KR102135493B1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Provides a liquid crystal aligning agent capable of forming a liquid crystal aligning film capable of enhancing adhesion between a sealing agent and a liquid crystal aligning film, suppressing the occurrence of uneven display in the vicinity of the frame of an element under high temperature and high humidity conditions, and suppressing a decrease in voltage retention. do. (B) containing at least one polymer selected from the group consisting of a polyimide precursor obtained by reacting a component (A) containing a compound represented by the formula [1] and a diamine component and a tetracarboxylic acid component, and a polyimide ) Liquid crystal aligning agent containing a component. (X ¹ : A divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring, X ² : Formula [1-1] to Formula [1- 5] is selected from) (W ¹ : hydrogen atom or benzene ring)

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element {LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY ELEMENT}

The present invention relates to a liquid crystal aligning agent used in manufacture of a liquid crystal display element, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal aligning film.

A film made of an organic material such as a polymer material has attracted attention for ease of formation and insulation performance, and is widely used as an interlayer insulating film or a protective film in the field of electronic devices. Among them, in a liquid crystal display device well known as a display device, an organic film made of polyimide is used as a liquid crystal alignment film.

The liquid crystal alignment film is used for the purpose of controlling the alignment state of liquid crystal. In recent years, with the high definition of liquid crystal display elements, there is a demand for a reduction in contrast of liquid crystal display elements and suppression of display defects caused by long-term use.

For such a problem, in the case of using polyimide as a liquid crystal alignment film, as a method of increasing liquid crystal alignment and preventing display defects from occurring in the periphery of the liquid crystal display screen, a liquid crystal alignment treatment agent added with an alkoxysilane compound is used. A liquid crystal alignment film has been proposed (see, for example, Patent Document 1 or 2).

Japanese Laid-Open Patent Publication No. 61-171762 Japanese Patent Laid-Open Publication No. Hei 11-119226

Recently, liquid crystal display elements have been used for mobile applications such as smartphones and mobile phones. In these applications, in order to secure as many display surfaces as possible, it is necessary to make the width of the sealing agent used for bonding between the substrates of the liquid crystal display element narrower than in the prior art. Further, for the reasons described above, it is also required to set the drawing position of the sealing agent to a position in contact with the end portion of the liquid crystal alignment film having poor adhesion to the sealing agent, or to the upper portion of the liquid crystal alignment film. In such a case, water is easily mixed in the liquid crystal display element between the sealing agent and the liquid crystal aligning film by use under high temperature and high humidity conditions, and display unevenness occurs near the frame of the liquid crystal display element.

In addition, when water is mixed in the liquid crystal display element, the voltage retention rate, which is one of the electrical characteristics of the liquid crystal display element, is greatly reduced, and ghost failure (also referred to as line ghost), which is one of the display failures of the liquid crystal display element, is liable to occur. A liquid crystal display element with high reliability cannot be obtained.

Therefore, it is an object of the present invention to combine the above characteristics, to increase the adhesion between the sealing agent and the liquid crystal aligning film, to suppress the occurrence of uneven display in the vicinity of the frame of the liquid crystal display element under high temperature and high humidity conditions, and to reduce the voltage retention. It is to provide a liquid crystal aligning agent capable of providing a liquid crystal aligning film which can be suppressed, and a liquid crystal display element having the liquid crystal aligning film.

As a result of intensive research, the present inventors have found that a liquid crystal aligning agent containing a compound having a specific structure and at least one polymer selected from the group consisting of a polyimide precursor and a polyimide is very effective in achieving the above object. It found out that it came to complete the present invention.

That is, the present invention has the following summary.

(1) The liquid-crystal aligning agent characterized by containing the following (A) component and (B) component.

(A) Component: A compound represented by the following formula [1].

Component (B): At least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

[Formula 1]

(X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring, and X ² is the following formula [1-1] to Represents a structure selected from formula [1-5])

[Formula 2]

(W ¹ represents a hydrogen atom or a benzene ring)

(2) The liquid crystal aligning agent according to (1), wherein X ¹ of the formula [1] is an alkylene group having 1 to 10 carbon atoms.

(3) The liquid crystal aligning agent according to the above (1) or (2), wherein X ² of the formula [1] is a structure selected from formulas [1-1], [1-2] and [1-4] .

