film after forming a resist film on a part of the surface of the liquid crystal alignment film, rubbing in a direction different from the previous rubbing process. In this case, the viewing angle characteristic of the obtained liquid crystal display element can be improved. A liquid crystal alignment film suitable for a VA type liquid crystal display element may also be suitably used for a polymer sustained alignment (PSA) type liquid crystal display element.

[Step (1-3): Construction of liquid crystal cell]

A liquid crystal cell is produced by preparing two substrates on which the liquid crystal aligning film is formed as described above, and disposing liquid crystals between the two substrates facing each other. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, the two substrates are arranged facing each other through a gap (cell gap) so that the liquid crystal alignment films face each other, and the peripheral parts of the two substrates are bonded together using a sealing material, and the cell divided by the substrate surface and the sealing material is After filling the liquid crystal into the gap, the injection hole is sealed to manufacture a liquid crystal cell. In addition, the second method is a method called a liquid crystal drop filling (One Drop Fill, ODF) method. On one of the two substrates on which the liquid crystal alignment film is formed, apply a UV-curable sealant, and then drop liquid crystals on several predetermined positions on the surface of the liquid crystal alignment film. A liquid crystal cell can be produced by laminating another substrate with the liquid crystal alignment film facing it, spreading the liquid crystal over the entire surface of the substrate, and then irradiating the entire surface of the substrate with ultraviolet light to harden the sealing material. In the case of using either method, it is desirable to further heat the liquid crystal cell manufactured in the above-mentioned manner until the temperature at which the liquid crystal used acquires an isotropic phase, and then slowly cool it to room temperature, thereby eliminating Flow orientation during liquid crystal filling.

As a sealing material, what is generally used as an adhesive agent for liquid crystals can be used, for example, the epoxy resin etc. which contain a hardening|curing agent can be used. In addition, the sealing material may also contain alumina balls as spacers.

Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred, for example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenyl Cyclohexane-based liquid crystals, ester-based liquid crystals, terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals, and the like. In addition, the following substances can also be added to these liquid crystals: for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate. crystal); chiral agents sold under the trade names "C-15", "CB-15" (manufactured by Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate, etc.

Then, the liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. The polarizing plate attached to the outer surface of the liquid crystal cell includes: a polarizing plate in which a polarizing film called "H film" is sandwiched between cellulose acetate protective films, or a polarizing plate including the H film itself. "H film" is a film in which polyvinyl alcohol absorbs iodine while stretching and aligning.

[Retardation film]

Next, the method of manufacturing a phase difference film using the liquid crystal aligning agent of this invention is demonstrated. When manufacturing the phase difference film of the present invention, it is not only possible to suppress dust or static electricity in the steps, but also to form a uniform liquid crystal alignment film, and to be able to form a uniform liquid crystal alignment film on the substrate by using an appropriate photomask when irradiating light. It is preferable to utilize the photo-alignment method at the point which arbitrarily forms the some area|region which differs in a liquid crystal orientation direction. Specifically, it can be produced by passing through the following steps (2-1) to (2-3).

Step (2-1): a step of applying a liquid crystal aligning agent on a substrate to form a coating film.

Step (2-2): a step of irradiating the coating film with light.

Step (2-3): a step of applying a polymerizable liquid crystal on the light-irradiated coating film and curing it.

[Process (2-1): Formation of Coating Film Using Liquid Crystal Aligning Agent]

First, the liquid crystal aligning agent of this invention is apply|coated on a board|substrate, and a coating film is formed. The substrate used here can suitably be exemplified: triacetyl cellulose (triacetyl cellulose, TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide , polymethyl methacrylate, polycarbonate and other synthetic resin transparent substrates. Among these substrates, TAC is generally used as a protective layer of a polarizing film in a liquid crystal display element. In addition, polymethyl methacrylate can be preferably used as a substrate for a retardation film from the point of low hygroscopicity of the solvent, the point of good optical characteristics, and the point of low cost. Moreover, in order to make the board|substrate surface and the adhesiveness of a coating film more favorable about the board|substrate used for coating of a liquid crystal aligning agent, you may give conventionally well-known pretreatment to the surface which forms a coating film among the board|substrate surfaces.

In many cases, a retardation film is used in combination with a polarizing film. At this time, in order to exhibit desired optical characteristics, the angle of the retardation film with respect to the polarization axis of the polarizing film must be precisely controlled to a specific direction, and the retardation film must be bonded. Therefore, here, by forming a liquid crystal aligning film having liquid crystal aligning ability in the direction of a predetermined angle on a substrate such as a TAC film or polymethyl methacrylate, it is possible to omit the need to form a phase difference film while controlling the angle of the phase difference film. The step of pasting on the polarizing film. Moreover, it can contribute to improvement of the productivity of a liquid crystal display element by this. In order to form the liquid crystal aligning film which has the ability to align liquid crystals in the direction of a predetermined angle, it is preferable to perform by the photo-alignment method.

