TW201739837A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the same - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent which can obtain a liquid crystal alignment film which can maintain a voltage holding ratio even after being irradiated with light without impairing liquid crystal alignment. The liquid crystal alignment agent of the present invention contains the following (A) component, (B) component, (C) component, and an organic solvent, and (A) component: using a tetracarboxylic acid derivative component and containing the following formula a diamine compound having a structure of [A-1], a diamine compound having a structure of the following formula [A-2], and at least one diamine having a diamine compound having a structure of the following formula [A-3] a polyimine precursor obtained from a diamine component of the compound and at least one polymer selected from the group consisting of polyimine, and a component (B) selected from the group consisting of a structural unit represented by the following formula (2) At least one polymer of the amine precursor and the ruthenium imidized polymer of the polyimide precursor, and the component (C): a compound containing two or more crosslinkable functional groups. □□ (The definition of the symbol in the formula is as described in the manual).

Description

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

The present invention relates to a liquid crystal alignment agent used for the production of a liquid crystal display element, a liquid crystal alignment film obtained by the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film.

For liquid crystal display elements such as liquid crystal televisions, navigation, smart phones, etc., a liquid crystal alignment film for controlling the alignment state of liquid crystals is usually provided in the elements. The liquid crystal alignment film has a function of controlling the alignment of liquid crystal molecules in a specific direction in a liquid crystal display element or a phase difference plate using a polymerizable liquid crystal. For example, the liquid crystal display element has a structure in which liquid crystal molecules constituting the liquid crystal layer are caught by the liquid crystal alignment film formed on the respective surfaces of the pair of substrates. Therefore, the liquid crystal molecules are aligned in a specific direction by the pretilt angle by the liquid crystal alignment film, and a voltage is applied to the electrode provided between the substrate and the liquid crystal alignment film to generate a response. As a result, the liquid crystal display element performs desired image display by utilizing the alignment change caused by the response of the liquid crystal molecules.

The liquid crystal alignment film has hitherto mainly used a polyimine precursor or a soluble polyazide which will be a polyamic acid or the like. A liquid crystal alignment agent containing a solution of an amine as a main component is applied onto a glass substrate or the like to form a polyimine-based liquid crystal alignment film after firing.

Along with the high performance of liquid crystal display elements, in addition to exhibiting excellent liquid crystal alignment or stable pretilt angle, liquid crystal alignment films also require high voltage holding ratio, less residual charge when DC voltage is applied, and/or The residual charge accumulated by the DC voltage is rapidly relaxed, and the like, but in recent years, in order to reduce the power consumption of the liquid crystal display element, a high voltage holding ratio material is particularly required.

In order to meet the above requirements, there are various proposals. For example, a liquid crystal alignment agent containing a tertiary amine of a specific structure (for example, refer to Patent Document 1) or a liquid crystal alignment agent containing an additive of an isocyanate structure (for example, a poly-proline or a polyamido acid containing a quinone group) is proposed. Refer to Patent Document 2) and the like.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-316200

[Patent Document 2] WO2014/178406

[Inventive invention]

With the high performance of liquid crystal display elements in recent years, large paintings Liquid crystal display elements are used for high-definition LCD TVs or for automotive applications such as car navigation systems or instrument panels. In such a use, in order to obtain high brightness, there is a case where a backlight having a large amount of heat is used. Therefore, the liquid crystal alignment film requires high stability for light from the backlight. In particular, when the voltage holding ratio of one of the electrical characteristics of the liquid crystal display element is lowered by the light irradiation from the backlight, the image sticking defect (also referred to as line residual image) which is one of display defects of the liquid crystal display element is likely to occur, and the image retention is not obtained. Highly reliable liquid crystal display element.

Therefore, in addition to the initial characteristics of the liquid crystal alignment film, for example, it is also required that the voltage holding ratio is not easily lowered even after long-time light irradiation. Further, in order to reduce power consumption, low frequency driving is also required, and an alignment film having high voltage holding ability is further required.

When a liquid crystal alignment agent in which various crosslinking agents are added to polyamic acid is used, a liquid crystal display element having excellent voltage holding characteristics can be obtained, but the liquid crystal alignment property may be impaired. Further, the effect of the crosslinking agent may not be sufficiently exhibited due to the combination with the polymer species contained in the liquid crystal alignment agent, and the voltage holding ratio may be insufficient.

The inventors of the present invention have completed the present invention in order to solve the above problems and carefully review the results. That is, the technical features of the present invention are as follows.

A liquid crystal alignment agent containing the following components (A), (B), (C), and an organic solvent.

(A) component: a tetracarboxylic acid derivative component and a diamine compound containing a structure selected from the group consisting of the following formula [A-1], a diamine compound having a structure of the following formula [A-2], and a polyimine precursor obtained from a diamine component of at least one diamine compound of the diamine compound having the structure of the following formula [A-3], and at least one polymer selected from the polyimine. (R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group represented by the following formula (1), and at least one of them is a thermal desorption property of a protecting group substituted with a hydrogen atom by heat. a group, R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms which may have a substituent, and D is a thermal debonding group substituted with a protecting group of a hydrogen atom by heat. .)

(B) component: at least one polymer selected from the group consisting of a polyimine precursor having a structural unit represented by the following formula (2) and a quinone imidized polymer of the polyimine precursor , (X ₁ is a tetravalent organic group represented by the following formula (X-1), Y ₁ is a divalent organic group, R ₁ is a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and each of A ₁ to A ₂ Independently a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms which may have a substituent)

Component (C): A compound containing two or more crosslinkable functional groups.

According to the liquid crystal alignment agent of the present invention, it is possible to obtain a liquid crystal alignment film which does not impair the liquid crystal alignment property over a long period of time, and particularly maintains a voltage holding ratio even after light irradiation. Thereby, the liquid crystal display element which has the liquid crystal alignment film obtained by the liquid-crystal alignment agent of this invention can provide the outstanding display used for a liquid crystal television, a smart phone, car navigation, etc..

[Formation of the Invention] <(A) component>

The component (A) contained in the liquid crystal alignment agent of the present invention has a tetracarboxylic acid derivative component and a diamine compound selected from the group consisting of the following formula [A-1], and has the following formula [A-2] Polydiimide compound having a structure of a diamine compound having a structure of a diamine compound having a structure of the following formula [A-3], and a polyimine component obtained by disodium imide of at least one diamine compound selected from the following At least one type of polymer (hereinafter also referred to as a specific polymer (A)).

In the formula [A-1], R ¹ , R ² and A are as defined above. Here, at least one or both of R ¹ and R ² are heat-releasing groups which are substituted with a protecting group of a hydrogen atom by heat. From the viewpoint of the strength of the alignment film at the time of rubbing, it is particularly preferable that only one of R ¹ and R ² is a heat-releasing group.

The heat-releasing group is preferably not removed at room temperature from the viewpoint of storage stability of the liquid crystal alignment agent, and is preferably 80 ° C or higher, and more preferably 100 ° C or higher. The heat-releasing group is preferably a group represented by the following formula (1) or a 9-fluorenylmethoxycarbonyl group.

In the formula (1), A is a single bond or a hydrocarbon group having 1 to 4 carbon atoms, preferably a divalent group derived from an alkylene group. From the viewpoint of the temperature of the detachment, a third butoxycarbonyl group is preferred.

A preferred example of the diamine having a structure represented by the above formula [A-1] in the molecule is a diamine represented by the following formula [A-1-1].

In the above formula [A-1-1], R ¹ and R ² each preferably contain the same, and are the same as in the case of the formula [A-1]. The two n are each independently an integer of 0 to 3, and the easiness from the raw material is preferably 0 or 1, more preferably 1.

Further, in the formula [A-1-1], the amine group (-NH ₂ ) in the respective benzene rings may be adjacent to, or in the vicinity of, the bonding position with respect to the alkylene group, but From the viewpoint of easiness of synthesis and polymerization reactivity, it is preferably a meta position or a para position, and more preferably a para position.

Preferable examples of the diamine represented by the formula [A-1-1] include the following compounds.

In the formula [A-2], R ₃ and R ₄ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. In particular, when a large volume of a substituent is used, the liquid crystal alignment property may be lowered, so that a hydrogen atom, a carbon number of 1 to 6 alkyl groups, or a phenyl group is preferable, and a hydrogen atom or a methyl group is particularly preferable.

D is a thermally detachable group substituted with a protecting group of a hydrogen atom by heat, and also includes the preferred aspect as defined in the above formula [A-2]. Particularly preferred is a third butoxycarbonyl group.

The diamine having the structure represented by the above formula [A-2] is preferably represented by the following formula [A-2-1].

In the case of the following formula [A-2-2], the liquid crystal alignment film obtained by the liquid crystal alignment film has a high liquid crystal alignment property, which is particularly preferable.

A ¹ and A ⁵ are each independently a single bond or an alkylene group having 1 to 5 carbon atoms. From the viewpoint of reactivity with a functional group in the sealant, a single bond or a methylene group is preferred. A ² and A ⁴ are an alkylene group having 1 to 5 carbon atoms, preferably a methylene group or a vinyl group.

A ³ is an alkylene group having a carbon number of 1 to 6, or a cycloalkyl group. From the viewpoint of reactivity with a functional group in the sealant, a methylene group or a vinyl group is preferred.

B ¹ and B ² are each independently a single bond, -O-, -NH-, -NMe-, -C(=O)-, -C(=O)O-, -C(=O)NH-,- C(=O)NMe-, -OC(=O)-, -NHC(=O)-, or -N(Me)C(=O)-. From the viewpoint of liquid crystal alignment of the obtained liquid crystal alignment film, a single bond or -O- is preferable.