(4) The liquid crystal according to any one of (1) to (3), wherein the diamine component in the polymer of the component (B) contains at least one diamine compound having a structure represented by the following formula [2]. Orientation treatment agent.

[Formula 3]

(Y represents a substituent of the structure selected from the following formulas [2-1] to [2-6], and m represents an integer of 1 to 4)

[Formula 4]

(a represents the integer of 0-4, b represents the integer of 0-4.

Y ¹ represents a single bond, -(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO-, and Y ² is a single bond or- (CH ₂ ) _b- (b is an integer of 1 to 15) is represented, Y ³ is a single bond, -(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ Represents O-, -COO- or -OCO-, and Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, and Any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom, Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocycle, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms. May be substituted with a fluorine-containing alkyl group of 3, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4, Y ⁶ is an alkyl group having 1 to 18 carbon atoms, containing fluorine having 1 to 18 carbon atoms An alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group,

Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH-, or -NHCO-, and Y ⁸ represents an alkyl group having 8 to 22 carbon atoms.

Y ⁹ and Y ¹⁰ each independently represents a hydrocarbon group having a carbon number of 1 to 12, Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms.)

(5) The liquid crystal aligning agent in any one of said (1)-(4) containing the compound represented by following formula [3] in the tetracarboxylic acid component in the polymer of the said (B) component.

[Formula 5]

(Z ¹ is a group having a structure selected from the following formulas [3a] to [3j])

[Formula 6]

(Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, respectively, and Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and may be the same or different, respectively)

(6) The liquid crystal aligning agent according to any one of (1) to (5), wherein the polymer of the component (B) is a polyimide obtained by dehydrating and cyclizing a polyamic acid.

(7) The liquid crystal aligning agent according to any one of (1) to (6), wherein the component (A) is 0.1 to 30 parts by mass per 100 parts by mass of the component (B).

(8) A liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of said (1)-(7).

(9) A liquid crystal aligning film obtained by an ink jet method using the liquid crystal aligning agent according to any one of (1) to (7) above.

(10) A liquid crystal display device comprising the liquid crystal alignment film according to (8) or (9).

(11) A liquid crystal composition containing a polymerizable compound that has a liquid crystal layer between a pair of substrates with electrodes, and is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and the The liquid crystal alignment film according to (8) or (9), which is used in a liquid crystal display device manufactured by polymerizing the polymerizable compound while applying a voltage between electrodes.

(12) A liquid crystal display device having the liquid crystal alignment film according to (11) above.

(13) A liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates with a liquid crystal layer between the pair of substrates with electrodes, and the electrode The liquid crystal alignment film according to (8) or (9), which is used in a liquid crystal display device manufactured by polymerizing the polymerizable group while applying a voltage therebetween.

(14) A liquid crystal display device comprising the liquid crystal alignment film according to (13) above.

According to the present invention, the liquid crystal alignment treatment agent containing a compound having a specific structure and at least one polymer selected from the group consisting of a polyimide precursor and a polyimide enhances the adhesion between the sealing agent and the liquid crystal alignment film, and provides high temperature and high humidity. Also under the conditions, it is possible to form a liquid crystal alignment film capable of suppressing the occurrence of display unevenness in the vicinity of the frame of the liquid crystal display element and further suppressing a decrease in voltage retention. That is, the liquid crystal display element having a liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention is excellent in reliability, and can be preferably used for a large-screen, high-definition liquid crystal television or the like.

The present invention is a liquid crystal aligning agent containing the following (A) component and (B) component, a liquid crystal aligning film obtained by using the liquid crystal aligning agent, and further, a liquid crystal display element having the liquid crystal aligning film.

(A) Component: A compound represented by the following formula [1] (also referred to as a specific compound).

Component (B): At least one type of polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component (also referred to as a specific polymer).

[Formula 7]

(X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring, and X ² is the following formula [1-1] to Represents a structure selected from formula [1-5])

[Formula 8]

(W ¹ represents a hydrogen atom or a benzene ring).

In the liquid crystal aligning agent of the present invention, the O=C=N-group (also referred to as an isocyanate group) in a specific compound is by heating at the time of producing the liquid crystal aligning agent or the firing step at the time of producing the liquid crystal aligning film, It is thought that it is chemically bonded with a carboxyl group in a specific polymer. Therefore, in spite of the simple means of mixing the liquid crystal aligning agent of this invention in an organic solvent, in the liquid crystal aligning film obtained from it, it thinks that a specific compound and a specific polymer are combining efficiently.