The coating of the liquid crystal aligning agent on the substrate can utilize an appropriate coating method, for example, can adopt: roll coater method, spinner method, printing method, inkjet method, rod coater method, extrusion die method, direct Gravure coater method, chamber doctor coater method, offsetgravure coater method, single roll kiss coater method, use Small-diameter gravure roll reverse kiss coater method, three reverse roll coater method, four reverse roll coater method, slot die method, air knife Air doctor coater method, positive rotation roll coater method, blade coater method, knife coater method, dip coater Method, MB coater method, MB reverse coater method, etc.

After coating, the coated surface is heated (baked) to form a coating film. The heating temperature at this time is preferably 40°C to 150°C, more preferably 80°C to 140°C. The heating time is preferably 0.1 minute to 15 minutes, more preferably 1 minute to 10 minutes. The film thickness of the coating film formed on the substrate is preferably 1 nm to 1,000 nm, more preferably 5 nm to 500 nm.

[Step (2-2): Light irradiation step]

Then, by irradiating light to the coating film formed on the board|substrate as mentioned above, the liquid crystal aligning ability is given to a coating film, and a liquid crystal aligning film is produced. Regarding the type of light to be irradiated, the direction of irradiation, and the light source, the description of the above step (1-2) can be applied. The amount of light irradiation is preferably 0.1 mJ/cm ² to 1,000 mJ/cm ² , more preferably 1 mJ/cm ² to 500 mJ/cm ² , and particularly preferably 2 mJ/cm ² to 200 mJ/cm ² .

[Step (2-3): Formation of Liquid Crystal Layer]

Next, a polymerizable liquid crystal is applied and cured on the coating film irradiated with light as described above. Thereby, a coating film (liquid crystal layer) containing a polymerizable liquid crystal is formed. The polymerizable liquid crystal used here is a liquid crystal compound or a liquid crystal composition that is polymerized by at least one of heating and light irradiation. Such polymerizable liquid crystals can be used conventionally known liquid crystals, specifically, for example, Non-Patent Document 1 ("Ultraviolet (UV) Curable Liquid Crystals and Their Applications", "Liquid Crystals" Volume 3 No. 1 (1999) ), the nematic liquid crystal described in pages 34 to 42). In addition, a cholesteric liquid crystal; a discotic liquid crystal; a twisted nematic alignment type liquid crystal to which a chiral agent is added, etc. may be used. The polymerizable liquid crystal may also be a mixture of various liquid crystal compounds. The polymerizable liquid crystal may be a composition further containing a known polymerization initiator, a suitable solvent, and the like.

When coating the above-mentioned polymerizable liquid crystal on the formed liquid crystal aligning film, for example, an appropriate coating method such as a bar coater method, a roll coater method, a spinner method, a printing method, or an inkjet method can be used. .

Next, the coating film of the polymerizable liquid crystal formed as described above is subjected to one or more treatments selected from heating and light irradiation to harden the coating film to form a liquid crystal layer. It is preferable to perform these treatments overlappingly because good orientation can be obtained.

The heating temperature of the coating film can be appropriately selected according to the type of polymerizable liquid crystal to be used. For example, when RMS03-013C manufactured by Merck is used, it is preferable to heat at a temperature in the range of 40°C to 80°C. The heating time is preferably 0.5 minutes to 5 minutes.

As the irradiation light, it is preferable to use non-polarized ultraviolet rays having a wavelength in the range of 200 nm to 500 nm. The irradiation amount of light is preferably set at 50 mJ/cm ² to 10,000 mJ/cm ² , and more preferably set at 100 mJ/cm ² to 5,000 mJ/cm ² .

The thickness of the formed liquid crystal layer can be appropriately set according to desired optical characteristics. For example, in the case of manufacturing a 1/2 wavelength plate in visible light with a wavelength of 540nm, the thickness of the retardation film to be formed is selected to be 240nm to 300nm, and if it is a 1/4 wavelength plate, the retardation is selected to be 120nm ~150nm thickness. The thickness of the liquid crystal layer for obtaining the target retardation varies depending on the optical characteristics of the polymerizable liquid crystal used. For example, when RMS03-013C manufactured by Merck is used, the thickness for producing the 1/4 wavelength plate is in the range of 0.6 μm to 1.5 μm.

The retardation film obtained in this manner can be preferably used as a retardation film of a liquid crystal display element. The operation mode of the liquid crystal display element using the retardation film of the present invention is not limited, for example, it can be applied to various known modes such as TN type, STN type, IPS type, FFS type, and VA type. The retardation film is used by affixing the substrate-side surface of the retardation film to the outer surface of the polarizing plate disposed on the viewing side of the liquid crystal display element. Therefore, it is preferable to make the substrate of the retardation film into a TAC or acrylic base material, and to make the substrate of the retardation film function also as a protective film of the polarizing film.