D ₁ is a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. From the viewpoint of the temperature of deprotection, a third butoxycarbonyl group is preferred. a is 0 or 1.

Specific examples of the diamine represented by the formula (A-2-2) include the following formulas (2-1) to (2-21).

In the formulae (2-1) to (2-21), Me represents a methyl group, and D ₂ represents a third butoxycarbonyl group.

Among them, the formula (2-1) to (2-4) is more preferable, and the formula (2-1) is particularly preferable.

The diamine having the structure represented by the above formula [A-3] is preferably represented by the following formula [A-3-1] or the following formula [A-3-2].

Wherein, it is represented by the following formula [A-3-3] and the following formula [A-3-4] In the case of the liquid crystal alignment film, the liquid crystal alignment property of the obtained liquid crystal alignment film becomes high, which is particularly preferable.

In the formula [A-3-1] and the formula [A-3-3], A ¹ , A ⁵ , B ¹ and B ² also include a preferred example, and the A described in the formula [A-2-1] ¹ , A ⁵ , B ¹ , and B ^{2 are the} same definition. R _{5 is} each independently a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms which may have a substituent. From the viewpoint of liquid crystal alignment, R _{5 is} preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom.

A ⁶ is a single bond or an alkylene group having 1 to 6 carbon atoms. From the viewpoint of liquid crystal alignment, a single bond, a methylene group, a vinyl group, or a propylene group is preferred, and a single bond or a methylene group is more preferred.

D ₁ is a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group, and a third butoxycarbonyl group is preferred from the viewpoint of the temperature of deprotection. a is 0 or 1.

In the formula [A-3-2] and the formula [A-3-4], preferred examples of A ⁶ , R ₅ and D ₁ are also the A ⁶ and R described in the formula [A-2-1]. ₅ , and D _{1 have the} same definition.

Specific examples include the following formula (3-1) to formula (3-5).

In the formulae (3-1) to (3-5), D ₂ represents a third butoxycarbonyl group.

Among them, the formula (3-1) to the formula (3-4) is more preferable, and the formula (3-1) is particularly preferable.

At least 1 selected from the group consisting of a diamine having the structure represented by the above formula [A-1], a diamine having the structure represented by the above formula [A-2], and a diamine having the structure represented by the above formula [A-3] The content of the diamine is used for the production of the polyimine precursor used in the component (A) contained in the liquid crystal alignment agent of the present invention and the ruthenium imidized polymer of the polyimide precursor. The total diamine component is preferably from 5 to 80 mol%, more preferably from 10 to 50 mol%.

The diamine component used for the component (A) contained in the liquid crystal alignment agent of the present invention may be a diamine selected from the structures represented by the above formulas [A-1], [A-2] and [A-3]. At least one diamine and other diamines.

Examples of the other diamines mentioned above include 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, and 4,4'-diamine. Biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'- Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy- 4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3, 4'-Diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diamino Diphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-di Aminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diamine Diphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, Bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiobisanilide, 3,3'-thiobisaniline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2, 2'-Diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl (3, 3'-Diaminodiphenyl)amine, N-methyl (3,4'-di Diphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'- Diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diamine Benzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8- Diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-amine Phenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl) Propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl) Methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-amine Phenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene , 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]diphenylamine, 4,4'-[1,3- Phenyl bis(methylene)]diphenylamine, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine, 3,4'-[1,3-phenylene double (methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3'-[1,3-phenylene bis(methylene) )]Diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylphenylbis[(3-aminophenyl)methanone], 1,3 - phenyl bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4-) Amino benzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3- Phenyl bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis (4) -aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzene Promethamine), N, N'-(1,3-phenylene) (4-Aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene) Bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)-p-benzene Dimethylamine, N,N'-bis(4-aminophenyl)m-xylyleneamine, N,N'-bis(3-aminophenyl)m-xylyleneamine, 9,10 - bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy) Phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2, 2'-bis(3-aminophenyl)hexafluoro Propane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3- Aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-double ( 3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis ( 4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-double (3-Aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-double (4-Aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9- Bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-( 4-aminophenoxy)undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-aminophenoxy)dodecane, 1,12- (3-Aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1 , 4-diaminobutane, 1,5-diamino Alkane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminoguanidine Alkane, 1,11-diaminoundecane or 1,12-diaminododecane, and such amines are amines of the second amine group.

The other diamine compound used for the component (A) contained in the liquid crystal alignment agent of the present invention is based on the solubility of the component (A) in the solvent or the coating property of the liquid crystal alignment agent, and the liquid crystal alignment as the liquid crystal alignment film. One or two or more kinds of properties, such as properties, voltage retention ratio, and accumulated charge, can be used.

<tetracarboxylic acid derivative component>

The tetracarboxylic acid derivative component for the component (A) contained in the liquid crystal alignment agent of the present invention is not only a tetracarboxylic dianhydride but also a tetracarboxylic acid or a tetracarboxylic acid of a tetracarboxylic acid derivative thereof. Or a dialkyl tetracarboxylate or a dialkyl dicarboxylate. Among them, at least one selected from the group consisting of tetracarboxylic dianhydride represented by the following formula [4] and a tetracarboxylic acid dialkyl ester thereof represented by the following formula [4] is preferred. The tetracarboxylic dianhydride represented by the following formula [4] and its derivative are collectively referred to as a specific tetracarboxylic acid component.

In the formula (4), Z represents a structure selected from at least one selected from the group consisting of the following formulas [4a] to [4q].

Z ¹ to Z ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group.

From the viewpoint of easiness of synthesis or easiness of polymerization reactivity in producing a polymer, Z is preferably a formula [4a], a formula [4c] to a formula [4g], a formula [4k] to a formula [4m] or a formula. [4p]. More preferably, it is a formula [4a], a formula [4e]~ a formula [4g], a formula [4l], a formula [4m] or a formula [4p]. Particularly preferred is [4a], formula [4e], formula [4f], formula [4l], formula [4m] or formula [4p].

Further, specifically, it is preferably the following formula [4a-1] or formula [4a-2].

(A) a specific tetracarboxylic acid component in the composition, in all four The carboxylic acid derivative component is preferably 100 to 100 mol%, more preferably 70 to 100 mol%, and particularly preferably 80 to 100 mol%, in 100 mol%.

The specific tetracarboxylic acid component can be used according to the solubility of the specific polymer (A) to the solvent, the applicability of the liquid crystal alignment agent, the liquid crystal alignment property when the liquid crystal alignment film is used, the voltage retention ratio, and the charge accumulation. Type or more than two types.

In the polyimine-based polymer of the specific polymer (A), a tetracarboxylic acid component other than the specific tetracarboxylic acid component may be used.

Examples of the other tetracarboxylic acid component include a tetracarboxylic acid, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide, a dicarboxylic acid dialkyl ester, or a tetracarboxylic acid dialkyl ester dihalide.

Examples of the other tetracarboxylic acid component include 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, and 3. 3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4 , 4'-benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyl Phenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)methicone Base decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3 , 3',4,4'-diphenylstilbenetetracarboxylic acid, 3,4,9,10-decanetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutane IV Carboxylic acid, etc.

The other tetracarboxylic acid component described above is in accordance with the solubility of the specific polymer (A) in the solvent or the coating property of the liquid crystal alignment agent, the liquid crystal alignment property as a liquid crystal alignment film, the voltage retention ratio, and the accumulated charge. It is also possible to use one type or a mixture of two or more types.

<(B) component>

The component (B) contained in the liquid crystal alignment agent of the present invention is selected from the group consisting of a polyimine precursor having a structural unit represented by the following formula (2) and a ruthenium imidized polymer of the polyimide precursor. At least one type of polymer (hereinafter also referred to as a specific polymer (B)) in a group.

In the formula (2), X ₁ , Y ₁ , R ₁ and A ₁ to A ₂ are as defined above. Among them, R _{1 is} preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. A ₁ to A _{2 are} preferably a hydrogen atom or a methyl group.

Specific examples of the above alkyl group in R ₁ include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, and an n-pentylene group. Base. From the viewpoint of being easily imidized by heating, R _{1 is} preferably a hydrogen atom or a methyl group.

The preferred content ratio of the structural unit of the above (2) is 5 to 90 mol%, more preferably 10 to 90 mol%, still more preferably 10 to 80 mol%, in the same polymer.

Further, the polymer of the component (B) may have a structural unit of the following formula (3) in addition to the structural unit represented by the above formula (2).

The component (B) of the present invention may be a polymer having a structural unit represented by the formula (2) and a structural unit of the formula (3), or a polymer having the structural unit represented by the formula (2) and a formula (3). a mixture of polymers of structural units, but the former is preferred. The content ratio of the structural unit of the formula (3) contained in the polymer of the component (B) is 5 to 90 mol%, preferably 10 to 90 mol%, more preferably 20 to 20% in the polymer. 90% by mole.

In the above formula (3), X ₂ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and the structure thereof is not particularly limited. X ₂ may be mixed in two or more types. When a specific example of X ₂ is shown, the following formula (X-2) - (X-44) is mentioned.

In the above formula (X-2), R ₈ to R ₁₁ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group or a phenyl group. When R ₈ to R ₁₁ are in a large-volume structure, the alignment of the liquid crystal may be lowered, so that a hydrogen atom, a methyl group or an ethyl group is preferable, and a hydrogen atom or a methyl group is particularly preferable.

In the formula (3), X _{2 is} obtained from a monomer, and preferably contains a structure selected from (X-2) to (X-14).