Moreover, it is known that the double bonding site|part of formula [1-1]-formula [1-5] which is X ² in a specific compound reacts by irradiation of heat or ultraviolet rays. Moreover, these double bonding sites are sites also contained in the compound contained in the sealing agent.

Therefore, in the case of using the liquid crystal aligning agent of the present invention, the double bonding site in the liquid crystal aligning film and the compound in the sealing agent are formed by the curing process of the sealing agent when manufacturing a liquid crystal display element, that is, an ultraviolet irradiation process or a firing process. A chemical reaction is carried out, and the sealing agent and the liquid crystal aligning film are chemically bonded to each other, and their adhesiveness can be improved.

From the above point of view, the liquid crystal aligning agent containing the specific compound and the specific polymer of the present invention has high adhesion to the sealing agent, suppresses the occurrence of uneven display in the vicinity of the frame of the liquid crystal display element even under high temperature and high humidity conditions, and further A liquid crystal alignment film capable of suppressing a decrease in voltage retention can be formed.

<Specific compound>

The specific compound of the present invention is a compound represented by the following formula [1].

[Formula 9]

(X ¹ and X ² have the same meaning as defined above, and X ² represents a structure selected from the following formulas [1-1] to [1-5])

[Formula 10]

(W ¹ represents a hydrogen atom or a benzene ring)

In formula [1], X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring. Among these, from the viewpoint of availability and production of the compound, an alkylene group having 1 to 10 carbon atoms is preferable, and more preferably an alkylene group having 1 to 5 carbon atoms.

In Formula [1], X ² is a structure selected from Formula [1-1]-Formula [1-5].

In formula [1-3], W ¹ represents a hydrogen atom or a benzene ring. Among them, a hydrogen atom is preferable.

In Formula [1], X ² is preferably a structure represented by Formula [1-1], Formula [1-2], or Formula [1-4] from the viewpoint of reactivity by irradiation with heat or ultraviolet rays.

More specifically, the structure represented by the following formula [1a]-formula [1d] is mentioned.

[Formula 11]

(X ³ represents an alkylene group having 1 to 5 carbon atoms, a benzene ring or a cyclohexane ring, and X ⁴ represents an alkylene group having 1 to 5 carbon atoms, a benzene ring or a cyclohexane ring)

[Formula 12]

(X ⁵ represents an alkylene group having 1 to 5 carbon atoms, a benzene ring or a cyclohexane ring, and X ⁶ represents an alkylene group having 1 to 5 carbon atoms, a benzene ring or a cyclohexane ring)

<Specific polymer>

The specific polymer which is the component (B) of the present invention is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

The polyimide precursor is a structure represented by the following formula [A].

[Formula 13]

(R ¹ is a tetravalent organic group, R ² is a divalent organic group, A ¹ and A ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and may be the same or different, respectively, and A ³ and A ⁴ Represents a hydrogen atom, a C1-C5 alkyl group or an acetyl group, each may be the same or different, and n represents a positive integer)

As the diamine component, it is a diamine compound having two primary or secondary amino groups in the molecule, and as the tetracarboxylic acid component, a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound , A tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound.

The specific polymer is a repeating unit represented by the following formula [D] because it can be obtained relatively simply by using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] as raw materials. A polyamic acid having the structural formula of or a polyimide obtained by imidating the polyamic acid is preferable.

[Formula 14]

(R ¹ and R ² have the same meaning as defined in formula [A]).

[Formula 15]

(R ¹ and R ² have the same meaning as defined in formula [A]).

In addition, in the polymer of formula [D] obtained above by a conventional synthesis method, an alkyl group having 1 to 8 carbon atoms of A ¹ and A ² represented by formula [A] and A ³ and A ⁴ represented by formula [A] It is also possible to introduce an alkyl group or an acetyl group having 1 to 5 carbon atoms.

<Diamine component>

As the diamine component for producing the specific polymer which is the component (B), a known diamine compound can be used.

Among them, it is preferable to use at least one or more diamine compounds (also referred to as specific diamine compounds) having a structure represented by the following formula [2].

