KR102554992B1 - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

The liquid crystal aligning agent which can form the liquid crystal aligning film containing the polymer which has an aromatic heterocyclic ring, a primary amino group, and a secondary amino group in structure, and such a liquid crystal aligning film. It is preferable that the said aromatic heterocyclic ring and the said primary amino group and the secondary amino group generate|occur|produce at the time of baking of a liquid crystal aligning film, and a liquid crystal aligning agent is specifically at least 1 selected from the following component (A) and the following component (B) Contains at least one polymer selected from polyamic acid, which is a reaction product of tetracarboxylic dianhydride, and polyimide, which is an imide of a diamine component containing a diamine containing a diamine of a species and a skeleton of the following component (C) do. In addition, the definition of the symbol in each chemical formula is as described in the specification. Component (A): diamine having at least one structure selected from the following formula (1-1) and following formula (1-2) (B) component: diamine (C) component having a structure of the following formula (2) : Diamine having at least one structure selected from the following formula (a) and the following formula (b)

Description

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

This invention relates to the liquid crystal display element using the liquid crystal aligning agent used in manufacture of a liquid crystal display element, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and this liquid crystal aligning film.

BACKGROUND OF THE INVENTION A liquid crystal display element is known as a display device of light weight, thin shape, and low power consumption. In recent years, even in high-precision liquid crystal display elements exclusively for mobile phones and tablet-type terminals, which have rapidly expanded their share, remarkable progress has been made to the extent that high display quality is sought.

A liquid crystal display element is comprised by sandwiching a liquid crystal layer with a pair of transparent board|substrates provided with electrodes. And in a liquid crystal display element, the organic film which consists of an organic material is used as a liquid crystal aligning film so that a liquid crystal may become a desired orientation state between board|substrates. That is, the liquid crystal alignment film, as a constituent member of the liquid crystal display element, is formed on a surface in contact with the liquid crystal of a substrate holding the liquid crystal, and plays a role of orienting the liquid crystal in a certain direction between the substrates.

In recent years, liquid crystal display elements have been used exclusively for mobile applications such as smart phones and mobile phones. In these uses, in order to secure as many display surfaces as possible, it is necessary to narrow the width of the sealant used for adhering between the substrates of liquid crystal display elements compared to the prior art. Moreover, it is also calculated|required by the reason mentioned above to make the position of sealing compound the position which contacted the edge part of the liquid crystal aligning film with weak adhesiveness with sealing compound, or the upper part of a liquid crystal aligning film. In such a case, particularly in use under high-temperature, high-humidity conditions, water is likely to mix between the sealant and the liquid crystal aligning film, and display nonuniformity occurs near the frame of the liquid crystal display element.

In order to solve this problem, the liquid crystal aligning agent using the additive of a specific structure is proposed (refer patent document 1).

International Publication No. 2015/072554

However, in recent years, further improvement in the adhesion between the liquid crystal aligning film and the sealing compound is required.

Among these, in the characteristic improvement from the sealing agent, it is known that the coexistence of the adhesion property of the sealing compound and the liquid crystal aligning film and the moisture permeation prevention property of the sealing agent is difficult, and from the above viewpoint, the characteristic improvement from the liquid crystal aligning film is requested|required. .

Then, this invention aims at providing the liquid crystal aligning agent which can improve the adhesiveness of sealing compound and a liquid crystal aligning film, and can suppress generation|occurence|production of the display nonuniformity of frame vicinity of a liquid crystal display element on high temperature, high humidity conditions.

As a result of earnestly examining in order to solve the said subject, the present inventors came to complete this invention by using the liquid crystal aligning film containing the polymer which has a specific aromatic heterocyclic ring, a primary amino group, and a secondary amino group in a structure.

The 1st aspect of this invention which achieves the said object exists in the liquid crystal aligning film characterized by containing the polymer which has an aromatic heterocyclic ring, a primary amino group, and a secondary amino group in a structure.

A second aspect of the present invention to achieve the above object is a film made of a fired product, characterized in that the skeleton of the aromatic heterocyclic ring, the primary amino group, and the secondary amino group are contained in a structure formed by firing. , It exists in the liquid crystal aligning film of a 1st aspect.

The 3rd aspect of this invention which achieves the said object exists in the liquid crystal alignment film of 1st aspect or 2nd aspect characterized by the said aromatic heterocyclic ring being a pyridine skeleton, a benzimidazole skeleton, or an imidazole skeleton.

The 4th aspect of this invention which achieves the said objective exists in the liquid crystal aligning film of 2nd aspect characterized by the said baked material being produced|generated by the baking temperature of 100 degreeC - 300 degreeC.

The 5th aspect of this invention which achieves the said object exists in the liquid crystal display element characterized by being equipped with the liquid crystal aligning film of any one of the 1st aspect - 4th aspect.

The 6th aspect of this invention which achieves the said objective exists in the liquid crystal aligning agent for obtaining the liquid crystal aligning film of any one of the 1st aspect - the 4th aspect.

The 7th aspect of this invention which achieves the said object is a diamine component containing at least 1 sort(s) of diamine selected from the following component (A) and the following component (B) and the diamine containing the skeleton of the following component (C), and , It is in the liquid crystal aligning agent of the 6th aspect characterized by containing at least 1 polymer chosen from the polyamic acid which is a reactant of tetracarboxylic dianhydride, and the polyimide which is an imide product thereof.

Component (A): diamine having at least one structure selected from the following formula (1-1) and the following formula (1-2)

[Formula 1]

(Wherein, D represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring, D may have various substituents, and E is a single bond or a divalent A saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group having 1 to 20 carbon atoms, F represents a single bond or an ether bond (-O-) or an ester bond (-OCO-, -COO-), and m is , 1 or 0, R represents a thermal leaving group, and * represents a bond with another atom.)

Component (B): diamine having a structure of the following formula (2)

[Formula 2]

(Wherein, X ₁ is at least one type of divalent oil selected from the group consisting of -O-, -NQ ¹ -, -CONQ ¹ -, -NQ ¹ CO-, -CH ₂ O-, and -OCO- group, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ₂ is a single bond or at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group. One kind of divalent organic group, X ₃ is a single bond, or -O-, -NQ ² -, -CONQ ² -, -NQ ² CO-, -COO-, -OCO-, and -O(CH ₂ ) _m - at least one divalent organic group selected from the group consisting of (m is an integer of 1 to 5), Q ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ₄ is an aromatic heterocyclic ring; , * indicates a bond with another atom.)

Component (C): diamine having at least one structure selected from the following formula (a) and the following formula (b)

[Formula 3]

(In the formula, X ¹ is an oxygen atom or a sulfur atom, A ¹ to A ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and the total number of carbon atoms is 1 to 9. In addition, * is represents a bond with an atom.)