The liquid crystal display element of the present invention can be effectively applied to various devices, for example, it can be used in clocks, portable game machines, word processors (word processors), note type personal computers (note type personal computers), car navigation systems (car Navigation system), camcorder (camcorder), personal digital assistant (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart phone, various monitors, LCD TV, information display and other display devices.

[Example]

Hereinafter, the present invention will be further specifically described through examples, but the present invention is not limited to these examples.

The imidization rate of the polyimide in the following synthesis examples and the solution viscosity of each polymer solution were measured by the following method.

[Imidation rate of polyimide]

The solution containing polyimide was put into pure water, and the obtained precipitate was fully dried under reduced pressure at room temperature, and dissolved in deuterated dimethyl sulfoxide, using tetramethylsilane as a reference substance, at room temperature ¹ H-NMR (Nuclear Magnetic Resonance, NMR) was measured. From the obtained ¹ H-NMR spectrum, the imidization rate [%] was calculated|required using the following numerical formula (1).

Imidization rate [%] = (1-A ¹ /A ² ×α) × 100 (1)

(In formula (1), A ¹ is the peak area of protons derived from the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of other protons relative to the polymer ( The number ratio of 1 proton of NH group in polyamic acid)

[Solution Viscosity of Polymer Solution]

The solution viscosity [mPa·s] of the polymer solution is measured at 25° C. using an E-type rotational viscometer for a solution prepared using a predetermined solvent so as to have a polymer concentration of 15% by weight.

＜Synthesis of Polyamic Acid＞

[Synthesis Example 1; Synthesis of Polymer (PAA-1)]

90 molar parts of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 10 molar parts of pyromellitic dianhydride, 98 molar parts of p-phenylenediamine as diamine and 2 molar parts of 3,6-bis(4-aminobenzoyloxy)cholestane, dissolved in N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), at 60°C The reaction was carried out for 6 hours at a lower temperature to obtain a polyamic acid solution having a solid content concentration of 15% by weight. A small amount of the obtained polyamic acid solution was fractionated, and the solution viscosity measured was 420 mPa·s.

[Synthesis Example 2, Synthesis Example 3; Synthesis of Polymer (PAA-2) and Polymer (PAA-3)]

Except having changed the kind and quantity of the tetracarboxylic dianhydride and diamine used to the point described in following Table 1, it was similar to the synthesis example 1, and obtained the solution containing a polyamic acid.

＜Synthesis of Polymer (P)＞

[Synthesis Example 4; Synthesis of Polymer (PHF-1)]

By the same operation as in Synthesis Example 1, a polyamic acid solution having a solid content concentration of 15% by weight was obtained. After adding 200 mol parts of triethylamine (TEA) to this polyamic-acid solution with respect to 100 mol parts of the total amount of the tetracarboxylic dianhydride used for synthesis, it stirred at room temperature for 24 hours. Then, while stirring at 0° C., while spending 1 hour, in the reaction solution, 200 molar parts of trifluoroacetic anhydride (trifluoroacetic anhydride, TFAA), then stirred at room temperature for 24 hours. After the reaction, the resulting solution was poured into a large amount of excess acetone to precipitate the reaction product. The collected precipitate was washed with acetone, and then dried at 40° C. for 15 hours under reduced pressure to obtain a polymer.

Then, the obtained polymer was dissolved again in NMP, 100 mol parts of methanol was added to this with respect to 100 mol parts of the total amount of the tetracarboxylic dianhydride used for synthesis, and it stirred for 24 hours. Thereby, the solution containing the polymer (PHF-1) which has an amic acid ester structure and an isoimide ring structure was obtained.

[Synthesis Example 5 to Synthesis Example 8; Synthesis of Polymer (PHF-2) to Polymer (PHF-5)]

In addition to changing the type and amount of tetracarboxylic dianhydride and diamine used, and the amount of methanol used to the aspects described in Table 1 below, polymers containing ( PHF-2) ~ polymer (PHF-5) solution.

[Synthesis Example 9; Synthesis of Polymer (PHF-6)]

By the same operation as in Synthesis Example 1, a polyamic acid solution having a solid content concentration of 15% by weight was obtained. After adding 100 mol parts of triethylamine (TEA) to this polyamic-acid solution with respect to 100 mol parts of total amounts of the tetracarboxylic dianhydride used for synthesis, it stirred at room temperature for 24 hours. Then, while stirring at 0° C., 1 hour was added to the reaction solution to add 100 molar parts of trifluoroacetic anhydride (TFAA) to the total amount of tetracarboxylic dianhydride used for synthesis of 100 molar parts, Then, it was stirred at room temperature for 24 hours. After the reaction, the resulting solution was poured into a large amount of excess acetone to precipitate the reaction product. The collected precipitate was washed with acetone, and then dried at 40° C. under reduced pressure for 15 hours to obtain a polymer (PHF-6) having an amic acid structure and an isoimide ring structure.