[Formula 16]

(Y represents a substituent of the structure selected from the following formulas [2-1] to [2-6], and m represents an integer of 1 to 4)

[Formula 17]

In formula [2-1], a represents the integer of 0-4. Among them, 0 or 1 is preferable from the viewpoint of availability of raw materials and ease of synthesis.

In formula [2-2], b represents the integer of 0-4. Among them, an integer of 0 or 1 is preferable from the viewpoint of availability of raw materials and ease of synthesis.

In formula [2-3], Y ¹ is a single bond, -(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- Show. Among them, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, -(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- desirable. More preferable ones are a single bond, -(CH ₂ ) _a- (a is an integer of 1 to 10), -O-, -CH ₂ O-, or COO-.

In formula [2-3], Y ² represents a single bond or -(CH ₂ ) _b- (b is an integer of 1 to 15). Especially, a single bond or -(CH ₂ ) _b- (b is an integer of 1 to 10) is preferable.

In formula [2-3], Y ³ is a single bond, -(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- Show. Among them, from the viewpoint of ease of synthesis, a single bond, -(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO- is preferable. More preferable one is a single bond, -(CH ₂ ) _c- (c is an integer of 1 to 10), -O-, -CH ₂ O-, or -COO-.

In formula [2-3], Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a hetero ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms. It may be substituted with an alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. In addition, Y ⁴ may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a steroid skeleton. Among them, from the viewpoint of ease of synthesis, an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton is preferable.

In formula [2-3], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, and any hydrogen atom on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms It may be substituted with an alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Among them, a benzene ring or a cyclohexane ring is preferable.

In formula [2-3], n represents the integer of 0-4. Among them, 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferable thing is 0-2.

In formula [2-3], Y ⁶ represents a C 1 to C 18 alkyl group, a C 1 to C 18 fluorine-containing alkyl group, a C 1 to C 18 alkoxyl group, or a C 1 to C 18 fluorine-containing alkoxyl group. Among them, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, it is a C1-C12 alkyl group or a C1-C12 alkoxyl group. Particularly preferably, they are a C1-C9 alkyl group or a C1-C9 alkoxyl group.

As a preferable combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2-3] for constituting the substituent Y in the formula [2], International Publication WO2011/ The same combinations as (2-1) to (2-629) published in Tables 6 to 47 on pages 13 to 34 of 132751 (published on October 27, 2011) are mentioned. In addition, Y1 ~ Y6 in the respective tables of the International Patent Publication, and by reading the change Y ¹ ~ Y ⁶ of the present invention.

In formula [2-4], Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH-, or -NHCO-. Among them, -O-, -CH ₂ O-, -COO- or -CONH- is preferable. More preferably, they are -O-, -COO-, or -CONH-.

In formula [2-4], Y ⁸ represents an alkyl group having 8 to 22 carbon atoms.

In formula [2-5], Y ⁹ and Y ¹⁰ independently represent a hydrocarbon group having 1 to 12 carbon atoms.

In formula [2-6], Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms.

The method of producing the specific diamine compound represented by formula [2] is not particularly limited, but preferred methods include those shown below.

As an example, the specific diamine compound represented by formula [2] is obtained by synthesizing a dinitro compound represented by the following formula [2-A] and further reducing the nitro group to convert it into an amino group.

[Formula 18]

(Y represents a substituent of the structure selected from the above formulas [2-1] to [2-6], and m represents an integer of 1 to 4)

The method of reducing the dinitro group of the dinitro compound represented by the formula [2-A] is not particularly limited, and is usually palladium in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane, and alcohol-based solvents. There is a method of reacting under hydrogen gas, hydrazine or hydrogen chloride using carbon, platinum oxide, Ranickel, platinum black, rhodium-alumina, platinum sulfide carbon, or the like as a catalyst.

Below, although the specific structure of the specific diamine compound represented by Formula [2] is mentioned, it is not limited to these examples.

As a specific diamine compound, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,4-diaminophenol, In addition to 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, and 4,6-diaminoresorcinol, the following formulas [2-7] to [2-47] The diamine compound of the structure represented by] is mentioned.