By using the liquid crystal aligning agent of this invention, the adhesiveness of sealing compound and liquid crystal aligning film can be improved, and the liquid crystal aligning film which can suppress generation|occurence|production of the display nonuniformity of frame vicinity of a liquid crystal display element on high temperature, high humidity conditions can be obtained. Therefore, the liquid crystal display element which has a liquid crystal aligning film obtained by this can solve the display nonuniformity of frame vicinity by improving the adhesiveness of a sealing compound and a liquid crystal aligning film, and can be used suitably for a large-screen and high-definition liquid crystal display.

Each structural requirement of the liquid crystal aligning film of this invention is explained in full detail below.

<Liquid crystal alignment film>

The liquid crystal aligning film of this invention contains the polymer which has an aromatic heterocyclic ring, a primary amino group, and a secondary amino group in a structure.

After the liquid crystal aligning film of the present invention applies and bakes a liquid crystal aligning agent on a substrate to form a film (hereinafter, also referred to as a film) of a polymer contained in the liquid crystal aligning agent, alignment treatment by rubbing treatment, light irradiation, etc. It is produced by In the case of vertical alignment applications, etc., it can be used as a liquid crystal alignment film without orientation treatment.

The substrate used at this time is not particularly limited as long as it is a substrate having high transparency, and plastic substrates such as acrylic substrates and polycarbonate substrates can be used in addition to glass substrates. From the viewpoint of process simplification, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed. In addition, in the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used as long as it is only a substrate on one side, and a material that reflects light such as aluminum can be used as an electrode in this case.

Although the coating method of a liquid crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, offset printing, flexographic printing, inkjet, etc. is common. Other coating methods include dip, roll coater, slit coater, spinner, and the like, and these may be used depending on the purpose.

After applying the liquid crystal aligning agent on the substrate, the solvent is evaporated at 100 ° C to 300 ° C, preferably 100 ° C to 250 ° C, more preferably 150 ° C to 250 ° C by a heating means such as a hot plate, and the polymer It can be made into a film (hereafter, this step is also referred to as a firing step).

In the firing step, the thermal leaving group protecting the amino group in the polymer is desorbed by heat to generate highly reactive primary and secondary amino groups, and some of them undergo a cyclization reaction with other sites in the polymer, It is preferable from the viewpoint of the effect of this invention and the storage stability of a liquid crystal aligning agent that an aromatic heterocyclic ring arises and that the liquid crystal aligning film of this invention is obtained as a result.

The structure of the amino group preferably contained in the polymer of the present invention, to which the thermal leaving group is bonded, is shown, for example, as follows.

[Formula 4]

In the above formula (a), X ¹ is an oxygen atom or a sulfur atom, A ¹ to A ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and the total number of carbon atoms is 1 to 9. Moreover, in the said formula (a) and the said formula (b), * represents a bond with another atom.

Examples of structures capable of generating an aromatic heterocyclic ring through a cyclization reaction with a primary amino group include the following structures.

[Formula 5]

In formula, D represents a divalent C1-C20 saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring, and D may have various substituents. Further, E is a single bond, or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring, and F is a single bond or an ether bond (-O-) or an ester bond (-OCO -, -COO-). m is 1 or 0. R is a structure represented by the formula (a).

If the thickness of the film after the baking step is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, it is preferably 5 nm to 300 nm, more preferably Preferably, it is 10 nm to 100 nm. When horizontally aligning or obliquely aligning liquid crystal, the coating after baking is aligned by a known method such as rubbing or polarized ultraviolet irradiation.

<Aromatic Heterocycle>

Examples of the aromatic heterocyclic ring contained in the polymer in the liquid crystal alignment film of the present invention include a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, and a thiazole ring. , 5-membered aromatic heterocyclic rings such as isothiazole rings; six-membered aromatic heterocyclic rings such as pyridine rings, pyrimidine rings, pyridazine rings, pyrazine rings, and triazine rings; and polycyclic aromatic heterocyclic compounds such as quinoline, isoquinoline, coumarin, indole, benzimidazole, and benzofuran.

Among the above, a pyridine ring, an imidazole ring, and a benzimidazole ring are preferable, and an imidazole ring and a benzimidazole ring are particularly preferable, from the viewpoint of exhibiting the effect of the present invention more remarkably.

Although the said aromatic heterocyclic ring exhibits the effect of this invention even if it already exists in the polymer contained in the said liquid crystal aligning agent, it is preferable that an aromatic heterocyclic skeleton is formed at the time of baking of a liquid crystal aligning film from the viewpoint mentioned above. . Moreover, the aromatic heterocycle which already exists in the polymer contained in a liquid crystal aligning agent, and the aromatic heterocycle formed at the time of baking may coexist.

<Polymer>

The liquid crystal aligning agent of the present invention and the polymer contained in the liquid crystal aligning film obtained using the same are not particularly limited as long as they have an aromatic heterocyclic ring and a primary amino group and a secondary amino group in the structure, but the properties and reliability of the obtained liquid crystal display element From a viewpoint, it is preferable that it is at least 1 sort(s) of polymer chosen from the polyimide precursor which is a reaction product of a diamine component and a tetracarbon derivative component, and polyimide which is an imide product thereof.

A polyimide precursor here refers to polyamic acid or polyamic acid ester.

<diamine>

The liquid crystal aligning agent of the present invention and the polymer contained in the liquid crystal aligning film obtained using the same are preferably at least one polymer selected from a polyimide precursor and a polyimide that is an imide of a polyimide precursor, but the diamine used for the production thereof is preferred. Among the components, at least one selected from the group consisting of a diamine having a structure generating an aromatic heterocyclic ring (hereinafter also referred to as specific diamine 1) and a diamine having an aromatic heterocyclic ring in the structure (hereinafter also referred to as specific diamine 2) A diamine and a diamine having a structure generating a primary amino group or a secondary amino group (hereinafter also referred to as specific diamine 3) are used.

Each diamine is described in detail below.

<Specific diamine 1>

Specific diamine 1 has a structure selected from the following formula (1-1) and formula (1-2).

[Formula 6]

In the formula (1-1), D represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring, and D may have various substituents. In the above formula (1-2), E is a single bond, or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring, and F is a single bond or an ether bond (- O-) and an ester bond (-OCO-, -COO-). In the formula (1-1), m is 1 or 0. In the formula (1-1) and the formula (1-2), R represents a thermal leaving group.