Further, the reliability of the obtained liquid crystal alignment film is further improved, and X _{2 is} preferably a structure formed only of aliphatic groups such as (X-2) to (X-7) and (X-10), more preferably (X). -2). Further, in order to exhibit good liquid crystal alignment, X ₂ is more preferably a formula (X2-1) or (X2-2).

In the above formulas (2) and (3), each of A ₁ and A _{2 is} independently a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and a carbon number of 2 to 10 which may have a substituent. An alkynyl group having 2 to 10 carbon atoms which may have a substituent.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, and a dicyclohexyl group. The alkenyl group may be one in which one or more CH-CH structures present in the above alkyl group are substituted with a C=C structure, and more specifically, a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, and the like. 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl, and the like. Examples of the alkynyl group include a structure in which one or more CH ₂ -CH ₂ groups present in the alkyl group are substituted with a C≡C structure, and more specifically, an ethynyl group, a 1-propynyl group, and a 2-propynyl group are mentioned. Wait.

The alkyl group, the alkenyl group, and the alkynyl group may further contain a substituent, and a ring structure may be formed by a substituent. Further, the formation of a ring structure by a substituent means that the substituents are bonded to each other or a part of the substituent to a part of the parent skeleton to form a ring structure.

Examples of the substituent include a halogen group, a hydroxyl group, a mercapto group, a nitro group, an aryl group, an organic oxy group, an organothio group, an organomethylalkyl group, a decyl group, an ester group, and a thioester. Thioester), phosphate, decyl, alkyl, alkenyl, alkynyl.

Examples of the halogen group of the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The aryl group of the substituent may, for example, be a phenyl group. This aryl group may also be substituted with the other substituents described above.

The organooxy group of the substituent may represent a structure represented by O-R. These R may be the same or different, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group and the like. These R may also be resubstituted by the aforementioned substituents. Specific examples of the organic oxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.

The organothiol group of the substituent may represent a structure represented by -S-R. Examples of the R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These R may also be resubstituted by the aforementioned substituents. Specific examples of the organic thiol group include a methylthiol group, an ethyl thiol group, a propyl thiol group, and the like. Butyl thiol group, pentyl thiol group, hexyl thiol group, heptyl thiol group, octyl thiol group and the like.

The organomethylmercaptoalkyl group of the substituent may represent a structure represented by -Si-(R) ₃ . These R may be the same or different, and examples thereof include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These R may also be resubstituted by the aforementioned substituents. Specific examples of the organomethylmercaptoalkyl group include trimethylcarbinyl group, triethylcarbenyl group, tripropylcarbenyl group, tributylcarbenyl group, tripentylmethyl decyl group, and trihexylmethyl decyl group. Pentyl dimethyl methoxyalkyl, hexyl dimethyl methoxyalkyl, and the like.

The thiol group of the substituent may represent a structure represented by -C(O)-R. Examples of the R include the aforementioned alkyl group, alkenyl group, aryl group and the like. These R may also be resubstituted by the aforementioned substituents. Specific examples of the mercapto group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a benzamidine group, and the like.

The ester group of the substituent may represent a structure represented by -C(O)O-R or -OC(O)-R. Examples of the R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These R may also be resubstituted by the aforementioned substituents.

The thioester group of the substituent may represent a structure represented by -C(S)O-R or -OC(S)-R. Examples of the R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These R may also be resubstituted by the aforementioned substituents.

The phosphate group of the substituent may represent a structure represented by -OP(O)-(OR) ₂ . These R may be the same or different, and examples thereof include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. These R may also be resubstituted by the aforementioned substituents.

The amide group of the substituent may be represented by -C(O)NH ₂ , or -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ , -NRC(O) R represents the structure. These R may be the same or different, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group and the like. These R may also be resubstituted by the aforementioned substituents.

The aryl group of the substituent may be the same as the above aryl group. This aryl group may also be substituted with the other substituents described above.

The alkyl group of the substituent may be the same as the alkyl group described above. This alkyl group may also be substituted with the other substituents described above.

The alkenyl group of the substituent may be the same as the above alkenyl group. This alkenyl group may also be resubstituted with the other substituents described above.

The alkynyl group of the substituent may be the same as the alkynyl group described above. This alkynyl group may also be resubstituted with the other substituents described above.

When a large volume structure is introduced, the reactivity of the amine group or the liquid crystal alignment property may be lowered. Therefore, A ₁ and A _{2 are more} preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, particularly preferably A hydrogen atom, a methyl group or an ethyl group.

In the formula (2) and the formula (3), Y ₁ is derived from a divalent organic group of a diamine, and examples thereof include the following Y-1 to Y-118.

In the formula (Y-109), m and n are independently 1 to 11, m+n is 2 to 12, in the formula (Y-114), h is 1 to 3, and the formula (Y-111), (Y- In 117), j is 0~3.

From the viewpoint of the liquid crystal alignment property or the pretilt angle of the obtained liquid crystal alignment film, Y _{1 is more} preferably at least one selected from the structures represented by the following formulas (5) and (6).

In the formula (5), R ₁₂ is a single bond or a divalent organic group having 1 to 30 carbon atoms, R ₁₃ is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 30 carbon atoms, and a is a 1 to 4 In the case where a is 2 or more, R ₁₂ and R ₁₃ may be the same or different from each other, and R ₁₄ is a single bond, -O-, -S-, -NR ₁₅ -, guanamine bond in the formula (6). And an ester bond, a urea bond, or a divalent organic group having 1 to 40 carbon atoms, and R ₁₅ is a hydrogen atom or a methyl group.

Specific examples of the formula (5) and the formula (6) include the following structures.

When the linear structure is high as a liquid crystal alignment film, the alignment of the liquid crystal can be improved, so Y ₁ is more preferably Y-7, Y-21, Y-22, Y-23, Y-25, Y-43, Y. -44, Y-45, Y-46, Y-48, Y-63, Y-71, Y-72, Y-73, Y-74, Y-75, Y-98, Y-99, Y-100 , Y-118. The ratio of the above structure which can improve the liquid crystal alignment property is preferably 20 mol% or more, more preferably 60 mol% or more, and still more preferably 80 mol% or more of the entire Y ₁ .

In the case of a liquid crystal alignment film, in order to increase the pretilt angle of the liquid crystal, it is preferred that the side chain has a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination of Y ₁ . Such Y _{1 is} preferably Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86. Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, Y-97. To increase the ratio of the structure when the pretilt angle, all of Y ₁ is preferably 1 to 30 mole%, more preferably from 1 to 20 mole%.

The polyimine precursor used in the present invention is obtained by reacting a diamine component with a tetracarboxylic acid derivative, and examples thereof include polyglycolic acid or polydecylamine.

<(C) component>

The component (C) contained in the liquid crystal alignment agent of the present invention is a compound containing two or more crosslinkable functional groups. Examples of the crosslinkable functional group include a hydroxyl group, a hydroxyalkylguanamine group, a (meth)acrylate group, a blocked isocyanate group, an oxetanyl group, an epoxy group, and the like, but are not limited thereto. And so on.

Among them, from the viewpoint of the effect of improving the availability and the voltage retention ratio, a hydroxyl group, a blocked isocyanate group or an epoxy group is preferred, and a hydroxyl group or an epoxy group is more preferred. Further, the structure of the component (C) may have two or more of the same crosslinkable functional groups, or may have two or more kinds of crosslinkable functional groups different from each other.

For the compound containing two or more hydroxyl groups, for example, a compound represented by the following formula (7) can be mentioned.

X ₃ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group, n is an integer of 2 to 6, and R ₆ and R ₇ are each independently a hydrogen atom or may have a substituent. The alkyl group having 1 to 4 carbon atoms, the alkenyl group having 2 to 4 carbon atoms, or the alkynyl group having 2 to 4 carbon atoms, and at least one of R ₆ and R ₇ are represented by the following formula (6).

R ₈ to R ₁₁ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group. Similarly to the above, X _{3 is} preferably an aliphatic hydrocarbon group, more preferably a carbon number of 1 to 10, from the viewpoint of liquid crystal alignment and solubility. n represents an integer of 2 to 6, but from the viewpoint of solubility, n is preferably 2 to 4.

Specifically, the following compounds are mentioned.

Examples of the compound containing two or more blocked isocyanate groups include compounds represented by the following formula (9).

Each of the four Z groups is independently an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or an organic group represented by the following formula (10), and at least one of Z is an organic group represented by the following formula (10).

Specifically, the following compounds are mentioned, for example.

Examples of the compound containing two or more blocked isocyanate groups other than the above formula (11) include the following compounds.

Specific examples of the compound containing two or more epoxy groups include the following compounds.

Specific examples of the compound containing two or more (meth) acrylate groups include the following compounds.

Other examples include the following compounds.

<Content ratio of each component>

The content ratio of the component (A), the component (B), and the component (C) contained in the liquid crystal alignment agent of the present invention, wherein the content of the component (A) is in the liquid crystal alignment, preferably 20 to 80. The mass% is more preferably 20 to 60% by mass, particularly preferably 30 to 50% by mass.

Further, the content ratio of the component (B) is preferably 20 to 80% by mass, more preferably 40 to 80% by mass, even more preferably 50 to 70% by mass, based on the component (A).

Further, the content ratio of the component (C) is preferably from 1 to 30% by weight, more preferably from 3 to 20% by weight, particularly preferably from 3 to 15% by weight based on the total of the components (A) and (B). %.

<Production of Polyimine Precursor-Polyamic Acid>

The polyaminic acid of the polyimine precursor used in the above (A) component and (B) component is manufactured by the following method. Specifically, the tetracarboxylic acid component such as tetracarboxylic dianhydride and the diamine component are allowed to react in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes. It is produced by reacting for 24 hours, preferably 1 to 12 hours.