＜Synthesis of Polyimide＞

[Synthesis Example 10; Synthesis of Polymer (PI-1)]

By the same operation as in Synthesis Example 1, a polyamic acid solution having a solid content concentration of 15% by weight was obtained. NMP was added to this polyamic acid solution so that the solid content concentration was 10% by weight, and 300 mol parts of pyridine and acetic anhydride were added to a total of 100 mol parts of tetracarboxylic dianhydride, respectively, and 4 Hour dehydration ring closure reaction. After the dehydration ring-closing reaction, use new NMP to replace the solvent in the system (by this operation, the pyridine and acetic anhydride used in the imidation reaction are removed from the system), and the imidation rate is obtained. 85% solution of polyimide. The obtained polymer (PI-1) was prepared as a solution using NMP so as to be 15% by weight, and the viscosity of the solution was measured to be 520 mPa·s.

＜Synthesis of Polyisoimide＞

[Synthesis Example 11; Synthesis of Polymer (Piso-1)]

By the same operation as in Synthesis Example 1, a polyamic acid solution having a solid content concentration of 15% by weight was obtained. After adding 200 mol parts of triethylamine (TEA) to this polyamic-acid solution with respect to 100 mol parts of total amounts of the tetracarboxylic dianhydride used for synthesis, it stirred at room temperature for 24 hours. Next, while stirring at 0° C., 200 mol parts of trifluoroacetic anhydride (TFAA) was added to the reaction solution for 1 hour with respect to 100 mol parts of the total amount of tetracarboxylic dianhydride used in the synthesis, and then , stirred at room temperature for 24 hours. After the reaction, the resulting solution was poured into a large amount of excess acetone to precipitate the reaction product. Polyisoimide was obtained by washing|cleaning the recovered deposit with acetone, and drying at 40 degreeC under reduced pressure for 15 hours. The obtained polymer (Piso-1) was prepared as a solution using NMP so as to be 15% by weight, and the viscosity of the solution was measured to be 540 mPa·s.

＜Synthesis of polyamic acid ester＞

[Synthesis Example 12; Synthesis of Polymer (PAE-1)]

By the same operation as in Synthesis Example 11, a polyisoimide solution having a solid content concentration of 15% by weight was obtained. To this polyisoimide solution, 300 mol parts of methanol was added with respect to 100 mol parts of total amounts of the tetracarboxylic dianhydride used for synthesis, and it stirred for 24 hours. After the reaction, the resulting solution was poured into a large amount of excess acetone to precipitate the reaction product. After washing|cleaning the recovered deposit with acetone, it dried at 40 degreeC under reduced pressure for 15 hours, and obtained the polyamic acid ester. The obtained polymer (PAE-1) was prepared as a solution using NMP so as to be 15% by weight, and the viscosity of the solution was measured to be 400 mPa·s.

The composition of the compounds used in the synthesis of the polymer is shown in Table 1 below.

The numerical value in Table 1 shows the usage ratio (mol part) of each compound with respect to 100 mol parts of the total amount of the tetracarboxylic dianhydride used for the synthesis|combination of a polymer. The numerical value of "PAE/isoimide ratio" is a calculated value of the ratio (molar ratio) of an amic acid ester structure and an isoimide ring structure with respect to all the repeating units in a polymer. The numerical value of "PAA/isoimide ratio" is a calculation value of the ratio (molar ratio) of an amic acid structure and an isoimide ring structure with respect to the whole repeating unit in a polymer.

In Table 1, the abbreviations of the compounds have the following meanings, respectively.

(tetracarboxylic dianhydride)

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

AN-2: 2,3,5-Tricarboxycyclopentylacetic dianhydride

AN-3: Pyromellitic dianhydride

(diamine)

DA-1: p-phenylenediamine

DA-2: the compound represented by the formula (d-1)

DA-3: 3,6-bis(4-aminobenzoyloxy)cholestane

DA-4: 3-(3,5-Diaminobenzoyloxy)cholestane

DA-5: 2,2'-Dimethyl-4,4'-diaminobiphenyl

DA-6: 3,5-Diaminobenzoic acid

[Example 1: TN type liquid crystal display element]

(1) Preparation of liquid crystal aligning agent

In the solution containing the polymer (PHF-1) obtained in Synthesis Example 4, γ-butyl lactone (BLANT), NMP and diethylene glycol diethyl ether (DEDG) were added and dissolved to prepare BLANT:NMP: A solution of DEDG=55:30:15 (weight ratio), and a solid content concentration of 6.0% by weight. A liquid crystal aligning agent was prepared by filtering this solution with a filter with a pore diameter of 0.2 μm.