In the formulas (1-1) and (1-2), * represents a bond with another atom. In the case of bonding with an amino group, the substitution position of the amino group is not particularly limited, but from the viewpoint of the difficulty of synthesis and availability of reagents, the meta or para position is preferred based on the amide bond, and from the viewpoint of liquid crystal orientation, the para position is particularly preferred. In addition, also in aminobenzene having no amino group protected by a thermal leaving group, the meta or para position is similarly preferred with respect to the amide bond, the meta position is preferred from the viewpoint of solubility, and from the viewpoint of liquid crystal orientation The location of the para is preferred. Moreover, the hydrogen of aminobenzene which does not have -NHR may be substituted by halogen atoms, such as an organic group and fluorine.

In addition, * in the above formula (1-1) may be bonded to the same structure of the above formula (1-1) or the structure of the above formula (1-2), or through another atom, the above formula (1 -1) or the structure of formula (1-2) above.

Although D in the said formula (1-1) and E in the said formula (1-2) are the same as the definition above, the details are not specifically limited, Dicarboxylic acid or tetracarboxylic dianhydride used as a raw material Depending on the structure of the back, various structures can be selected. As D, from a solubility viewpoint, a bivalent hydrocarbon group etc. are preferable, and a linear alkylene group, a cyclic alkylene group, etc. are mentioned as preferable examples, and this hydrocarbon group may have an unsaturated bond. Moreover, from a viewpoint of liquid-crystal orientation and electrical characteristics, a bivalent aromatic hydrocarbon group, a heterocyclic ring, etc. are preferable. From the viewpoint of liquid crystal orientation, it is preferable that D does not have a substituent, but from the viewpoint of solubility, it is preferable that the hydrogen atom is substituted with a carboxylic acid group or a fluorine atom.

<Specific diamine 2>

Specific diamine 2 has a structure of the following formula (2).

[Formula 7]

In the formula (2), X ₁ is at least one selected from the group consisting of -O-, -NQ ¹ -, -CONQ ¹ -, -NQ ¹ CO-, -CH ₂ O-, and -OCO- A divalent organic group, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ₂ is a single bond or a group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group. At least one selected divalent organic group, X ₃ is a single bond, or -O-, -NQ ² -, -CONQ ² -, -NQ ² CO-, -COO-, -OCO-, and -O (CH ₂ ) _m - at least one divalent organic group selected from the group consisting of (m is an integer of 1 to 5), Q ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ₄ is aromatic It is a complex ring.

* represents a bond with another atom. When bonding with an amino group, the bonding position of the two amino groups (-NH ₂ ) is not limited. Specifically, with respect to the bonding group (X ₁ ) of the side chain, positions 2 and 3 on the benzene ring, positions 2 and 4, positions 2 and 5, positions 2 and 6, positions 3 and 4, 3, 5 can be located. Among these, if the viewpoint of reactivity at the time of synthesizing a polyamic acid and the ease at the time of synthesizing a diamine compound are taken into account, the bonding position of the two amino groups is the position of 2 and 4, the position of 2 and 5, and the position of 3 and 5 Location is particularly preferred.

Moreover, * may be bonded to the same structure of the above formula (2), or may be bonded to the structure of the above formula (2) via another atom.

X ₁ is at least one divalent organic group selected from the group consisting of -O-, -NQ ¹ -, -CONQ ¹ -, -NQ ¹ CO-, -CH ₂ O-, and -OCO-. Especially, -O-, ^-NQ1- , ^-CONQ1- , and ^-NQ1CO- are preferable. Moreover, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group.

X ₂ is a single bond or at least one divalent organic group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group.

The aliphatic hydrocarbon group of 1 to 20 carbon atoms may be linear or branched. Moreover, you may have an unsaturated bond. It is preferably an aliphatic hydrocarbon group of 1 to 10 carbon atoms.

X ₃ is a single bond, or -O-, -NQ ² -, -CONQ ² -, -NQ ² CO-, -COO-, -OCO-, and -O(CH ₂ ) _m - (m is 1 to 5 is at least one divalent organic group selected from the group consisting of), preferably a single bond, -O-, -CONQ ² -, -NQ ² CO-, -COO-, -OCO-, -O(CH ₂ ) _m - (m is an integer from 1 to 5). Most preferably, it is a single bond, -OCO-, or -OCH ₂ -. Moreover, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group.

X ₄ is an aromatic heterocyclic ring. Examples and preferred structures thereof are the same as those described above.

Particularly preferable combinations of X ₁ , X ₂ , X ₃ , X ₄ and n are as shown in Tables 1 to 3 below. In addition, Q ¹ and Q ² have the same meaning as the above definition.

<Specific diamine 3>

Specific diamine 3 is a diamine having a structure generating a primary amino group or a secondary amino group, and has a structure of an amino group protected by a thermal leaving group in the structure. Although such a structure is not particularly limited, it is preferable to contain at least one type of structure selected from the following structures from the viewpoint of easiness of thermal detachment and the like.

[Formula 8]

In the above formula (a), X ¹ is an oxygen atom or a sulfur atom, A ¹ to A ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and the total number of carbon atoms is 1 to 9. In the above formula (a) and above formula (b), * represents a bond with another atom.

In the formula (a), X ¹ is an oxygen atom or a sulfur atom, and an oxygen atom is preferable. A ¹ to A ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably having 1 carbon atom. Moreover, the total number of carbon atoms is 1-9, and 3-6 are preferable. In the above formula (a) and above formula (b), * represents a bond with another atom.

As diamine which has at least 1 sort(s) of structure chosen from said formula (a) and said formula (b) in a structure, the diamine of the following structures is mentioned, for example. In addition, "Boc" in the formula is a tert-butoxycarbonyl group.

[Formula 9]

<Diamine having an amino group not involved in polymerization>

For production of the liquid crystal aligning agent for obtaining the liquid crystal aligning film of the present invention, diamine having a structure generating a primary amino group or a secondary amino group, that is, diamine having a structure of an amino group protected by a thermal leaving group in the structure is used, A diamine having an amino group that is not protected and does not participate in polymerization may be used. Such diamines are exemplified below.

[Formula 10]

<Other diamines>

In producing the polyimide precursor preferably used as a polymer contained in the liquid crystal aligning agent of the present invention, even if it contains diamines other than specific diamines (hereinafter, also referred to as other diamines) within the limit of exhibiting the effect of the present invention. do. Such diamine is represented by the following general formula (3).

[Formula 11]

In the formula (3), Y is a divalent organic group derived from diamine, and the structure thereof is not particularly limited. If the specific example of the structure of Y is shown, the following formula (Y-1) - formula (Y-99) will be mentioned.

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

In the formula (Y-90), m and n are each an integer of 1 to 11, m + n is an integer of 2 to 12, and in the formula (Y-95), h is an integer of 1 to 3, In the above formula (Y-92) and the above formula (Y-98), j is an integer of 0 to 3.