The reaction of the diamine component with the tetracarboxylic acid component is usually carried out in an organic solvent. The organic solvent to be used at this time is not particularly limited as long as it is a polyimide precursor which can be produced by dissolution. Specific examples of the organic solvent used in the following reaction include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, and N. , N-dimethylacetamide, dimethyl hydrazine or 1,3-dimethyl-imidazolidinone.

Further, when the solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula may be used. [D-1]~ an organic solvent represented by the formula [D-3].

In the formula [D-1] to [D-3], D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² represents an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms.

These solvents may be used singly or in combination. Further, even a solvent which does not dissolve the polyimide precursor can be used in the above solvent within a range in which the produced polyimide intermediate does not precipitate. Further, the water in the solvent hinders the polymerization reaction and causes the produced polyimine precursor to be hydrolyzed. Therefore, it is preferred that the solvent be dehydrated and dried.

The concentration of the poly-proline polymer in the reaction system is less likely to cause precipitation of the polymer, and a high molecular weight body is easily obtained, so that it is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass.

The obtained polylysine can be precipitated and recovered by sufficiently stirring the reaction solution while being injected into a weak solvent. Further, after several times of precipitation, it is washed with a weak solvent, and then dried at room temperature or under heating to obtain a purified polyamine acid powder. The weak solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like.

<Manufacture of Polyimine Precursor-Polyurethane>

The polyphthalamide of the polyimide precursor can be produced by the method (1), (2) or (3) shown below.

(1) Cases made of polylysine

Polyammonium esters can be produced by esterifying the polyamic acid produced as described above. Specifically, the polyglycine and the esterifying agent can be reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably at 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably. It is made for 1~4 hours.

The esterifying agent is preferably one which can be easily removed by purification, and examples thereof include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide diethyl acetal. N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dineopentyl butyl acetal, N,N-dimethylformamide di-t-butyl Acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene, 4 -(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylchlorinated porphyrin salt and the like. The amount of the esterifying agent added is 1 mol with respect to the repeating unit of polyglycolic acid, preferably 2 to 6 mol.

The organic solvent may, for example, be N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide. , dimethyl hydrazine or 1,3-dimethyl-imidazolidinone. Further, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or The solvent represented by the above formula [D-1] to formula [D-3].

These solvents may be used singly or in combination. In addition, even if it is a solvent that does not dissolve the polyimide precursor, the resulting polyimide precursor will not Within the range of precipitation, it can be used in combination with the above solvent. Further, the water in the solvent hinders the polymerization reaction and causes the produced polyimine precursor to be hydrolyzed. Therefore, it is preferred that the solvent be dehydrated and dried.

The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ -butyrolactone in terms of solubility of the polymer, and these may be used. Two or more types are used in combination or in combination. The concentration at the time of production is less likely to cause precipitation of the polymer and is easy to obtain a high molecular weight body, and is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass.

(2) A case produced by the reaction of a tetracarboxylic acid diester dichloride with a diamine

Polyammonium esters can be made from tetracarboxylic acid diester dichlorides and diamines.

Specifically, the reaction can be carried out for 30 minutes by using a tetracarboxylic acid diester dichloride and a diamine in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C. It is manufactured in 24 hours, preferably 1 to 4 hours.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used, but in order to stably carry out the reaction, pyridine is preferred. The amount of the base to be added is easily removed, and the viewpoint of easily obtaining a high molecular weight body is preferably 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride.

The solvent to be used in the above reaction is preferably N-methyl-2-pyrrolidone or γ -butyrolactone in terms of the solubility of the monomer and the polymer. These may be used alone or in combination of two or more. use. The polymer concentration at the time of production is less likely to cause precipitation of the polymer, and is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint of easily obtaining a high molecular weight body. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferred that the solvent used for the production of the polyglycolate is dehydrated as much as possible, and it is preferably carried out in a nitrogen atmosphere in order to prevent the incorporation of outside air. .

(3) Cases produced by tetracarboxylic acid diester and diamine

Polyammonium esters can be produced by polycondensation of a tetracarboxylic acid diester with a diamine. Specifically, the reaction can be carried out for 30 minutes to 24 hours by using a tetracarboxylic acid diester and a diamine in the presence of a condensing agent, a base, and an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C. It is preferably manufactured in 3 to 15 hours.

As the condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholine, O-(benzotriazol-1-yl)-N,N,N',N'-four Methylurea tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylmethylurea hexafluorophosphate, (2,3-dihydrogen) 2-Dithiol thioxo-3-benzoxazolyl)phosphonate. The amount of the condensing agent added is preferably 2 to 3 moles per mole of the tetracarboxylic acid diester.

As the base, a tertiary amine such as pyridine or triethylamine can be used. The amount of the base to be added is easily removed, and the viewpoint of easily obtaining a high molecular weight body is preferably 2 to 4 times the molar amount of the diamine component.

Further, in the above reaction, the reaction is efficiently carried out by adding a Lewis acid as an additive. The Lewis acid is preferably a lithium halide such as lithium chloride or lithium bromide. The addition amount of the Lewis acid is preferably 0 to 1.0 times the molar amount of the diamine component.

In the method for producing the above three kinds of polyphthalate, in order to obtain a high molecular weight polyphthalate, the method of the above (1) or (2) is particularly preferable.

The solution of the polyphthalate obtained as described above is poured into a weak solvent while being sufficiently stirred, whereby the polymer can be precipitated. After several times of precipitation and washing with a weak solvent, the purified polyphthalate powder can be obtained at room temperature or by heating. The weak solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like.

<polyimine]

The polyimine used in the present invention can be produced by subjecting the aforementioned polyphthalate or polylysine to ruthenium. In the case of producing a polyimine from a polyphthalate, a basic catalyst is added to the polyphthalate solution or a polyamic acid solution obtained by dissolving a polyphthalate resin powder in an organic solvent. The chemical hydrazine imidization is relatively simple. The chemical hydrazine imidization is preferred for the ruthenium imidization reaction at a lower temperature, and it is less likely to cause a decrease in the molecular weight of the polymer during the imidization process.

The chemical hydrazine imidization can be chemically imidized by stirring the polyamidated phthalocyanate in an organic solvent in the presence of a basic catalyst. As the organic solvent, the solvent used in the above polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. In particular, triethylamine is preferred because it has sufficient alkalinity for carrying out the reaction.

The temperature at which the hydrazine imidization reaction is carried out is -20 ° C to 140 ° C, It is preferably from 0 ° C to 100 ° C and the reaction time is from 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, per mole of the phthalate group. The oxime imidization ratio of the obtained polymer can be controlled by adjusting the amount of the catalyst, the temperature, and the reaction time. In the solution after the imidization reaction, since the added catalyst or the like remains, the obtained quinone imidized polymer is recovered by the means described below, and re-dissolved in an organic solvent to obtain a liquid crystal alignment agent. good.

In the case where the polyimine is produced from polylysine, the chemical ruthenium imidization of the catalyst in the solution of the polyamic acid obtained by the reaction of the diamine component and the tetracarboxylic dianhydride is relatively simple. The chemical oxime imidization is preferably carried out at a lower temperature for the ruthenium imidization reaction, and it is less likely to cause a decrease in the molecular weight of the polymer during the imidization.

The chemical ruthenium iodization can be chemically imidized by stirring the polyaminic acid to be imidized in an organic solvent in the presence of an alkaline catalyst and an acid anhydride. As the organic solvent, the solvent used in the above polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has a moderate basicity required for carrying out the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. When acetic anhydride is used, purification after completion of the reaction becomes easy, which is preferable.

The temperature at which the ruthenium imidization reaction is carried out may be from -20 ° C to 140 ° C, preferably from 0 ° C to 100 ° C, and the reaction time is from 1 to 100 hours. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the anhydride is 1 to 50 moles, preferably 3 to the amidate group. 30 moles Times. The oxime imidization ratio of the obtained polymer can be controlled by adjusting the amount of the catalyst, the temperature, and the reaction time.

In the solution after the imidization reaction of the polyperurethane or polylysine, since the added catalyst or the like remains, the obtained ruthenium-imided polymer is recovered by the means described below. The organic solvent is redissolved as the liquid crystal alignment agent of the present invention.

The solution of the polyimine obtained as described above can be precipitated by being sufficiently stirred while being injected into a weak solvent. Further, after several times of precipitation, it is washed with a weak solvent, and then dried at room temperature or under heating to obtain a purified polyphthalate powder.

The weak solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention has a form of a solution in which the specific polymer (A), the specific polymer (B), and the component (C) are dissolved in an organic solvent. The molecular weight of the specific polymer (A) and the specific polymer (B) preferably has a weight average molecular weight of 2,000 to 500,000, more preferably 5,000 to 300,000, still more preferably 10,000 to 100,000. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, still more preferably from 5,000 to 50,000.

The content (concentration) of the polymer containing the specific polymer (A) and the specific polymer (B) in the liquid crystal alignment agent of the present invention, The thickness of the coating film to be formed is appropriately changed, but when it is formed into a uniform and defect-free coating film, it is preferably 1% by mass or more, and is preferably 10% by mass or less from the viewpoint of storage stability of the solution. Among them, it is preferably 2 to 7 mass%, particularly preferably 3 to 6 mass%.

The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as it is uniformly soluble in a specific structural polymer. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl fluorene, γ - Butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. Among them, preferred is N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone.

Further, in the case where the solubility of the polymer to the solvent is high, it is preferred to use the solvent represented by the above formula [D-1] to formula [D-3].

The good solvent in the liquid crystal alignment agent is preferably 20% by mass to 99% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, it is preferably from 20 to 90% by mass. More preferably 30 to 80% by mass.