[Formula 19]

(A ¹ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group)

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Chemical Formula 29]

[Formula 30]

[Formula 31]

(R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -or -CH ₂ OCO-, and R ² is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine Represents a containing alkoxy group)

[Formula 32]

(R ³ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -or -CH ₂ -, and R ⁴ is an alkyl group having 1 to 22 carbon atoms , An alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group)

[Formula 33]

(R ⁵ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -or -O-, and R ⁶ is a fluorine group, Cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group)

[Formula 34]

(R ⁷ represents an alkyl group having 3 to 12 carbon atoms. In addition, the cis-trans isomer of 1,4-cyclohexylene is preferably a trans isomer, respectively.)

[Formula 35]

(R ⁸ represents an alkyl group having 3 to 12 carbon atoms. The cis-trans isomer of 1,4-cyclohexylene is preferably a trans isomer, respectively.)

[Formula 36]

(B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, B ³ represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and B ² represents an oxygen atom or -COO-* (However, the bond hand given "*" bonds with B ³ ), and B ¹ represents an oxygen atom or -COO-* (however, the bond hand giving "*" bonds with (CH ₂ )a ² In addition, a ¹ represents an integer of 0 or 1, a ² represents an integer of 2 to 10, and a ³ represents an integer of 0 or 1.)

Among the specific diamine compounds represented by the above formula [2], a liquid crystal aligning film was formed using a liquid crystal aligning agent obtained from a specific polymer in which the substituent Y in the formula [2] used a diamine compound having a structure represented by formula [2-3]. In this case, the pretilt angle of the liquid crystal can be increased. In order to increase the pretilt angle, it is preferable to use the diamine compound represented by the formula [2-25] to the formula [2-40] or the formula [2-43] to the formula [2-47] among the diamine compounds. A more preferable thing is a diamine compound represented by Formula [2-29]-Formula [2-40] or Formula [2-43]-Formula [2-47].

It is preferable that the amount of the diamine compound used in order to increase a pretilt angle is 5 mol% or more and 80 mol% or less of the whole diamine component. More preferably, it is 5 mol% or more and 60 mol% of the whole diamine component from the point of the coating property of a liquid crystal aligning agent and electric characteristics as a liquid crystal aligning film.

The specific diamine compound represented by formula [2] is one or two types depending on characteristics such as solubility and coating properties of a specific polymer in a solvent, alignment properties of the liquid crystal in the case of a liquid crystal alignment film, voltage retention, and accumulated charge. The above can be mixed and used.

As the diamine component for producing a specific polymer, diamine compounds (also referred to as other diamine compounds) other than the specific diamine compound represented by formula [2] can be used as the diamine component. Below, although the specific example of another diamine compound is given, it is not limited to these examples.

For example, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 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'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl Ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfo Nyldianiline, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodi Aniline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-dia Minodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N- Methyl(3,4'-diaminodiphenyl)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'-diaminobenzophenone, 2,3'-dia Minobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diamino Naphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)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-aminophenoxy)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)]dianiline, 4,4'-[1 ,3-phenylenebis(methylene)]dianiline, 3,4'-[1,4-phenylenebis(methylene)]dianiline, 3,4'-[1,3-phenylenebis(methylene)] Dianiline, 3,3'-[1,4-phenylenebis(methylene)]dianiline, 3,3'-[1,3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis [(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl)methanone], 1,3 -Phenylenebis[(3-aminophenyl)methanone], 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenyl Renbis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-amino Phenyl) isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene) Bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenz) Amide), N,N'-bis(4-aminophenyl) terephthalamide, N,N'-bis(3-aminophenyl) terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, N ,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylsulfone, 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)hexafluoropropane, 2,2'-ratio S(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-bis(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-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1 ,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-amino Phenoxy) nonane, 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-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane , 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, or 1,12-diaminododecane.

In addition, examples of other diamine compounds include those having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocycle in the diamine side chain, and those having a large-cyclic substituent comprising these groups. Specifically, the diamine compound represented by the following formulas [DA1] to [DA7] can be illustrated.

[Formula 37]

[Formula 38]

[Formula 39]

(A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, and A ² is a C1-C22 linear Or a branched alkyl group or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms)

[Formula 40]

(p represents the integer of 1-10)

As other diamine compounds, as long as the effects of the present invention are not impaired, diamine compounds represented by the following formulas [DA8] to [DA13] can also be used.

[Formula 41]

[Formula 42]

(m represents the integer of 0-3, n represents the integer of 1-5)

Moreover, as long as the effect of this invention is not impaired, the diamine compound represented by the following formula [DA14]-formula [DA17] can also be used.