<Tetracarboxylic dianhydride>

When manufacturing the polyimide precursor used suitably as a polymer contained in the liquid crystal aligning agent of this invention, tetracarboxylic dianhydride used is represented by following formula (4).

[Formula 27]

In the formula (4), X is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. Among the polyimide precursors, two or more types of X may be mixed. If the specific example of X is shown, the structures of following formula (X-1) - following formula (X-44) will be mentioned.

Moreover, when manufacturing polyamic acid ester, it can manufacture using the dicarboxylic acid diester corresponding to the various structures of the tetracarboxylic dianhydride mentioned here.

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

R ₁ to R ₄ in the formula (X-1) are each independently a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group, or a phenyl group. When R ₁ to R ₄ have a bulky structure, a hydrogen atom, a methyl group, or an ethyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable, since there is a possibility of lowering the liquid-crystal orientation.

In the above formula (4), it is preferable that X contains a structure selected from the above formula (X-1) to the above formula (X-14) from the viewpoint of availability of the monomer.

From the viewpoint of further enhancing the reliability of the obtained liquid crystal aligning film, the structure of X has a structure consisting of only aliphatic groups such as the above formula (X-1) to the above formula (X-7) and the above formula (X-10). It is preferable, and the structure represented by the said formula (X-1) is more preferable. Moreover, since favorable liquid-crystal orientation is shown, as a structure of X, the following formula (X1-1) or the following formula (X1-2) is more preferable.

[Formula 32]

<liquid crystal aligning agent>

The liquid crystal aligning agent of this invention has the form of the solution in which the above polyimide precursor or its imidation polymer (henceforth a polymer of a specific structure) was dissolved in the organic solvent. The molecular weight of the polymer having a specific structure is preferably from 2,000 to 500,000, more preferably from 5,000 to 300,000, still more preferably from 8,000 to 100,000 in terms of weight average molecular weight. Moreover, the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, still more preferably 4,000 to 50,000.

The concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed according to the setting of the thickness of the coating film to be formed, but it is preferably 1% by weight or more in terms of forming a uniform and defect-free coating film, and the solution From the viewpoint of storage stability of , it is preferable to set it as 10% by weight or less. A particularly preferred concentration of the polymer is 2 to 8% by mass.

The organic solvent contained in the liquid crystal aligning agent used for this invention will not be specifically limited if the polymer of a specific structure melt|dissolves uniformly. For example, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrroly Money, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, dimethylsulfone, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3- Methoxy-N,N-dimethylpropanamide etc. are mentioned. You may use these 1 type or in mixture of 2 or more types. Moreover, even if it is a solvent which cannot dissolve a polymer uniformly by itself, you may mix with said organic solvent as long as it is a range in which a polymer does not precipitate. Especially, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone.

In addition, as for the organic solvent contained in the liquid crystal aligning agent, in addition to the above solvents, it is common to use a mixed solvent in which a solvent that improves the coating property at the time of applying the liquid crystal aligning agent and the surface smoothness of the coating film is used in combination, and this Also in the liquid crystal aligning agent of the invention, such a mixed solvent is preferably used. Although the specific example of the organic solvent used together is given below, it is not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 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, 2,6-dimethyl-4-heptanol, 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, diisopropyl ether , dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-hep Thanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 4,6-dimethyl-2-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2- Ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol 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, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, 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, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol Acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxymethylpropionate, 3-ethoxyethylpropionate, 3-ethoxymethylethylpropionate, 3-methoxyethylpropionate, 3-ethoxypropionate, 3-methoxypropionate, 3-methoxypropylpropionate, 3- Butyl methoxypropionate, methyl lactate ester, ethyl lactate ester, n-propyl lactate ester, n-butyl lactate ester, isoamyl lactate ester, solvents represented by the following formula [D-1] to the following formula [D-3], etc. can be heard

[Formula 33]

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

Among them, preferred combinations of solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, and propylene glycol monobutyl ether. Butyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene Glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, γ-butyrolactone, dipropylene glycol dimethyl ether, and the like. The type and content of such a solvent are appropriately selected depending on the application device, application conditions, and application environment of the liquid crystal aligning agent.

In addition to the above, in the liquid crystal aligning agent of the present invention, as long as the effect of the present invention is not impaired, polymers other than the polymer described in the present invention, dielectric or conductive material for the purpose of changing electrical properties such as dielectric constant or conductivity of the liquid crystal aligning film , A silane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, a cross-linkable compound for the purpose of increasing the hardness and density of the film when used as a liquid crystal alignment film, and also an image by heating the polyimide precursor when baking the coating film You may add an imidation promoter etc. for the purpose of advancing deification efficiently.

In addition, in order to improve the adhesiveness of the coating film with respect to a board|substrate, additives, such as a silane coupling agent, may be added to the liquid crystal aligning agent of this invention, and another resin component may be added.

As a compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, a functional silane containing compound and an epoxy group containing compound are mentioned, For example, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureido Propyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-Trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethine Toxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltri Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis (oxyethylene)-3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N, N-diglycidyl aminomethyl) cyclohexane or N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

Moreover, you may add the following additives to the liquid crystal aligning agent of this invention in order to raise the mechanical strength of a film|membrane.

[Formula 34]

[Formula 35]

It is preferable that these additives are 0.1-30 mass parts with respect to 100 mass parts of the polymer components contained in a liquid crystal aligning agent. If it is less than 0.1 part by mass, no effect can be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal will be reduced. Therefore, it is more preferably 0.5 part by mass to 20 parts by mass.

<Liquid crystal display element>

The liquid crystal display element of this invention obtains the board|substrate with a liquid crystal aligning film from the liquid crystal aligning agent of this invention by the above-mentioned method, and orientation-processes by a rubbing process etc., Then, it is set as a liquid crystal display element by a known method.

The manufacturing method of the liquid crystal cell of the liquid crystal display element is not particularly limited, but if an example is given, a pair of substrates on which a liquid crystal alignment film is formed, the liquid crystal alignment film surface is turned inside, preferably 1 μm to 30 μm, more preferably A method in which a 2 μm to 10 μm spacer is interposed therebetween, the periphery is fixed with a sealant, liquid crystal is injected, and sealed is common. The liquid crystal sealing method is not particularly limited, and examples thereof include a vacuum method in which liquid crystal is injected after depressurizing the inside of the produced liquid crystal cell, and a dropping method in which liquid crystal is dropped and then sealed. Since the liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention as described above has excellent characteristics, liquid crystal display elements such as VA, TN, STN, TFT, transverse electric field type, and by extension, ferroelectric and antiferroelectric liquid crystal display elements It can be used as a liquid crystal aligning film for.