The liquid crystal alignment agent of the present invention can use a solvent (also referred to as a weak solvent) for improving the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment agent is applied, within a range not impairing the effects of the present invention. Specific examples of the following weak solvents include, but are not limited to, and the like.

For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1 -butanol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentyl Alcohol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl Cyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1 , 4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, two Propyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol Methyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone , 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, B Diol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2 -(hexyloxy)ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-( Butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, two Ethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, three Ethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxypropionic acid Methyl ester, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, N-butyl lactate, isoamyl lactate or the above formula [D-1]~form [D-3].

Among them, preferred are 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, or dipropylene glycol dimethyl ether.

These weak solvents are preferably from 1 to 80% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, it is preferably from 10 to 80% by mass. More preferably, it is 20 to 70% by mass.

In addition to the above, the liquid crystal alignment agent of the present invention may be added with a polymer other than the polymer described in the present invention so as to change the dielectric constant or conductivity of the liquid crystal alignment film, as long as it does not impair the effects of the present invention. a cross-linking compound for the purpose of improving the adhesion or density of the liquid crystal alignment film, and a cross-linking compound for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, and a dielectric material or a conductive material for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, and In order to heat the coating film, the ruthenium imidization accelerator for the purpose of ruthenium imidization is more efficiently carried out by heating the polyimide precursor.

<Liquid alignment film>

In the liquid crystal alignment film of the present invention, the liquid crystal alignment agent is applied onto a substrate, and the obtained film is dried and fired. The substrate to which the liquid crystal alignment agent is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate, or a polycarbonate substrate can be used, and the process can be simplified. Point of view, using a liquid crystal drive A substrate such as an ITO (Indium Tin Oxide) electrode is preferred. Further, in the case of a reflective liquid crystal display device, when it is only a single-sided substrate, an opaque material such as a germanium wafer may be used, and in this case, a material that reflects light such as aluminum may be used as the electrode.

Examples of the method of applying the liquid crystal alignment agent include a spin coating method, a printing method, an inkjet method, and the like. The drying and baking steps after coating the liquid crystal alignment agent may be selected to any temperature and time. Usually, in order to sufficiently remove the organic solvent contained, it is dried at 50 ° C to 120 ° C for 1 minute to 10 minutes, and then baked at 150 ° C to 300 ° C for 5 minutes to 120 minutes. The thickness of the coating film after firing is not particularly limited. However, when the thickness is too thin, the reliability of the liquid crystal display element is lowered, so that it is 5 to 300 nm, preferably 10 to 200 nm.

The method of performing the alignment treatment of the obtained liquid crystal alignment film may, for example, be a rubbing method or a photo-alignment treatment method.

The rubbing treatment can utilize existing friction devices. The material of the rubbing cloth at this time may, for example, be cotton, nylon or rayon. The conditions of the rubbing treatment generally use a rotation speed of 300 to 2000 rpm, a conveying speed of 5 to 100 mm/s, and a pushing amount of 0.1 to 1.0 mm. Then, using pure water or alcohol, the residue due to friction is removed by ultrasonic cleaning.

Specific examples of the photo-alignment treatment method include a method in which the surface of the coating film is irradiated with radiation that is biased in a certain direction, and may be further heat-treated at a temperature of 150 to 250 ° C to impart alignment energy to the liquid crystal. The radiation can use ultraviolet rays and visible rays having a wavelength of 100 to 800 nm. Among them, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and those having a wavelength of 200 to 400 nm are particularly preferable. Further, in order to improve the liquid crystal alignment property, the coated substrate may be heated at 50 to 250 ° C while irradiating the radiation. The irradiation amount of the radiation is preferably from 1 to 10,000 mJ/cm ² , particularly preferably from 100 to 5,000 mJ/cm ² . As described above, the liquid crystal alignment film allows the liquid crystal molecules to be stably aligned in a specific direction.

The higher the extinction ratio of the polarized ultraviolet light, the higher the anisotropy, the better. Specifically, the extinction ratio of the ultraviolet light of the linearly polarized light is preferably 10:1 or more, more preferably 20:1 or more.

The film irradiated with the polarized radiation described above may be subjected to a contact treatment by containing at least one solvent selected from the group consisting of water and an organic solvent.

The solvent to be used in the contact treatment is not particularly limited as long as it is a solvent capable of dissolving a decomposition product generated by light irradiation. Specific examples thereof include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, and butyl cellosolve. Agent, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. These solvents may be used in combination of two or more kinds.

From the viewpoint of versatility or safety, it is more preferably at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol, and ethyl lactate. Particularly preferred are water, 2-propanol, and a mixed solvent of water and 2-propanol.

The contact treatment of the film irradiated with the polarized radiation and the solution containing the organic solvent is carried out by a treatment such as immersion treatment, spray treatment, or the like, in which the film and the liquid are desirably sufficiently contacted. Wherein, in the solution containing the organic solvent, it is preferably 10 seconds to 1 hour, more preferably 1 to 30 minutes. The method of immersing the film is preferred. The contact treatment may be carried out at room temperature or may be heated, preferably from 10 to 80 ° C, more preferably from 20 to 50 ° C. Further, if necessary, a means for improving contact such as ultrasonic waves can be implemented.

After the above contact treatment, in order to remove the organic solvent in the use solution, it may be washed (cleaned) or dried by a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone. One or both.

Further, the film subjected to the contact treatment by the solvent described above can be heated at 150 ° C or higher for drying of the solvent and realignment of the molecular chains in the film.

The heating temperature is preferably from 150 to 300 °C. The higher the temperature, the more the reorientation of the molecular chain is promoted, but when the temperature is too high, there is a concern that the decomposition of the molecular chain is accompanied. Therefore, the heating temperature is preferably 180 to 250 ° C, and particularly preferably 200 to 230 ° C.

When the heating time is too short, the effect of reorientation of the molecular chain may not be obtained. When the temperature is too long, the molecular chain may be decomposed, preferably from 10 seconds to 30 minutes, more preferably from 1 minute to 10 minutes.

<Liquid crystal display element>

The liquid crystal display element of the present invention is provided with a liquid crystal alignment film obtained by the method for producing a liquid crystal alignment film. In the liquid crystal display device, a liquid crystal alignment film is obtained by a method for producing a liquid crystal alignment film, and a liquid crystal cell is produced by a conventional method, and a liquid crystal cell is used as a liquid crystal display element.

A liquid crystal display element having a passive matrix structure as an example of a method for fabricating a liquid crystal cell will be described. Further, a liquid crystal display element having an active matrix structure in which switching elements such as TFTs (Thin Film Transistors) are provided in each pixel portion constituting the image display may be used.

First, a substrate made of transparent glass is prepared, and a common electrode (Common Electrode) is provided on one of the substrates, and a segment electrode is provided on the other substrate. These electrodes, for example, can be patterned as ITO electrodes to display a desired image. Next, an insulating film is provided on each of the substrates to cover the common electrode and the segment electrode. The insulating film may be, for example, a film made of SiO ₂ -TiO ₂ formed by a sol-gel method.

Next, the liquid crystal alignment film of the present invention is formed on each of the substrates. Then, the alignment film surface of the substrate between the other substrate and the other substrate overlaps in the opposite direction, and the sealing material is used in the periphery. In the sealing material, in order to control the gap of the substrate, a spacer can usually be mixed. Further, it is preferable that the in-plane portion in which the sealing material is not provided is also spread over the spacer for controlling the substrate gap. One part of the sealing material is provided with an opening portion which can be filled with an external liquid.

Next, a liquid crystal material is injected into a space surrounded by the two substrates and the sealing material by being provided in the opening of the sealing material. Then, this opening portion was sealed with an adhesive. At the time of injection, a vacuum injection method or a method using a capillary phenomenon in the atmosphere may be used. Next, a polarizing plate is provided. Specifically, a pair of polarizing plates are adhered to the surface on the opposite side to the liquid crystal layer of the two substrates. Through the above steps, the liquid crystal display element of the present invention can be obtained.

As the sealant, for example, a resin having an epoxy group, an acryloyl group, a methacryloyl group, a hydroxyl group, an allyl group, an ethyl fluorenyl group or the like, which is cured by ultraviolet irradiation or heating can be used. In particular, it is preferred to use a hardening resin having both a reactive group of an epoxy group and a (meth)acryl fluorenyl group.

The sealant may be formulated with an inorganic filler in order to improve adhesion and moisture resistance. The inorganic filler which can be used is not particularly limited, and specific examples thereof include spherical cerium oxide, molten cerium oxide, crystalline cerium oxide, titanium oxide, titanium black, cerium carbide, cerium nitride, and boron nitride. , calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesia, zirconia, aluminum hydroxide, calcium citrate, aluminum silicate, lithium aluminum niobate, zirconium silicate, titanium Acid bismuth, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably spherical cerium oxide, molten cerium oxide, crystalline cerium oxide, titanium oxide, titanium black, cerium nitride, boron nitride, calcium carbonate , barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium citrate, aluminum citrate. The inorganic filler may be used in combination of two or more kinds.

[Examples]

Hereinafter, the present invention will be described in more detail with reference to examples but the present invention is not limited thereto. The abbreviations and measurement methods of the following compounds are as follows.