[Formula 43]

(A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N( Represents CH ₃ )CO-, m ¹ and m ² each represent an integer of 0 to 4, m ¹ + m ² represents an integer of 1 to 4, in formula [DA15], m ³ and m ⁴ Each represents an integer of 1 to 5, and in formula [DA16], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, m ⁵ represents an integer of 1 to 5, and A ³ represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-, m ⁶ represents the integer of 1-4)

Moreover, as another diamine compound, a diamine compound represented by the following formula [DA18] and a formula [DA19] can also be used.

[Formula 44]

Furthermore, as long as the effect of the present invention is not impaired, a diamine compound represented by the following formula [DA20] can also be used.

[Formula 45]

(A ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- and -N(CH ₃ ) A divalent organic group selected from CO-, A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, and A ³ is a single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- and -O(CH ₂ ) _m- (m is an integer of 1 to 5) is a divalent group selected from, A ⁴ is a nitrogen-containing aromatic heterocycle, and n is an integer of 1 to 4)

The other diamine compounds described above are one or two depending on characteristics such as solubility of a specific polymer in a solvent, coating property of a liquid crystal aligning agent, alignment property of a liquid crystal in the case of a liquid crystal aligning film, voltage retention, and accumulated charge. You can also mix and use more than one kind.

<Tetracarboxylic acid component>

As the tetracarboxylic acid component for producing the specific polymer which is the component (B) of the present invention, tetracarboxylic dianhydride represented by the following formula [3], tetracarboxylic acid, and tetracarboxylic acid derivatives thereof It is preferable to use a carboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound (all are collectively referred to as a specific tetracarboxylic acid component).

[Chemical Formula 46]

In formula [3], Z ¹ is a group having a structure selected from the following formulas [3a] to [3j].

[Chemical Formula 47]

The formula ^{[3a], Z 2 ~ Z} 5 is may be a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, respectively, be the same or different.

In formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and may be the same or different, respectively.

In the structure represented by formula [3], which is the specific tetracarboxylic acid component, Z ¹ is the formula [3a], formula [3c], in terms of ease of synthesis and ease of polymerization reactivity when producing a polymer. A structure represented by formula [3d], formula [3e], formula [3f], or formula [3g] is preferable. A more preferable thing is a structure represented by a formula [3a], a formula [3e], a formula [3f], or a formula [3g], and a formula [3e], a formula [3f], or a formula [3g] is especially preferable.

It is preferable that the specific tetracarboxylic acid component is 1 mol% or more in all the tetracarboxylic acid components. A more preferable thing is 5 mol% or more, and a particularly preferable thing is 10 mol% or more. Especially, 15 to 100 mol% is more preferable.

Moreover, when using the specific tetracarboxylic acid component of the structure of Formula [3e], Formula [3f], or Formula [3g], it is preferable to make the use amount into 20 mol% or more of the whole tetracarboxylic acid component . More preferably, it is 30 mol% or more. Moreover, all of the tetracarboxylic acid components may be a tetracarboxylic acid component of the structure of Formula [3e], Formula [3f], or Formula [3g].

In the specific polymer, other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used as long as the effect of the present invention is not impaired.

As other tetracarboxylic acid components, tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, or tetracarboxylic acid dialkyl ester dihalide compounds shown below Can be mentioned.

That is, as other tetracarboxylic acid components, pyromellitic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 1,4,5, 8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid Acid, 2,3,3',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis( 3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3- Hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylsilane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3 ,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9 , 10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

The specific tetracarboxylic acid component and other tetracarboxylic acid components are the solubility of the specific polymer of the present invention in the solvent, the coating property of the liquid crystal aligning agent, the alignment of the liquid crystal in the case of a liquid crystal aligning film, the voltage retention, and the accumulation Depending on characteristics such as electric charge, one type or two or more types may be used in combination.

<Method for producing a specific polymer>

The method of synthesizing a specific polymer is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic acid component. In general, polyamic acid is obtained by reacting at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acid and its derivatives with a diamine component comprising one or more diamine compounds. Specifically, there are the following methods.

(1) A method of obtaining polyamic acid by polycondensing a tetracarboxylic dianhydride and a primary or secondary diamine compound.

(2) A method of obtaining polyamic acid by subjecting a tetracarboxylic acid and a primary or secondary diamine compound to a dehydration polycondensation reaction.