Example

Below, the present invention will be specifically described by giving examples and the like, but the present invention is not limited to these examples. In addition, the symbol of a compound and a solvent is as follows.

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

BCS: butyl cellosolve

DA-1: the following structural formula (DA-1)

DA-2: the following structural formula (DA-2)

DA-3: the following structural formula (DA-3)

DA-4: the following structural formula (DA-4)

DA-5: the following structural formula (DA-5)

DA-6: the following structural formula (DA-6)

DA-7: the following structural formula (DA-7)

DA-8: the following structural formula (DA-8)

DA-9: the following structural formula (DA-9)

DA-10: the following structural formula (DA-10)

CA-1: the following structural formula (CA-1)

CA-2: the following structural formula (CA-2)

CA-3: the following structural formula (CA-3)

CA-4: the following structural formula (CA-4)

[Formula 36]

[Formula 37]

[Formula 38]

<Viscosity>

In the synthesis example, the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) at a sample amount of 1.1 ml, a cone rotor TE-1 (1 ° 34 ', R24), and a temperature of 25 ° C. did

<Measurement of imidization rate of polyimide>

The imidation rate of the polyimide in the synthesis example was measured as follows. 30 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethylsulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) was mixed with product) (0.53 ml) was added, and ultrasonic was applied to dissolve completely. A 500 MHz proton NMR was measured for this solution with an NMR measuring device (JNW-ECA500) (manufactured by JEOL Datum Co., Ltd.). The imidation rate is defined as a proton derived from a structure that does not change before and after imidation as a reference proton, and the peak integrated value of this proton and the proton peak integrated value derived from the NH group of amic acid appearing around 9.5 ppm to 10.0 ppm was obtained using the following formula.

Imidization rate (%) = (1 - α x / y) × 100

In the above formula, x is the proton peak integration value derived from the NH group of the amic acid, y is the peak integration value of the reference proton, and α is the NH of the amic acid in the case of polyamic acid (imidization ratio is 0%) It is the ratio of the number of reference protons to one group proton.

(Example 1)

86.0 g (352 mmol) of DA-1, 53.4 g (95.9 mmol) of DA-2, and 76.5 g (191 mmol) of DA-3 were weighed into a 1-liter four-necked flask equipped with a stirrer and a nitrogen inlet tube. This was added, 1580 g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. Stirring this diamine solution under water cooling, 93.2g (416 mmol) of CA-1 was added, 168g of NMP was added, and it stirred at 40 degreeC by nitrogen atmosphere for 3 hours. Furthermore, 28.2 g (143 mmol) of CA-2 was added, 160 g of NMP was further added, and the mixture was stirred under a nitrogen atmosphere at 23°C for 4 hours to obtain a polyamic acid solution (PAA-1). The viscosity in the temperature of 25 degreeC of this solution of a polyamic acid was 200 mPa*s.

30.7 g of this polyamic acid solution (PAA-1) was separated into a 200 ml Erlenmeyer flask equipped with a stirrer, 9.07 g of NMP, 26.2 g of GBL, and 1 mass of 3-glycidoxypropyltriethoxysilane were added. 3.93 g of NMP solution containing % and 17.4 g of BCS were added, and it stirred with the magnetic stirrer for 2 hours, and obtained the solution (A-1) of a polyamic acid.

(Example 2)

800 g of the polyamic acid solution (PAA-1) obtained in Example 1 was separated into a 3 L Erlenmeyer flask containing a stirrer bar, 700 g of NMP, 69.7 g of acetic anhydride, and 18.0 g of pyridine were added, and the mixture was cooled to room temperature. After stirring for 30 minutes, it was made to react at 55 degreeC for 3 hours. The precipitate obtained by throwing in this reaction solution in 5600 g of methanol was separated by filtration. After washing this precipitate with methanol, it was made to dry under reduced pressure at the temperature of 60 degreeC, and the powder of polyimide was obtained. The imidation ratio of the powder of this polyimide was 75%.

20.4 g of this polyimide powder was separated and collected in a 300 ml Erlenmeyer flask with a stirrer bar, 115 g of NMP was added, and the mixture was stirred and dissolved at 50°C for 20 hours. Further, 16.3 g of this solution was separated into a 100 ml Erlenmeyer flask with a stirrer, and an NMP solution containing 5.49 g of NMP, 14.3 g of GBL, and 1% by mass of 3-glycidoxypropyltriethoxysilane was prepared. 2.15g and 9.56g of BCS were added, and it stirred with the magnetic stirrer for 2 hours, and obtained the polyimide solution (A-2).

(Synthesis Example 1)

2.20 g (9.00 mmol) of DA-1, 2.04 g (5.97 mmol) of DA-4, and 1.62 g (15.0 mmol) of DA-5 were weighed into a 200 ml four-necked flask equipped with a stirrer and a nitrogen inlet pipe. This was added, 59.3 g of NMP was added, and the mixture was dissolved by stirring while blowing nitrogen. While stirring this diamine solution under water cooling, 6.32 g (28.1 mmol) of CA-1 was added, and 30.0 g of NMP was further added, followed by stirring under a nitrogen atmosphere at 40°C for 3 hours to obtain a polyamic acid solution (PAA-2) got The viscosity in the temperature of 25 degreeC of this polyamic acid solution was 220 mPa*s.

In a 200 ml Erlenmeyer flask equipped with a stirring bar, 21.1 g of this polyamic acid solution (PAA-2) was separated, 2.20 g of NMP, 15.3 g of GBL, and 1 mass of 3-glycidoxypropyltriethoxysilane were added. 2.30 g of NMP solution containing % and 10.2 g of BCS were added, and it stirred for 2 hours with a magnetic stirrer, and obtained the solution (B-1) of a polyamic acid.

(Synthesis Example 2)

90.0 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 1 was separated into a 500 ml Erlenmeyer flask with a stirrer bar, 45.0 g of NMP, 8.14 g of acetic anhydride, and 2.10 g of pyridine were added to room temperature. After stirring for 30 minutes, it was made to react at 55 degreeC for 3 hours. The precipitate obtained by throwing in this reaction solution in 600 g of methanol was separated by filtration. After washing this precipitate with methanol, it was made to dry under reduced pressure at the temperature of 60 degreeC, and the powder of polyimide was obtained. The imidation ratio of the powder of this polyimide was 67%.

5.50 g of this polyimide powder was separated and collected in a 300 ml Erlenmeyer flask with a stirring bar, 40.3 g of NMP was added, and the mixture was stirred and dissolved at 50°C for 20 hours. Further, 25.0 g of this solution was separated into a 200 ml Erlenmeyer flask with a stirrer, and an NMP solution containing 5.30 g of NMP, 20.0 g of GBL, and 1% by mass of 3-glycidoxypropyltriethoxysilane was prepared. 3.00 g and 13.3 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a polyimide solution (B-2).