(2) Evaluation of surface roughness of coating film

Using a liquid crystal aligning film printer (manufactured by Nippon Photo Printing Co., Ltd.), the prepared liquid crystal aligning agent was coated on a silicon wafer, and then prebaked for 1 minute with an 80° C. hot plate. Then, it heated (post-baked) for 15 minutes with the hotplate of 230 degreeC, and the coating film with an average film thickness of 100 nm was formed. The coating film was observed with an atomic force microscope (Nano Scope IIIa, manufactured by Digital Instrument Co., Ltd.), and the surface roughness Ra (arithmetic mean height) of the coating film was measured. The evaluation was performed as follows: when Ra was less than 2.0 nm, the surface roughness was evaluated as "good", when it was 2.0 nm or more and less than 5.0 nm, it was evaluated as "good", and when it was 5.0 nm or more, it was evaluated as "poor". In this example, Ra was 0.3 nm, and the surface unevenness was "good".

(3) Evaluation of printability

Using a liquid crystal alignment film printer (manufactured by Nippon Photo Printing Co., Ltd.), the prepared liquid crystal alignment agent is coated on the transparent electrode surface of a glass substrate with a transparent electrode comprising an ITO film, and heated on a heating plate at 80° C. Heating (pre-baking) for 1 minute to remove the solvent, and then heating (post-baking) on a hot plate at 200°C for 10 minutes to form an average film thickness of coating film. This coating film was observed with a microscope at a magnification of 20 times, and the presence or absence of film thickness unevenness, orange peel defect unevenness, and linear unevenness was investigated. The evaluation was carried out as follows: when there was no film thickness unevenness and the coating surface was uniform, the printability was evaluated as "good", when orange peel defect unevenness was observed, the printability was evaluated as "possible", and when orange peel defect unevenness was observed, the printability was evaluated as "possible"; Cases of skin defect unevenness and linear unevenness were evaluated as "poor" in printability. In this example, the unevenness of the film thickness was not observed, and the inside of the coating surface was uniform, and the printability was "good".

(4) Evaluation of storage stability of liquid crystal aligning agent

・Evaluation based on leaching properties

The liquid crystal aligning agent prepared above was stored at 5 degreeC for 1 month, and the liquid crystal aligning agent after storage was visually observed. The case where precipitation of insoluble matter was not observed was evaluated as "good", and the case where precipitation of insoluble matter was observed was evaluated as "poor". As a result, it was evaluated as "good" in this Example.

・Evaluation by viscosity change

About the liquid crystal aligning agent prepared above, the solution viscosity was measured immediately after preparation and after storing at 5 degreeC for 1 month, respectively, and viscosity change rate (DELTA)η was calculated|required by following formula (2). In addition, the solution viscosity [mPa·s] of a liquid crystal aligning agent was measured at 25 degreeC using the E-type rotational viscometer.

Δη=((η _AF -η _BF )÷η _BF )×100 (2)

(In formula (2), η _BF is the solution viscosity measured immediately after preparation, and η _AF is the solution viscosity measured after storage at 5°C for 1 month)

The storage stability was evaluated as follows: if the viscosity change rate Δη was 5% or less, the storage stability was evaluated as "good", if it was more than 5% and less than 10%, it was evaluated as "acceptable", and if it was 10% Above, it was evaluated as "poor". As a result, it was evaluated as "good" in this Example.

(5) Manufacture of TN-type liquid crystal unit

Use liquid crystal aligning film printing machine (manufactured by Nippon Photo Printing (Stock)), the liquid crystal aligning agent prepared in the described (1) is coated on the transparent electrode face of the glass substrate with the transparent electrode that comprises ITO film, at 80 After heating (pre-baking) on a heating plate at ℃ for 1 minute to remove the solvent, heat (post-baking) on a heating plate at 200 °C for 10 minutes to form an average film thickness of coating film. This coating film was subjected to a rubbing treatment with a rubbing machine having a roller wound with a rayon cloth at a roller rotation speed of 500 rpm, a platen moving speed of 3 cm/sec, and a bristle indentation length of 0.4 mm to impart liquid crystal orientation ability. Then, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a 100° C. clean oven for 10 minutes, whereby a substrate having a liquid crystal aligning film was obtained. Moreover, the said operation was repeated, and a pair (two) board|substrates which have a liquid crystal aligning film were obtained.

Next, for one of the substrates in the pair of substrates, the outer edge of the surface with the liquid crystal alignment film is coated with an epoxy resin adhesive with a diameter of 5.5 μm alumina balls, and the surface of the liquid crystal alignment film is coated with an epoxy resin adhesive. A pair of substrates are put on top of each other and pressure-bonded to harden the adhesive. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck) is filled between the pair of substrates from the liquid crystal injection port, and the liquid crystal injection port is sealed with an acrylic light-curable adhesive to manufacture TN. type liquid crystal unit.