(3) A method of polycondensing a tetracarboxylic acid dihalide and a primary or secondary diamine compound to obtain a polyamic acid.

In order to obtain an alkyl polyamic acid ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterification of a carboxylic acid group and a primary or secondary diamine compound, a tetracarboxylic acid dihalide obtained by dialkyl esterification of a carboxylic acid group And a method of polycondensing a primary or secondary diamine compound, or a method of converting the carboxyl group of a polyamic acid into an ester.

In order to obtain a polyimide, a method of cyclizing the polyamic acid or polyamic acid alkyl ester to form a polyimide is used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent containing a diamine component and a tetracarboxylic acid component. The organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Below, although the specific example of the organic solvent used for reaction is given, it is not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or And 1,3-dimethyl-imidazolidinone.

Moreover, when the solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D-1]-formula [ The solvent represented by D-3] can be used.

[Formula 48]

(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 may be used individually or may be mixed and used. Moreover, even if it is a solvent which does not melt|dissolve a polyimide precursor, you may mix and use with the said solvent in the range in which the produced|generated polyimide precursor does not precipitate. Moreover, since moisture in an organic solvent inhibits a polymerization reaction and furthermore causes hydrolysis of the produced polyimide precursor, it is preferable to use a dehydration-dried organic solvent.

When making a diamine component and a tetracarboxylic acid component react in an organic solvent, although there exist the following methods, for example, any method may be used.

(1) A method in which a solution obtained by dispersing or dissolving a diamine component in an organic solvent is stirred to add the tetracarboxylic acid component as it is or by dispersing or dissolving it in an organic solvent.

(2) Conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent.

(3) A method of adding a diamine component and a tetracarboxylic acid component alternately.

In the case of reacting using a plurality of diamine components or tetracarboxylic acid components, respectively, the reaction may be carried out in a premixed state, or may be individually sequentially reacted, or individually reacted low molecular weight substances are mixed and reacted to form a polymer. You can do it. The polymerization temperature in that case can select an arbitrary temperature of -20 to 150°C, but is preferably in the range of -5 to 100°C. Further, the reaction can be carried out at an arbitrary concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial reaction is carried out at a high concentration, and then, an organic solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component and the total number of moles of the tetracarboxylic acid component is preferably from 0.8 to 1.2. Similar to the normal polycondensation reaction, the closer this molar ratio is to 1.0, the greater the molecular weight of the resulting polyimide precursor.

The polyimide of the present invention is a polyimide obtained by cyclizing the above polyimide precursor, and in this polyimide, the cyclization rate of the amic acid group (also referred to as the imidation rate) is not necessarily 100%. It can be arbitrarily adjusted accordingly.

As a method of imidizing the polyimide precursor, thermal imidation in which the solution of the polyimide precursor is heated as it is, or catalytic imidization in which a catalyst is added to the solution of the polyimide precursor is exemplified.

When the polyimide precursor is thermally imidized in a solution, the temperature is 100 to 400°C, preferably 120 to 250°C, and it is preferable to carry out while removing water generated by the imidation reaction out of the system.

The catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor, and stirring at -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.5 to 30 mole times, preferably 2 to 20 mole times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times of the amic acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has a suitable basicity to advance the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferably used because purification after completion of the reaction becomes easy. The imidation rate by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

When the generated polyimide precursor or polyimide is recovered from the polyimide precursor or the reaction solution of polyimide, the reaction solution may be added to a solvent to precipitate. As a solvent used for precipitation, methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, etc. are mentioned. The polymer injected into the solvent and precipitated may be collected by filtration and then dried at room temperature or heated under normal pressure or reduced pressure. Further, by re-dissolving the polymer recovered by precipitation in an organic solvent and repeating the operation of reprecipitation recovery 2 to 10 times, impurities in the polymer can be reduced.

Examples of the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and when three or more solvents selected from these are used, the efficiency of purification is further increased, and thus it is preferable.

The molecular weight of the specific polymer is 5,000 to 1,000,000 as a weight average molecular weight measured by GPC (Gel Permeation Chromatography) when considering the strength of the liquid crystal alignment film obtained therefrom, workability at the time of forming the liquid crystal alignment film, and coating property. It is preferable, and more preferably, it is 10,000-150,000.