(Synthesis Example 3)

To a 200 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 0.540 g (4.99 mmol) of DA-5, 2.12 g (8.75 mmol) of DA-6, 0.826 g (2.50 mmol) of DA-7, 3.80 g (8.75 mmol) of DA-8 was weighed and placed, 41.3 g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. Stirring this diamine solution under water cooling, 3.12g (12.4 mmol) of CA-3 was added, 17.8g of NMP was added, and it stirred at 60 degreeC by nitrogen atmosphere for 3 hours. Furthermore, 2.42 g (12.3 mmol) of CA-2 was added, 14.1 g of NMP was further added, and the mixture was stirred under a nitrogen atmosphere at 40°C for 4 hours to obtain a solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of this polyamic acid solution was 115 mPa*s.

20.6 g of this polyamic acid solution was separated into a 200 ml Erlenmeyer flask equipped with a stirrer bar, and an NMP solution containing 10.6 g of NMP, 20.6 g of GBL, and 1% by mass of 3-glycidoxypropyltriethoxysilane. 3.09 g and 13.7 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a polyamic acid solution (B-3).

(Synthesis Example 4)

3.18 g (8.00 mmol) of DA-3, 2.38 g (6.00 mmol) of DA-9, and 1.79 g (6.00 mmol) of DA-10 were weighed into a 200 ml four-necked flask equipped with a stirrer and a nitrogen inlet pipe. This was added, 66.2 g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this diamine solution under water cooling, 4.25 g (19.5 mmol) of CA-4 was added, 18.9 g of NMP was further added, and the mixture was stirred under a nitrogen atmosphere at 50°C for 15 hours to obtain a solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of this polyamic acid solution was 264 mPa*s.

15.3 g of this polyamic acid solution was separated into a 100 ml Erlenmeyer flask equipped with a stirrer bar, and an NMP solution containing 0.300 g of NMP, 10.3 g of GBL, and 1% by mass of 3-glycidoxypropyltriethoxysilane. 1.54 g and 6.86 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a polyamic acid solution (B-4).

(Example 3)

5.42 g of the polyamic acid solution (A-1) obtained in Example 1 and 5.41 g of the polyamic acid solution (B-1) obtained in Synthesis Example 1 were weighed into a 50 ml Erlenmeyer flask equipped with a stirrer, and placed in a magnetic stirrer. It stirred for 2 hours and obtained the liquid crystal aligning agent (A-3).

(Example 4)

5.50 g of the polyimide solution (A-2) obtained in Example 2 and 5.51 g of the polyimide solution (B-2) obtained in Synthesis Example 2 were weighed and placed in a 50 ml Erlenmeyer flask equipped with a stirrer, and a magnetic stirrer was placed. It stirred for 2 hours and obtained the liquid crystal aligning agent (A-4).

(Example 5)

5.42 g of the polyamic acid solution (B-1) obtained in Synthesis Example 1 and 5.42 g of the polyamic acid solution (B-3) obtained in Synthesis Example 3 were weighed into a 50 ml Erlenmeyer flask equipped with a stirrer, and placed in a magnetic stirrer. It stirred for 2 hours and obtained the liquid crystal aligning agent (A-5).

(Example 6)

5.62 g of the polyamic acid solution (A-1) obtained in Example 1 and 5.62 g of the polyamic acid solution (B-4) obtained in Synthesis Example 4 were weighed into a 50 ml Erlenmeyer flask equipped with a stirrer, and placed in a magnetic stirrer. It stirred for 2 hours and obtained the liquid crystal aligning agent (A-6).

<Evaluation of seal adhesion>

After filtering the liquid crystal aligning agent obtained by the Example and the synthesis example with a 1.0 micrometer filter, it spin-coats on the glass substrate with a transparent electrode, and after drying on a 80 degreeC hot plate for 2 minutes, it baked at 230 degreeC for 20 minutes, and formed a film A coating film with a thickness of 100 nm was obtained. After preparing two board|substrates obtained by doing in this way and spread|dispersing a 4 micrometer bead spacer on the liquid crystal aligning film surface of one board|substrate, the sealing compound (XN-1500T by Kyoritz Chemical) was dripped. Then, it bonded together so that the liquid crystal aligning film surface of the other board|substrate might be made into an inside, and the overlapping width of a board|substrate might be set to 1 cm. At that time, the sealing agent dripping amount was adjusted so that the diameter of the sealing compound after bonding might be set to about 3 mm. After fixing the bonded two substrates with a clip, they were thermally cured at 120°C for 1 hour to prepare samples for adhesiveness evaluation.

Next, the fabricated sample was fixed with a tabletop precision universal testing machine AGS-X 500N manufactured by Shimadzu Corporation at the ends of the upper and lower substrates, then press-fitted from the upper part of the central portion of the substrate, and the force at the time of peeling (N ) was evaluated as seal adhesion.

(Examples 7 to 12)

After filtering each of the liquid crystal aligning agents (A-1) to (A-6) obtained in Examples 1 to 6 with a 1.0 μm filter, samples for adhesive evaluation were prepared as described above and seal adhesive force was evaluated. A result is shown in Table 4.

(Comparative Examples 1 to 4)

After filtering each of the liquid crystal aligning agents (B-1) to (B-4) obtained in Synthesis Examples 1 to 4 with a 1.0 µm filter, samples for adhesive evaluation were produced as described above and seal adhesion was evaluated. A result is shown in Table 4.

In the case of using the liquid crystal aligning agent described in Examples, the seal adhesive force was high and good.

(Example 13)

4.30 g (17.6 mmol) of DA-1, 2.67 g (4.80 mmol) of DA-2, and 3.27 g (9.57 mmol) of DA-4 were weighed into a 200 ml four-necked flask equipped with a stirrer and a nitrogen inlet pipe. This was added, 75.1 g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this diamine solution under water cooling, 4.66 g (20.7 mmol) of CA-1 was added, 9.34 g of NMP was added, and the mixture was stirred at 40°C under a nitrogen atmosphere for 3 hours. Furthermore, 1.78 g (9.08 mmol) of CA-2 was added, 8.00 g of NMP was further added, and the mixture was stirred under a nitrogen atmosphere at 23°C for 4 hours to obtain a solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of this polyamic acid solution was 304 mPa*s.