(6) Evaluation of liquid crystal orientation

For the liquid crystal cell produced in the above (5), the abnormal region in the light and dark change when the voltage of 5V was turned on and off (applied and released) was observed with a microscope under a crossed Nicols prism at a magnification of 50 times. Yes or no. When an abnormal region was not observed, it evaluated as liquid-crystal orientation "favorable", and when an abnormal region was observed, it evaluated as liquid-crystal orientation "poor". In this liquid crystal cell, the liquid crystal orientation was "favorable".

(7) Evaluation of voltage retention rate

For the liquid crystal cell produced in the above (5), after applying a voltage of 5V at 23° C. for an application time of 60 microseconds and a span of 167 milliseconds, the voltage holding ratio (Voltage Holding Ratio, VHR). In addition, as a measurement device, VHR-1 manufactured by Toyo Technica Co., Ltd. was used. The voltage retention rate of this liquid crystal cell was 97.8%.

(8) Evaluation of heat resistance

For the liquid crystal cell produced in (5) above, the voltage retention was measured in the same manner as in (7) above, and the value thereof was defined as initial VHR (VHR _BF ). Next, the liquid crystal display element after initial stage VHR measurement was left still in the oven of 100 degreeC for 300 hours. Then, this liquid crystal display element was left still at room temperature and left to cool to room temperature, and then the voltage retention (VHR _AF ) was measured in the same manner as described above. In addition, the change rate (ΔVHR (%)) of the voltage retention rate before and after application of thermal stress was obtained from the following formula (3).

ΔVHR＝((VHR _BF -VHR _AF )÷VHR _BF )×100 (3)

Evaluation of heat resistance was performed as follows: when the change rate ΔVHR was less than 4%, the heat resistance was evaluated as "good", when it was 4% or more and less than 5%, it was evaluated as "possible", and when it was 5% or more, it was evaluated as "good". The heat resistance was evaluated as "poor". As a result, in this example, ΔVHR=3.1%, and the heat resistance was "good".

[Example 2-Example 4, Example 7-Example 11, and Comparative Example 1-Comparative Example 7]

In Example 1, a liquid crystal aligning agent was prepared in the same manner as in Example 1, except that polymers of the types and amounts shown in the following Table 2 were used, and a TN type liquid crystal cell was produced and various evaluations were performed. . The evaluation results are shown in Table 3 below.

The numerical value in Table 2 shows the compounding ratio of each polymer with respect to 100 weight part of total amounts of the polymer used for preparing a liquid crystal aligning agent.

[table 3]

As shown in Table 3, in Examples 1 to 4, Example 7, Example 8, and Example 11 containing polymers (P) having an amic acid ester structure or an amic acid structure and an isoimide ring structure , the surface unevenness of the coating film, and the printability and storage stability of the liquid crystal aligning agent all obtained favorable results. Furthermore, in Examples 1 to 4, Example 7, Example 8, and Example 11, the liquid crystal orientation, voltage retention and heat resistance of the liquid crystal display element were "good" or "possible" results. It has various characteristics in a well-balanced manner. In addition, in Example 9 which is a combination of polyisoimide and polyamic acid ester, and Example 10 which is a combination of polyisoimide and polyamic acid, the surface roughness of the coating film, the effect of the liquid crystal aligning agent The printability and storage stability, and the liquid crystal orientation of a liquid crystal display element, a voltage retention rate, and heat resistance were the result of "good" or "possible".

On the other hand, in the comparative example, any one of the surface unevenness of a coating film, printability, the storage stability of a liquid crystal aligning agent, voltage retention, and heat resistance was evaluated as "poor".

[Example 5: Optical FFS type liquid crystal display element]

(1) Preparation of liquid crystal aligning agent

Using a solution containing the polymer (PAA-2) obtained in Synthesis Example 2 and a solution containing the polymer (PHF-2) obtained in Synthesis Example 5, the polymer (PAA-2): polymer (PHF- 2) After mixing in a method of =80:20 (weight ratio), add γ-butyl lactone (BLANT), NMP and diethylene glycol diethyl ether (DEDG) to make a solvent composition of BLANT:NMP:DEDG= 55:30:15 (weight ratio), a solution having a solid content concentration of 6.0% by weight. A liquid crystal aligning agent was prepared by filtering this solution with a filter with a pore diameter of 0.2 μm.

(2) Evaluation of surface roughness, printability and storage stability of liquid crystal aligning agent of coating film

Using the liquid crystal aligning agent prepared in (1), carry out the surface unevenness of the coating film, the printability and the storage stability of the liquid crystal aligning agent in the same manner as in Example 1 (2), (3) and (4). sexual evaluation. As a result, any characteristic was judged as "good".