NMP: N-methyl-2-pyrrolidone, GBL: γ-butyl lactone

BCS: butyl cellosolve, PB: propylene glycol monobutyl ether, IPA: isopropanol, DA-1:1, 2-bis(4-aminophenoxy)ethane DA-2: Refer to the following formula (DA-2), DA-3: 1,2-bis(4-aminophenoxy)methane, DA-4:p-phenylenediamine, DA-5:1, 2-bis(4-aminophenoxy)propane

DA-6: Refer to the following formula (DA-6), DA-7: 4,4'diaminodiphenylamine, DA-8: Refer to the following formula (DA-8), DA-9:4, 4'-Diaminodiphenylmethane, DAH-1:1, 2,3,4-cyclobutanetetracarboxylic dianhydride

DAH-2: Refer to the following formula (DAH-2), DAH-3: Refer to the following formula (DAH-3)

DAH-4: cyclobutane tetracarboxylic dianhydride

DAH-5: pyromellitic dianhydride

1,3DM-CBDE-Cl: dimethyl 1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4-dicarboxylate

[additive]

AD-1~3: crosslinkable additive, AD-4: hydrazine imidization accelerator

[ ¹ H NMR]

Device: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz, solvent: deuterated dimethyl hydrazine (DMSO-d ₆ ))

Reference material: tetramethyl decane (TMS), cumulative number: 8 or 32

[viscosity]

In the synthesis example, the viscosity of the polyimine and the polyaminic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a conical rotor TE-1 (1° 34'). , R24), temperature 25 ° C for measurement.

[molecular weight]

The molecular weight of the polyimine was measured by a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated from polyethylene glycol and polyethylene oxide equivalent values.

GPC device: manufactured by Shodex Corporation (GPC-101),

Pipe column: made by Shodex company (inline of KD803, KD805), column temperature: 50 °C

Dissolution: N,N-dimethylformamide (additive is lithium bromide-hydrate (LiBr.H ₂ O) is 30 mmol / L (liter), phosphoric acid. Anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) was 10 ml/L, flow rate: 1.0 ml/min

Standard sample for the production of calibration lines: TSK standard polyethylene oxide manufactured by Tosoh Corporation (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30,000), and polyethylene glycol (Polymer top molecular weight) manufactured by Polymer Laboratories (Mp) approximately 12,000, 4,000, 1,000). In order to avoid overlapping of peaks, it is possible to mix two samples of 900,000, 100,000, 12,000, and 1,000 types, and 2 samples of 150,000, 30,000, and 4,000 types of samples. Line measurement.

[Measurement of yttrium imidation rate]

20 mg of polyimine powder was placed in an NMR sample tube (NMR 5) (Φ5 (manufactured by Kusano Scientific)), and dimethylated dimethyl hydrazine (DMSO-d6, 0.05% TMS (tetramethyl decane) mixture was added. ) (0.53 ml), applying ultrasonic waves to completely dissolve them. This solution was measured for proton NMR at 500 MHz using an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Ltd.). The ruthenium imidization rate is based on a proton from a structure that has not changed before and after imidization, and the peak value of the proton is used, and the NH group derived from proline is present in the vicinity of 9.5 ppm to 10.0 ppm. The proton peak cumulative value is obtained by the following formula.

醯 imidization rate (%) = (1-α.x/y) × 100

In the above formula, x is the proton peak cumulative value derived from the NH group of the proline, the peak cumulative value of the y-based reference proton, and the number of the reference protons when the α-polylysine (the imidization ratio is 0%). The ratio of one of the NH protons relative to the proline.

[Evaluation of liquid crystal alignment]

The liquid crystal cell is held by the polarizing plate, and the liquid crystal cell is rotated in a state where the backlight is irradiated from the rear portion, and the change in brightness and darkness or the presence or absence of the flow alignment is visually observed, and the liquid crystal is aligned. At this time, it evaluated by the following criteria.

Evaluation basis

◎: The alignment of the liquid crystal can be confirmed, and there is no flow alignment

○: Although the liquid crystal is aligned, a number of flow alignments are observed.

X: The liquid crystal was aligned, but many flow alignments were observed.

(Synthesis Example 1)

In a 1000 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-1 (42.75 g (175 mmol)), DA-2 (59.7 g (175 mmol)), and NMP 586 g were added thereto, and nitrogen gas was fed thereto. Stir and dissolve. While stirring the diamine solution, DAH-1 (74.53 g (332.5 mmol)) was added, and NMP was added thereto to adjust the solid content concentration to 18% by mass, and the mixture was stirred at room temperature for 24 hours to obtain polyamine acid (PAA- 1) Solution (viscosity: 832 mPa.s).

(Synthesis Example 2)

In a 1000 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 200 g of the obtained polyaminic acid solution (PAA-1) was weighed, NMP (100 g) was added, and the mixture was stirred for 30 minutes. 21.78 g of acetic anhydride and 2.81 g of pyridine were added to the obtained polyamic acid solution, and the mixture was heated at 60 ° C for 3 hours to carry out chemical hydrazine imidization. The obtained reaction liquid was poured into 624.2 g of methanol while stirring, and the precipitate was collected by filtration, and then washed three times with 624.2 g of methanol and twice with 1248 g of methanol. The obtained resin powder was dried at 60 ° C for 12 hours. A polyimide resin powder was obtained. this The polyimide imidization ratio of the polyimide resin powder was 68%, and the molecular weight was Mn=9189 and Mw=18252.

32.70 g of the obtained polyimine resin powder was weighed in a sample tube containing 200 ml of a stir bar, and 239.8 g of NMP was added thereto, and the mixture was stirred at 70 ° C for 20 hours to be dissolved to obtain a polyimine solution (SPI-1). .

(Synthesis Example 3)

DA-3 (7.14 g (31 mmol)) was weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and 75.1 g of a 1:1 mixed solvent of NMP and GBL was added thereto, and the mixture was stirred while being fed with nitrogen gas. Dissolved. While stirring this diamine solution, DAH-3 (2.33 g (9.3 mmol)) was added and stirred overnight. Then, DAH-2 (6.13 g (20.8 mmol)) was further added, and a 1:1 mixed solvent of NMP and GBL was added to adjust the solid content to 15% by weight, and the mixture was stirred at room temperature for 5 hours to obtain polylysine ( Solution of PAA-2) (viscosity: 787 mPa.s).

(Synthesis Example 4)

DA-3 (5.53 g (24 mmol)) was weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and 72.7 g of a 1:1 mixed solvent of NMP and GBL was added thereto, and the mixture was stirred while being fed with nitrogen gas. Dissolved. While stirring the diamine solution, DAH-2 (6.87 g (23.4 mmol)) was added thereto, and a 1:1 mixed solvent of NMP and GBL was added to adjust the solid content to 12% by weight, and the mixture was stirred overnight to obtain a polyamic acid. (PAA-3) solution (viscosity: 520 mPa.s).

(Synthesis Example 5)

DA-4 (0.908 g (8.4 mmol)), DA-1 (1.37 g (5.6 mmol)), and DA-5 (2.17 g) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 8.4 mmol)), DA-6 (2.23 g (5.6 mmol)), 76.8 g of NMP was added, and it stirred and it stirred by nitrogen. While stirring this diamine solution, DAH-1 (5.99 g (26.7 mmol)) was added, NMP was added to make the solid content concentration 12% by weight, and stirring was carried out overnight to obtain a solution of polyamine acid (PAA-4) (viscosity). : 397mPa.s).

(Synthesis Example 6)

DA-7 (15.9 g (80 mmol)) and DA-8 (6.0 g (20 mmol)) were weighed in a 500 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and NMP 230.0 g was added thereto, and nitrogen gas was supplied thereto. Stir and dissolve. While stirring the diamine solution, DAH-4 (4.4 g (22.5 mmol)) was added, and stirred overnight. Then, DAH-3 (18.8 g (75 mmol)) was further added, NMP was added thereto so that the solid content concentration became 15% by weight, and the mixture was stirred at 50 ° C for 10 hours to obtain a solution of polyaminic acid (PAA-5) (viscosity: 1405 mPa). .s).

(Synthesis Example 7)

DA-7 (1.91 g (9.6 mmol)) and DA-8 (0.72 g) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. (2.4 mmol)), a 1:1 mixed solvent of NMP and GBL was added, and the mixture was stirred and dissolved while supplying nitrogen gas. While stirring the diamine solution, DAH-2 (3.40 g (11.6 mmol)) was added thereto, and a 1:1 mixed solvent of NMP and GBL was added to adjust the solid content to 12% by weight, and the mixture was stirred overnight to obtain polylysine ( Solution of PAA-6) (viscosity: 810 mPa.s).

(Synthesis Example 8)

DA-4 (10.00 g (92.4 mmol)) and DA-1 (13.60 g (55.5 mmol)) and DA-2 (12.60 g) were weighed in a 2 L four-necked flask equipped with a stirring device and a nitrogen introduction tube. 37.0 mmol)), NMP 379.00 g and GBL 1023.00 g and pyridine 34.60 g (0.43 mol) were added to dissolve. Next, 1,3DMCBDE-Cl (58.30 g (179.4 mmol)) was added while stirring the solution, and the reaction was allowed to proceed for 14 hours under water cooling. 2.41 g (26.6 mmol) of acrylonitrile chloride was added to the obtained polyamic acid solution, and after the reaction was further carried out for 4 hours, the solution was poured into 8653 ml of isopropyl alcohol while stirring, and a precipitated white precipitate was obtained by filtration. Next, 21635 ml of isopropyl alcohol was washed in 5 portions, and dried to obtain a white polyphthalate resin powder (PWD-1). The molecular weight of this polyphthalate was Mn = 24,366 and Mw = 54,808.

The polyphthalate resin powder (PWD-1) obtained above was dissolved in GBL to obtain a polyamine solution (PAE-1) having a solid concentration of 12% by mass.