90.0 g of this polyamic acid solution was separated into a 500 ml Erlenmeyer flask equipped with a stirrer, 79.0 g of NMP, 7.92 g of acetic anhydride, and 2.04 g of pyridine were added, stirred at room temperature for 30 minutes, and then heated to 55°C. reacted for 3 hours. The precipitate obtained by throwing in this reaction solution in 700 g of methanol was separated by filtration. After washing this precipitate with methanol, it was made to dry under reduced pressure at the temperature of 60 degreeC, and the powder of polyimide was obtained. The imidation ratio of the powder of this polyimide was 70%.

In a 200 ml Erlenmeyer flask with a stirrer bar, 6.07 g of this polyimide powder was separated and collected, 44.5 g of NMP was added, and the mixture was stirred and dissolved at 50°C for 20 hours. Further, 20.3 g of this solution was separated into a 200 ml Erlenmeyer flask with a stirrer, and an NMP solution containing 4.37 g of NMP, 16.2 g of GBL, and 1% by mass of 3-glycidoxypropyltriethoxysilane was prepared. 2.43g and 10.8g of BCS were added, and it stirred with the magnetic stirrer for 2 hours, and obtained the polyimide solution (A-7).

(Example 14)

In a 200 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 4.30 g (17.6 mmol) of DA-1, 2.67 g (4.80 mmol) of DA-2, 1.91 g (4.80 mmol) of DA-3, 1.64 g (4.80 mmol) of DA-4 was weighed and placed, 77.1 g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this diamine solution under water cooling, 4.66 g (20.7 mmol) of CA-1 was added, 8.88 g of NMP was added, and the mixture was stirred at 40°C under a nitrogen atmosphere for 3 hours. Furthermore, 1.71 g (8.69 mmol) of CA-2 was added, 8.00 g of NMP was further added, and the mixture was stirred under a nitrogen atmosphere at 23°C for 4 hours to obtain a solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of this polyamic acid solution was 312 mPa*s.

90.0 g of this polyamic acid solution was separated into a 500 ml Erlenmeyer flask containing a stirrer bar, 79.0 g of NMP, 7.02 g of acetic anhydride, and 1.81 g of pyridine were added, stirred at room temperature for 30 minutes, and then heated to 55°C. reacted for 3 hours. The precipitate obtained by throwing in this reaction solution in 700 g of methanol was separated by filtration. After washing this precipitate with methanol, it was made to dry under reduced pressure at the temperature of 60 degreeC, and the powder of polyimide was obtained. The imidation ratio of the powder of this polyimide was 71%.

6.03 g of this polyimide powder was separated into a 200 ml Erlenmeyer flask equipped with a stirrer bar, 44.2 g of NMP was added, and the mixture was stirred at 50°C for 20 hours to dissolve. Further, 21.0 g of this solution was separated into a 200 ml Erlenmeyer flask with a stirrer, and an NMP solution containing 4.48 g of NMP, 16.8 g of GBL, and 1% by mass of 3-glycidoxypropyltriethoxysilane was prepared. 2.52 g and 11.2 g of BCS were added, and it stirred with a magnetic stirrer for 2 hours to obtain a polyimide solution (A-8).

(Synthesis Example 5)

4.30 g (17.6 mmol) of DA-1 and 5.73 g (14.3 mmol) of DA-3 were placed in a 1-liter four-necked flask equipped with a stirrer and a nitrogen inlet tube, 73.6 g of NMP was added, and nitrogen was added. was dissolved by stirring while sending. While stirring this diamine solution under water cooling, 4.66 g (20.7 mmol) of CA-1 was added, 9.69 g of NMP was added, and the mixture was stirred at 40°C under a nitrogen atmosphere for 3 hours. Furthermore, 1.50 g (7.65 mmol) of CA-2 was added, 8.53 g of NMP was further added, and the mixture was stirred under a nitrogen atmosphere at 23°C for 4 hours to obtain a solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of this polyamic acid solution was 290 mPa*s.

90.0 g of this polyamic acid solution was separated into a 500 ml Erlenmeyer flask equipped with a stirrer bar, 79.0 g of NMP, 8.16 g of acetic anhydride, and 2.10 g of pyridine were added, stirred at room temperature for 30 minutes, and then heated to 55°C. reacted for 3 hours. The precipitate obtained by throwing in this reaction solution in 700 g of methanol was separated by filtration. After washing this precipitate with methanol, it was made to dry under reduced pressure at the temperature of 60 degreeC, and the powder of polyimide was obtained. The imidation ratio of the powder of this polyimide was 72%.

6.10 g of this polyimide powder was separated and collected in a 200 ml Erlenmeyer flask with a stirring bar, 44.7 g of NMP was added, and the mixture was stirred and dissolved at 50°C for 20 hours. Further, 25.0 g of this solution was separated into a 200 ml Erlenmeyer flask with a stirrer, and an NMP solution containing 4.90 g of NMP, 19.8 g of GBL, and 1% by mass of 3-glycidoxypropyltriethoxysilane was prepared. 3.00 g and 13.3 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a polyimide solution (B-5).

<Evaluation of liquid crystal orientation>

Below, the preparation method of the liquid crystal cell for evaluating liquid-crystal orientation is shown.

The liquid crystal cell provided with the structure of the liquid crystal display element of FFS system is produced. First, a substrate with electrodes was prepared. The substrate is a glass substrate having a size of 30 mm x 35 mm and a thickness of 0.7 mm. On the substrate, as a first layer, an IZO electrode constituting a counter electrode is formed over the entire surface. On the counter electrode of the first layer, as a second layer, a SiN (silicon nitride) film formed by the CVD method is formed. The film thickness of the second layer SiN film is 100 nm, and functions as an interlayer insulating film. On the SiN film of the 2nd layer, as a 3rd layer, the comb-shaped pixel electrode formed by patterning the IZO film is arrange|positioned, and two pixels, a 1st pixel and a 2nd pixel, are formed. The size of each pixel is 10 mm long and about 5 mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of the third layer has a comb-like shape, which is constituted by arranging a plurality of z-shaped electrode elements with bent central portions. The width of each electrode element in the width direction is 3 μm, and the interval between the electrode elements is 6 μm. Since the pixel electrode constituting each pixel is constituted by arranging a plurality of z-shaped electrode elements bent at the center, the shape of each pixel is not rectangular, but bent at the center like the electrode element. It has a shape resembling the character く in bold letters. Then, each pixel is divided up and down with the central bending part as a boundary, and has a first region above the bending part and a second region below the bending part.