(3) Manufacture of optical FFS type liquid crystal display element

The FFS type liquid crystal display element 10 shown in FIG. 1 was fabricated. First, a glass substrate 11a having an electrode pair on one side thereof, and a counter glass substrate 11b not provided with an electrode are taken as a pair. The silicon film and the top electrode 13 patterned into a comb shape are prepared in (1) by using a spinner on the surface with the transparent electrode of the glass substrate 11a and one of the sides facing the glass substrate 11b. liquid crystal aligning agent to form a coating film. Then, after prebaking the coating film on a hot plate at 80° C. for 1 minute, it was heated (post-baked) at 230° C. for 15 minutes in an oven replaced with nitrogen in the chamber to form an average film thickness of coating film. A schematic plan view of the top electrode 13 used here is shown in (a) and (b) of FIG. 2 . 2( a ) is a plan view of the top electrode 13 , and FIG. 2( b ) is an enlarged view of a portion C1 surrounded by a dotted line in FIG. 2( a ). In this example, the line width d1 of the electrodes was set to 4 μm, and the distance d2 between the electrodes was set to 6 μm. In addition, as the top electrode 13 , four driving electrodes of the electrode A, the electrode B, the electrode C, and the electrode D are used. The configuration of the driving electrodes used is shown in FIG. 3 . In this case, the bottom electrode 15 functions as a common electrode that acts on all the driving electrodes of the four systems, and the regions of the driving electrodes of the four systems serve as pixel regions.

Next, each surface of these coating films was irradiated with 300 J/m ² of polarized ultraviolet light including a bright line of 313 nm using a Hg-Xe lamp and a Glan-Taylor prism to obtain a pair of substrates having a liquid crystal aligning film. At this time, the irradiation direction of the polarized ultraviolet rays is from the normal direction of the substrate, so that the direction of the line segment projecting the polarization plane of the polarized ultraviolet rays onto the substrate is the direction of the double-headed arrows in (a) and (b) of FIG. 2 After setting the direction of the polarizing plane, it is provided for light irradiation treatment.

Then, on the periphery of the surface with the liquid crystal alignment film of one of the substrates, screen printing was used to apply an epoxy resin adhesive with a diameter of 5.5 μm alumina balls, and a pair of The liquid crystal aligning films of the substrates faced each other, and were laminated and pressure-bonded so that the direction in which the polarization plane of polarized ultraviolet light was projected on the substrate became parallel, and the adhesive was thermally cured at 150° C. for 1 hour. Next, after the liquid crystal "MLC-6221" manufactured by Merck was filled into the gap between the substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to eliminate the flow orientation at the time of liquid crystal injection, it was heated to 150° C. and then gradually cooled to room temperature.

Then, an FFS type liquid crystal display element was manufactured by bonding polarizing plates to both surfaces outside the substrate. At this time, one of the polarizers is attached in such a way that its polarization direction is parallel to the projection direction of the polarizing surface of the polarized ultraviolet light of the liquid crystal alignment film on the substrate surface, and the other is attached in a manner that its polarization direction is the same as that just now. Attach the polarizer so that the polarization direction is perpendicular to it.

(4) Evaluation of liquid crystal orientation, voltage retention and heat resistance

The optical FFS type liquid crystal display element manufactured in said (3) evaluated the liquid crystal orientation similarly to Example 1 (5), and the liquid crystal orientation of this liquid crystal display element was "good". In addition, the voltage retention rate (VHR _BF ) was measured in the same manner as in (6) of Example 1, and the heat resistance (voltage retention before and after thermal stress application) was performed in the same manner as in (7) of Example 1. rate of change). As a result, VHR _BF was 99.5%. In addition, ΔVHR was 2.8%, and the heat resistance was judged to be "good".

[Example 6: VA type liquid crystal display element]

(1) Preparation of liquid crystal aligning agent

80 parts by weight of the polymer (PAA-2) obtained in Synthesis Example 2 and 20 parts by weight of the polymer (PHF-3) obtained in Synthesis Example 6 were dissolved in (BLANT), NMP, and diethylene glycol diethyl ether (DEDG) in a mixed solvent (BLANT:NMP:DEDG=55:30:15 (weight ratio)) to prepare a solution with a solid content concentration of 6.0% by weight. A liquid crystal aligning agent was prepared by filtering this solution with a filter with a pore diameter of 0.2 μm.

(2) Evaluation of surface roughness, printability and storage stability of liquid crystal aligning agent of coating film

Except for using the liquid crystal aligning agent prepared in the above (1), the surface unevenness, printability and liquid crystal aligning agent of the coating film were carried out in the same manner as in Example 1 (2), (3) and (4). Evaluation of storage stability. As a result, any characteristic was judged as "good".