(Synthesis Example 9)

DA-7 (2.23 g (11.2 mmol)) and DA-9 (0.56 g (2.8 mmol)) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and NMP 26.4 g was added thereto. Stir under nitrogen to dissolve. While stirring this diamine solution, DAH-3 (2.63 g (9.3 mmol)) was added, and 4.4 g of NMP was added thereto, and the mixture was stirred at room temperature for 3 hours. Then, DAH-4 (0.58 g (2.94 mmol)) was further added, and a 1:1 mixed solvent of NMP and GBL was added to adjust the solid content to 12% by weight, and the mixture was stirred overnight at room temperature to obtain polylysine. (PAA-7) solution (viscosity: 630 mPa.s).

(Synthesis Example 10)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-7 (3.99 g (20 mmol)) and DA-9 (0.99 g (5.0 mmol)) were weighed, and NMP 74.8 g was added thereto and fed. The nitrogen gas was stirred to dissolve. The diamine solution was stirred, DAH-2 (5.15 g (17.5 mmol)) was added, and the mixture was stirred at room temperature for 5 hours. Then, DAH-4 (1.20 g (6.13 mmol)) was added, and NMP was added so that the solid content concentration became 12% by weight, and the mixture was stirred overnight to obtain a solution of polylysine (PAA-8) (viscosity: 398 mPa.s).

(Synthesis Example 11)

DA-5 (3.10 g (12 mmol)) and DA-6 (4.78 g (12 mmol)) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and 75% of NMP was added thereto, and nitrogen gas was supplied thereto. Stirring while stirring solution. While stirring the diamine solution, DAH-5 (4.97 g (22.8 mmol)) was added, NMP was added to adjust the solid content to 12% by weight, and stirring was carried out overnight to obtain a solution of polyglycine (PAA-9) (viscosity). : 273mPa.s).

(Example 1)

2.92 g of the polyimine solution (SPI-1) obtained in Synthesis Example 2 and 4.62 g of the polyaminic acid solution (PAA-2) obtained in Synthesis Example 3 were weighed in a 50 mL Erlenmeyer flask containing stirring. Add 2.83g of NMP, 3.45g of GBL, 3.60g of PB, add 0.495g of 10% NMP solution of AD-1, AD-4 (0.139g), stir with a magnetic stirrer overnight to obtain liquid crystal alignment agent (AL-1). ).

(Example 2)

2.92 g of the polyimine solution (SPI-1) obtained in Synthesis Example 2 and 4.62 g of the polyaminic acid solution (PAA-2) obtained in Synthesis Example 3 were weighed in a 50 mL Erlenmeyer flask containing stirring. NMP 3.32 g, GBL 3.45 g, and PB 3.60 g were added, and AD-2 (0.0297 g) and AD-4 (0.139 g) were further added thereto, and stirred with a magnetic stirrer overnight to obtain a liquid crystal alignment agent (AL-2).

(Example 3)

In a 50 mL Erlenmeyer flask containing stirring, 2.929 g of the polyimine solution (SPI-1) obtained in Synthesis Example 2 was weighed, and the polypethane obtained in Synthesis Example 3 was weighed. Amino acid solution (PAA-2) 4.62 g. NMP 3.32 g, GBL 3.45 g, and PB 3.60 g were added, and AD-3 (0.0297 g) and AD-4 (0.139 g) were further added, and stirred overnight with a magnetic stirrer to obtain a liquid crystal alignment agent (AL-3).

(Comparative Example 1)

2.92 g of the polyimine solution (SPI-1) obtained in Synthesis Example 2 and 4.62 g of the polyaminic acid solution (PAA-2) obtained in Synthesis Example 3 were weighed in a 50 mL Erlenmeyer flask containing stirring. NMP 3.32 g, GBL 3.45 g, PB 3.60 g, and AD-4 (0.139 g) were added, and stirred overnight with a magnetic stirrer to obtain a liquid crystal alignment agent (AL-A).

(Comparative Example 2)

2.29 g of the polyimine solution (SPI-1) obtained in Synthesis Example 2 and 5.90 g of the polyaminic acid solution (PAA-3) obtained in Synthesis Example 4 were weighed in a 50 mL Erlenmeyer flask containing stirring. Add NMP 2.19g, GBL 2.81g, PB 3.60g, add 1095 NMP solution of AD-1 to 0.495g, AD-4 (0.139g), stir with a magnetic stirrer overnight to obtain liquid crystal alignment agent (AL-B) .

(Example 4)

In a 50 mL Erlenmeyer flask containing stirring, 3.249 g of a polyaminic acid solution (PAA-4) obtained in Synthesis Example 5 and 3.60 g of a polyaminic acid solution (PAA-5) obtained in Synthesis Example 6 were weighed. Add NMP 5.40g, BCS 5.40 g, 0.45 g of a 10% NMP solution of AD-1 was added, and stirred overnight with a magnetic stirrer to obtain a liquid crystal alignment agent (AL-4).

(Example 5)

In a 50 mL Erlenmeyer flask containing stirring, 3.249 g of a polyaminic acid solution (PAA-4) obtained in Synthesis Example 5 and 3.60 g of a polyaminic acid solution (PAA-5) obtained in Synthesis Example 6 were weighed. 5.85 g of NMP and 5.40 g of BCS were added, AD-2 (0.027 g) was added, and the mixture was stirred overnight with a magnetic stirrer to obtain a liquid crystal alignment agent (AL-5).

(Example 6)

In a 50 mL Erlenmeyer flask containing stirring, 3.249 g of a polyaminic acid solution (PAA-4) obtained in Synthesis Example 5 and 3.60 g of a polyaminic acid solution (PAA-5) obtained in Synthesis Example 6 were weighed. 5.85 g of NMP and 5.40 g of BCS were added, AD-3 (0.045 g) was added, and the mixture was stirred overnight with a magnetic stirrer to obtain a liquid crystal alignment agent (AL-6).

(Comparative Example 3)

In a 50 mL Erlenmeyer flask containing stirring, 3.249 g of a polyaminic acid solution (PAA-4) obtained in Synthesis Example 5 and 3.60 g of a polyaminic acid solution (PAA-5) obtained in Synthesis Example 6 were weighed. N85 5.85 g and BCS 5.40 g were added, and stirred overnight with a magnetic stirrer to obtain a liquid crystal alignment agent (AL-C).

(Comparative Example 4)

In a 50 mL Erlenmeyer flask containing stirring, 3.249 g of the polyaminic acid solution (PAA-4) obtained in Synthesis Example 5 and 4.58 g of the polyaminic acid solution (PAA-6) obtained in Synthesis Example 7 were weighed. 4.42 g of NMP and 5.40 g of BCS were added, and then 0.45 g of a 10% NMP solution of AD-1 was added, and stirred overnight with a magnetic stirrer to obtain a liquid crystal alignment agent (AL-D).

(Example 7)

Into a 50 mL Erlenmeyer flask containing stirring, 3.30 g of a polyamidate solution (PAE-1) obtained in Synthesis Example 8 and 3.96 g of a polyamidonic acid solution (PAA-7) obtained in Synthesis Example 9 were weighed. NMP 1.54g, GBL 5.12g, BCS 3.60g were added, and then 0.495 g of 10% NMP solution of AD-1 was added, and stirred with a magnetic stirrer overnight to obtain a liquid crystal alignment agent (AL-7).

(Comparative Example 5)

Into a 50 mL Erlenmeyer flask containing stirring, 3.30 g of a polyamidate solution (PAE-1) obtained in Synthesis Example 8 and 3.96 g of a polyamidonic acid solution (PAA-7) obtained in Synthesis Example 9 were weighed. NMP 2.03g, GBL 5.12g, and BCS 3.60g were added, and stirred overnight with a magnetic stirrer to obtain a liquid crystal alignment agent (AL-E).

(Comparative Example 6)

In a 50 mL Erlenmeyer flask containing stirring, the synthesis example 8 was weighed. 3.30 g of a polyphthalate solution (PAE-1) and 4.94 g of a polyaminic acid solution (PAA-8) obtained in Synthesis Example 10 were obtained. NMP 0.56 g, GBL 5.12 g, BCS 3.60 g were added, and then 0.495 g of a 10% NMP solution of AD-1 was added, and stirred overnight with a magnetic stirrer to obtain a liquid crystal alignment agent (AL-F).

(Example 8)

In a 50 mL Erlenmeyer flask containing stirring, 1.87 g of the polyaminic acid solution (PAA-9) obtained in Synthesis Example 11 and 4.80 g of the polyaminic acid solution (PAA-7) obtained in Synthesis Example 9 were weighed. 5.58 g of NMP and 5.40 g of BCS were added, and then 0.45 g of a 10% NMP solution of AD-1 was added, and stirred overnight with a magnetic stirrer to obtain a liquid crystal alignment agent (AL-8).

(Comparative Example 7)

In a 50 mL Erlenmeyer flask containing stirring, 1.87 g of the polyaminic acid solution (PAA-9) obtained in Synthesis Example 11 and 4.80 g of the polyaminic acid solution (PAA-7) obtained in Synthesis Example 9 were weighed. NMP 6.03g and BCS 5.40g were added, and stirred overnight with a magnetic stirrer to obtain a liquid crystal alignment agent (AL-G).

(Comparative Example 8)

In a 50 mL Erlenmeyer flask containing stirring, 1.87 g of the polyaminic acid solution (PAA-9) obtained in Synthesis Example 11 and 5.99 g of the polyamidic acid solution (PAA-8) obtained in Synthesis Example 10 were weighed. Join NMP 4.50g, BCS 5.40 g, 0.45 g of a 10% NMP solution of AD-1 was further added, and stirred overnight with a magnetic stirrer to obtain a liquid crystal alignment agent (AL-H).