Comparing the 1st area and the 2nd area|region of each pixel, the formation direction of the electrode element of the pixel electrode which comprises them differs. That is, on the basis of the rubbing direction of the liquid crystal alignment film described later, in the first area of the pixel, the electrode element of the pixel electrode is formed so as to form an angle of +10° (clockwise direction), and in the second area of the pixel, the pixel The electrode elements of the electrode are formed to form an angle of -10° (clockwise). That is, in the first area and the second area of each pixel, the directions of rotation (in-plane switching) of the liquid crystal within the substrate surface caused by application of a voltage between the pixel electrode and the opposite electrode are opposite to each other. It is composed so that

Next, after filtering the liquid crystal aligning agent obtained by the Example and the synthesis example with a 1.0 micrometer filter, it apply|coated to the prepared said board|substrate with an electrode by spin-coating. After drying for 2 minutes on an 80 degreeC hot plate, it baked in a 230 degreeC hot-air circulation type oven for 20 minutes, and obtained the polyimide membrane of the film thickness of 60 nm. The polyimide film was rubbed with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 500 rpm, moving speed: 30 mm/sec, indentation length: 0.3 mm, rubbing direction: 10° tilted with respect to the third layer IZO comb electrode After washing, ultrasonic irradiation was performed in pure water for 1 minute to perform cleaning, and water droplets were removed by air blowing. Then, it was made to dry at 80 degreeC for 15 minute(s), and the board|substrate with a liquid crystal aligning film was obtained. Further, as a counter substrate, a glass substrate having a columnar spacer having a height of 4 μm and having an ITO electrode formed on the back surface was formed with a polyimide film in the same manner as above, and an orientation treatment was performed in the same procedure as above. A substrate with a liquid crystal alignment film was obtained. These two substrates with a liquid crystal alignment film are used as one set, a sealing compound is printed in a form leaving a liquid crystal inlet on the substrate, and the liquid crystal alignment film surfaces face each other, and the rubbing direction is antiparallel. did Thereafter, the sealing compound was cured to prepare an empty cell having a cell gap of 4 μm. Liquid crystal MLC-3019 (manufactured by Merck & Co., Ltd.) was injected into this empty cell by a vacuum injection method, the injection port was sealed, and a liquid crystal cell of the FFS system was obtained. Then, after heating the obtained liquid crystal cell at 120 degreeC for 1 hour and leaving it to stand at 23 degreeC overnight, it was used for evaluation of the liquid-crystal orientation.

Using this liquid crystal cell, the alternating voltage of 9 VPP was applied on the frequency of 30 Hz in a 60 degreeC constant temperature environment for 190 hours. Then, it was set as the state which short-circuited between the pixel electrode of a liquid crystal cell and the counter electrode, and it was left as it was at room temperature for 1 day.

After standing, the liquid crystal cell was installed between two polarizing plates arranged so that the polarization axes were orthogonal, the backlight was turned on with no voltage applied, and the angle of arrangement of the liquid crystal cell was adjusted so that the luminance of the transmitted light was minimized. And the rotation angle at the time of rotating the liquid crystal cell from the angle at which the 2nd area|region of the 1st pixel becomes the darkest to the angle at which the 1st area|region becomes the darkest was computed as angle (DELTA). Similarly, also in the second pixel, the second area and the first area were compared, and the same angle Δ was calculated. And the average value of the angle Δ value of the 1st pixel and the 2nd pixel was computed as angle Δ of a liquid crystal cell. That is, the smaller this angle, the better the liquid-crystal orientation.

(Examples 15 to 18)

After filtering each of the liquid crystal aligning agents (A-2), (A-4), (A-7) and (A-8) obtained in Examples 2, 4, 13, and 14 with a 1.0 μm filter, the above-described Table 5 shows the results of preparing samples for evaluating adhesiveness and evaluating seal adhesiveness as described above, and the angle Δ of the liquid crystal cell.

(Comparative Example 5)

After filtering the liquid crystal aligning agent (B-5) obtained in Synthesis Example 5 with a 1.0 μm filter, samples for adhesiveness evaluation were produced as described above, and the result of evaluating the seal adhesive force and the angle Δ of the liquid crystal cell A result is shown in Table 5.

When the liquid crystal aligning agent described in the Example was used, the seal adhesive force was high and the angle Δ of the liquid crystal cell after aging was small, and the liquid crystal orientation was also good.

The liquid crystal aligning agent of the present invention can solve display nonuniformity in the vicinity of the frame by increasing the adhesiveness of the sealant and the liquid crystal aligning film in a narrow frame liquid crystal display element capable of securing many display surfaces, and industrially useful.

Claims (7)

It is a reaction product of a diamine component containing at least one kind of diamine selected from the following component (A) and a diamine containing a skeleton of the following component (C) and a diamine represented by the following formula (3), and tetracarboxylic dianhydride A liquid crystal aligning agent characterized by containing at least one polymer selected from polyimides having an imidation ratio of 70% or more as a polyamic acid imidide.
Component (A): diamine having at least one structure selected from the following formula (1-1) and the following formula (1-2)

(Wherein, D represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring, D may have various substituents, and E is a single bond or a divalent A saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring, F represents a single bond, ether bond (-O-), or ester bond (-OCO-, -COO-), and m is , 1 or 0, R represents a thermal leaving group, * represents a bond with another atom, and the aromatic heterocycle is a pyridine skeleton, a benzimidazole skeleton, or an imidazole skeleton.)
Component (C): diamine having at least one structure selected from the following formula (a) and the following formula (b)

(In the formula, X ¹ is an oxygen atom or a sulfur atom, A ¹ to A ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and the total number of carbon atoms is 1 to 9. In addition, * is another represents a bond with an atom.)
Formula (3) diamine:

In the formula (3), Y is a divalent organic group other than a phenylene group, selected from the following formulas (Y-1) to (Y-5) and formulas (Y-9) to (Y-99) is at least one species.

(In the formula (Y-90), m and n are each an integer of 1 to 11, m + n is an integer of 2 to 12, and in the formula (Y-95), h is an integer of 1 to 3, , In the formulas (Y-92) and (Y-98), j is an integer from 0 to 3.) The liquid crystal aligning film characterized by containing the polymer which is obtained from the liquid crystal aligning agent of Claim 1, and which has an aromatic heterocyclic ring, a primary amino group, and a secondary amino group in a structure. According to claim 2,
A liquid crystal aligning film characterized in that it is a film made of a fired material, and the skeleton of the aromatic heterocyclic ring, the primary amino group, and the secondary amino group are contained in a structure formed by firing. According to claim 2,
The said aromatic heterocyclic ring is a pyridine skeleton, a benzimidazole skeleton, or an imidazole skeleton, The liquid crystal aligning film characterized by the above-mentioned. According to claim 3,
The liquid crystal aligning film characterized by the said baked material being produced|generated by the baking temperature of 100 degreeC - 300 degreeC. The liquid crystal display element characterized by being equipped with the liquid crystal aligning film in any one of Claims 2-5. delete