(3) Manufacture of VA liquid crystal unit

Using a liquid crystal alignment film printer (manufactured by Nippon Photo Printing Co., Ltd.), the liquid crystal alignment agent prepared in the above (1) was applied to the transparent electrode of a glass substrate (thickness: 1 mm) with a transparent electrode comprising an ITO film. On the surface, heat (pre-bake) on a hot plate at 80°C for 1 minute, and then heat (post-bake) on a hot plate at 200°C for 60 minutes to form an average film thickness of coating film (liquid crystal alignment film). This operation was repeated to obtain a pair (two pieces) of glass substrates having a liquid crystal aligning film on a transparent conductive film. Next, for one of the substrates in the pair of substrates, the outer edge of the surface with the liquid crystal alignment film is coated with an epoxy resin adhesive with a diameter of 5.5 μm alumina balls, and the surface of the liquid crystal alignment film is coated with an epoxy resin adhesive. A pair of substrates are laminated and pressure-bonded in a facing manner to harden the adhesive. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck) is filled between the pair of substrates from the liquid crystal injection port, and the liquid crystal injection port is sealed with an acrylic light-curing adhesive to manufacture a VA type. LCD unit.

(4) Evaluation of liquid crystal orientation, voltage retention and heat resistance

As a result of evaluating the liquid crystal orientation of the liquid crystal cell produced in the above (3) in the same manner as in (5) of Example 1, the liquid crystal orientation of this liquid crystal display element was "favorable". In addition, the voltage retention rate (VHR _BF ) was measured in the same manner as in (6) of Example 1, and the heat resistance (voltage retention before and after thermal stress application) was performed in the same manner as in (7) of Example 1. rate of change). As a result, VHR _BF was 98.9%. In addition, ΔVHR was 1.9%, and it was judged that the heat resistance was "good".

Claims (11)

1. A liquid crystal aligning agent comprising one or more polymers as a polymer component, and in the polymer component, a partial structure (a-1) represented by the following formula (1), and the partial structure (a-2) represented by the following formula (2), In formula (1) and formula (2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 12 carbons, -Si(R ⁷ ) ₃ , a monovalent group having a fluorine atom, having ( A monovalent group of a meth)acryloyl group or a monovalent group with a cinnamic acid structure, wherein ^R7 is an alkyl or alkoxy group, and multiple ^R7s can be the same or different, and ^R3 and ^R4 are independently independent is a hydrogen atom or a substituted or unsubstituted monovalent chain hydrocarbon group with 1 to 10 carbons; X ¹ and X ² are independently a tetravalent organic group, and Y ¹ and Y ² are independently a divalent organic group. base. The liquid crystal aligning agent of Claim 1 containing the polymer (P) which has the said partial structure (a-1) and the said partial structure (a-2) in 1 molecule. 3. The liquid crystal aligning agent according to claim 2, wherein the content ratio of the partial structure (a-1) and the partial structure (a-2) that the polymer (P) has is determined by the partial structure ( The molar ratio of a-1)/partial structure (a-2) is 1/99-99/1. The liquid crystal aligning agent according to claim 2, further comprising a polyamic acid. 5. The liquid crystal aligning agent according to claim 4, wherein the content ratio of the polymer (P) to the polyamic acid is 1/99 to 99 in the weight ratio of the polymer (P)/polyamic acid /1. 6. The liquid crystal aligning agent according to claim 4, wherein the polyamic acid has a structure represented by the following formula (3-1), a structure represented by the following formula (3-2), and nitrogen-containing At least one structure in the group consisting of heterocyclic rings, wherein, in the structure represented by formula (3-2), the acid anhydride group that tetracarboxylic dianhydride has and the amino group that diamine has react with Except those contained in the amide bond formed, In formula (3-1), R ⁵ is a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbons, or an alkoxy group with 1 to 10 carbons, and r is 1 or 2; when there are multiple R ⁵ Herein, a plurality of R ⁵ may be the same or different; * represents a bond; in formula (3-2), R ⁶ is a hydrogen atom or an alkyl group with 1 to 6 carbons; * represents a bond. The liquid crystal aligning agent of Claim 1 containing the 1st polymer which has the said partial structure (a-1), and the 2nd polymer which has the said partial structure (a-2). 8. The liquid crystal aligning agent according to any one of claims 1 to 7, wherein said R ¹ and said R ² are each independently an alkyl group having 1 to 5 carbon atoms. 9. The liquid crystal aligning agent according to any one of claims 1 to 7, wherein said X ¹ and said X ² are tetravalent groups derived from the compound selected from bicyclo[2.2.1 ]heptane-2,3,5,6-tetracarboxylic acid 2:3,5:6-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tri Carboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan -1,3-Diketone, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3- Diketone, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride , and at least one compound in the group consisting of pyromellitic dianhydride. The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-9. The liquid crystal display element provided with the liquid crystal aligning film of Claim 10.