(Example 9)

The liquid crystal alignment agent (AL-1) obtained in Example 1 was filtered using a filter having a pore size of 1.0 μm, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C for 2 minutes. Then, the film was fired in a hot air circulating oven at a temperature of 230 ° C for 20 minutes to obtain a ruthenium imidized film having a film thickness of 110 nm. For the fired film, ultraviolet rays of 254 nm of 200 mJ/cm ^{2 were} irradiated through a polarizing plate. Then, the substrate was washed with an IPA/water = 1:1 mixed solvent for 5 minutes, and then fired in a hot air circulating oven at 230 ° C for 20 minutes. Thereby, a substrate with a liquid crystal alignment film was obtained.

In order to evaluate the electrical characteristics of the liquid crystal cell, two substrates of the above liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on one of the liquid crystal alignment films. The sealant is printed thereon so that the liquid crystal alignment film faces each other, and the light alignment direction is parallel. After bonding the other substrate, the sealant is cured to form an empty cell. Liquid crystal ML-7026-100 (manufactured by Merck. Japan Co., Ltd.) was injected into the empty cell by a vacuum injection method, and the injection port was closed to obtain an IPS liquid crystal cell. The results of evaluating the initial alignment of the liquid crystal cell based on the above criteria are shown in Table 1 below. The empty cell was subjected to heat treatment at 120 ° C for 30 minutes to complete the liquid crystal cell.

Further, after the liquid crystal cell was placed on the backlight for 3 days, the voltage was applied at a temperature of 60 ° C for 60 μs at a voltage of 1 V, and the voltage after 500 ms was measured to determine how much the voltage can be maintained as a voltage holding ratio.

(Examples 10 and 11, Comparative Examples 9, 10)

The liquid crystal cell was produced and evaluated in the same manner as in Example 9 except that the liquid crystal alignment agent shown in Table 1 was used instead of the liquid crystal alignment agent AL-1. The results of the initial alignment and voltage retention of each liquid crystal cell are shown in Table 1.

(Embodiment 12)

The liquid crystal alignment agent (AL-4) obtained in Example 4 was filtered using a filter having a pore size of 1.0 μm, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C for 2 minutes. Then, the film was fired in a hot air circulating oven at a temperature of 230 ° C for 30 minutes to obtain a ruthenium imidized film having a film thickness of 100 nm. The fired film was irradiated with ultraviolet rays of 254 nm of 150 mJ/cm ² through a polarizing plate. Then, it was baked in a hot air circulating oven at 230 ° C for 30 minutes. Thereby, a substrate with a liquid crystal alignment film was obtained.

In order to evaluate the electrical characteristics of the liquid crystal cell, two sheets of the above-mentioned substrate with a liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on one of the liquid crystal alignment films. The sealant is printed thereon so that the liquid crystal alignment film faces each other, and the light alignment direction is parallel. After bonding the other substrate, the sealant is cured to form an empty cell. Liquid crystal ML-7026-100 (manufactured by Merck. Japan Co., Ltd.) was injected into the empty cell by a vacuum injection method, and the injection port was closed to obtain an IPS liquid crystal cell. The results of evaluating the initial alignment of the liquid crystal cell based on the above criteria are shown in Table 1 below. Heat treatment of this empty unit cell at 120 ° C for 30 minutes Complete the liquid crystal cell.

Further, after the liquid crystal cell was placed on the backlight for 3 days, the voltage was applied at a temperature of 60 ° C for 60 μs at a voltage of 1 V, and the voltage after 500 ms was measured to determine how much the voltage can be maintained as a voltage holding ratio.

(Examples 13, 14 and Comparative Examples 11, 12)

The liquid crystal cell was produced and evaluated in the same manner as in Example 9 except that the liquid crystal alignment agent shown in Table 1 was used instead of the liquid crystal alignment agent AL-4. The results of the initial alignment and voltage retention of each liquid crystal cell are shown in Table 1.

(Embodiment 16)

The liquid crystal alignment agent (AL-8) obtained in Example 8 was filtered using a filter having a pore size of 1.0 μm, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C for 2 minutes. Then, the film was fired in a hot air circulating oven at a temperature of 230 ° C for 20 minutes to obtain a ruthenium imidized film having a film thickness of 110 nm. For the fired film, the alignment treatment was performed by rubbing. Then, it was washed with running water for 1 minute, and dried at 80 ° C for 10 minutes. Thereby, a substrate with a liquid crystal alignment film was obtained.

In order to evaluate the electrical characteristics of the liquid crystal cell, two sheets of the above-mentioned substrate with a liquid crystal alignment film were prepared, and a spacer of 6 μm was spread on one of the liquid crystal alignment films. The sealant is printed thereon so that the liquid crystal alignment film faces each other, and the light alignment direction is parallel to bond the other substrate, and the sealant is hardened to form an empty cell. Liquid crystal ML-7026-100 (Merck.) by decompression injection method. Injected into the empty cell, the company has closed the injection port to obtain an IPS liquid crystal cell. The results of evaluating the initial alignment of the liquid crystal cell based on the above criteria are shown in Table 1 below. The empty cell was subjected to heat treatment at 120 ° C for 30 minutes to complete the liquid crystal cell.

Further, after the liquid crystal cell was placed on the backlight for 3 days, the voltage was applied at a temperature of 20 ° C for 60 μs at a voltage of 1 V, and the voltage after 500 ms was measured to determine how much the voltage can be maintained as a voltage holding ratio.

(Comparative Examples 15, 16)

The liquid crystal cell was produced and evaluated in the same manner as in Example 16 except that the liquid crystal alignment agent shown in Table 1 was used instead of the liquid crystal alignment agent AL-4. The results of the initial alignment and voltage retention of each liquid crystal cell are shown in Table 1.

The above results are shown in Table 1. In Table 1, component 1 means a polymer component containing a heat-releasing group.

[Industrial availability]

A liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is suitably used as a wide range of displays such as liquid crystal televisions, smart phones, and car navigation.

The entire contents of the specification, the scope of the patent application and the abstract of Japanese Patent Application No. 2016-001659, filed Jan.

Claims (13)

A liquid crystal alignment agent comprising the following (A) component, (B) component, (C) component, and an organic solvent; (A) component: using a tetracarboxylic acid derivative component and containing a compound having the following formula [A] a diamine compound having a structure of -1], a diamine compound having a structure of the following formula [A-2], and at least one diamine compound having a diamine compound having a structure of the following formula [A-3] a polyimine precursor obtained from a diamine component and at least one polymer selected from the group consisting of polyimine, (R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group represented by the following formula (1), and at least one of them is a thermal desorption property of a protecting group substituted with a hydrogen atom by heat. a group, R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms which may have a substituent, and D is a thermal debonding group substituted with a protecting group of a hydrogen atom by heat. (B) component: polymerization of at least one selected from the group consisting of a polyimine precursor having a structural unit represented by the following formula (2) and a ruthenium imidized polymer of the polyimine precursor Object, (X ₁ is a tetravalent organic group represented by the following formula (X-1), Y ₁ is a divalent organic group, R ₁ is a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and each of A ₁ to A ₂ Independently a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms which may have a substituent) Component (C): A compound containing two or more crosslinkable functional groups. The liquid crystal alignment agent of the first aspect of the invention, wherein the compound containing two or more crosslinkable functional groups contains two or more selected from the group consisting of a hydroxyl group, a hydroxyalkylguanamine group, and a (meth) acrylate group. A compound which blocks at least one functional group of an isocyanate group, an oxetanyl group, or an epoxy group. The liquid crystal alignment agent according to claim 1 or 2, wherein the compound containing two or more crosslinkable functional groups is a compound containing two or more hydroxyl groups. The liquid crystal alignment agent according to any one of the above aspects, wherein the compound containing two or more crosslinkable functional groups is 0.1 to the total of the components (A) and (B). 20% by mass. The liquid crystal alignment agent of any one of Claims 1 to 4, wherein the compound containing two or more crosslinkable functional groups is represented by the following formula (7). (X ₃ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group, n is an integer of 2 to 6, and R ₆ and R ₇ are each independently a hydrogen atom or may have a substituent The alkyl group having 1 to 4 carbon atoms, the alkenyl group having 2 to 4 carbon atoms, or the alkynyl group having 2 to 4 carbon atoms, and at least one of R ₆ and R ₇ represents a hydrocarbon group substituted with a hydroxyl group). The liquid crystal alignment agent of claim 5, wherein at least one of R ₆ and R ₇ is represented by the following formula (8), (R ₈ to R ₁₁ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group). The liquid crystal alignment agent according to any one of claims 1 to 6, wherein the component (C) is a compound represented by the following formula: The liquid crystal alignment agent according to any one of claims 1 to 7, wherein the heat-releasing group is a group represented by the following formula (1). (A is a single bond or a divalent group derived from a hydrocarbon group having 1 to 4 carbon atoms). The liquid crystal alignment agent according to any one of claims 1 to 8, wherein the aforementioned heat-releasing group is a third butoxycarbonyl group. The liquid crystal alignment agent according to any one of the items (1), wherein the polymer of the component (B) is a structural unit further represented by the following formula (3). (X ₁ is a tetravalent organic group (excluding the above formula (X-1)), Y ₁ is a divalent organic group, R ₁ is a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and each of A ₁ to A ₂ It is independently a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms which may have a substituent. A liquid crystal alignment film obtained by the liquid crystal alignment agent according to any one of claims 1 to 10. A liquid crystal display element comprising the liquid crystal alignment film of claim 11 of the patent application. A horizontal electric field driven liquid crystal display element, which is provided with Please refer to the liquid crystal alignment film of the eleventh patent.