<Liquid crystal orientation treatment agent>

The liquid crystal aligning agent of this invention is a coating solution for forming a liquid crystal aligning film (it is also called a resin film), and is a coating solution for forming a liquid crystal aligning film containing a specific compound, a specific polymer, and a solvent.

Content of a specific compound in a liquid crystal aligning agent is 0.1-30 mass parts with respect to 100 mass parts of a specific polymer. Among them, 0.5 to 30 parts by mass are preferable, and 1 to 20 parts by mass are particularly preferable.

All of the polymer components in the liquid crystal aligning agent may be the specific polymer of the present invention, or other polymers other than that may be mixed. In that case, the content of other polymers is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the specific polymer of the present invention. As another polymer other than that, the diamine compound represented by the said formula [2], and the polyimide type polymer which does not use a specific tetracarboxylic acid component can be mentioned. Furthermore, as a polymer other than that, a cellulose polymer, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, polysiloxane, etc. are mentioned.

From the viewpoint of forming a uniform liquid crystal aligning film by application, the solvent in the liquid crystal aligning agent is preferably 70 to 99.9 mass%, and more preferably 80 to 99 mass% of the solvent in the liquid crystal aligning agent. This content can be appropriately changed according to the film thickness of the target liquid crystal aligning film.

The solvent used for the liquid crystal aligning agent is not particularly limited as long as it is a solvent (also referred to as a good solvent) for dissolving a specific compound and a specific polymer. Below, although a specific example of a good solvent is given, it is not limited to these examples.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone. Furthermore, when the solubility of a specific compound and a specific polymer in a solvent is high, it is preferable to use a solvent represented by the above formulas [D-1] to [D-3].

It is preferable that the good solvent in a liquid crystal aligning agent is 10-100 mass% of the whole solvent contained in a liquid crystal aligning agent. Especially, 20 to 90 mass% is preferable. A more preferable thing is 30 to 80 mass %.

As the liquid crystal aligning agent, as long as the effect of the present invention is not impaired, a solvent (also referred to as a poor solvent) that improves the coating properties and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied can be used. Below, although a specific example of a poor solvent is given, 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, 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, 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, diethylene glycol methyl ethyl 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, 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, propylene glycol monobutyl ether, 1-(butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl 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 monoacetate Ethyl ether acetate, diethylene glycol monobutyl ether Leacetate, 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, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy Toxoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionate butyl, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, the above formula [D-1] -A solvent represented by formula [D-3], etc. are mentioned.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanedol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, or the above-described formula [D-1] to It is preferable to use the solvent represented by formula [D-3].

It is preferable that these poor solvents are 1 to 70 mass% of the whole solvent contained in a liquid crystal aligning agent. Especially, 1 to 60 mass% is preferable. More preferably, it is 5 to 60 mass %.

The liquid crystal aligning agent is at least one selected from the group consisting of a compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group, as long as the effect of the present invention is not impaired. A compound having a substituent of, and furthermore, a compound having a polymerizable unsaturated bond (collectively, also referred to as a crosslinkable compound) may be introduced. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.

As a crosslinkable compound having an epoxy group or an isocyanate group, for example, bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene , Tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyletherethane, triphenylglycidyletherethane, bisphenolhexafluoroacet Diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis( 2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidylmethaxylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2- (4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane, 1,3-bis(4-(1-(4-(2,3-epoxypro)) Foxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol, and the like.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

[Chemical Formula 49]

Specifically, crosslinkable compounds represented by formulas [4a] to [4k] published on pages 58 to 59 of WO2011/132751 (published on October 27, 2011) can be mentioned.

As a crosslinkable compound having a cyclocarbonate group, it is a crosslinkable compound which has at least two cyclocarbonate groups represented by the following formula [5].

[Formula 50]

Specifically, crosslinkable compounds represented by formulas [5-1] to [5-42] published on pages 76 to 82 of WO2012/014898 (published on February 2, 2012) can be mentioned.

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include, for example, an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, Guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin, and the like. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group or both can be used. This melamine derivative or benzoguanamine derivative may exist as a dimer or a trimer. It is preferable that these have an average of 3 or more and 6 or less of methylol groups or alkoxymethyl groups per one triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750 in which an average of 3.7 methoxymethyl groups per triazine ring is substituted, and MW in which an average of 5.8 methoxymethyl groups per triazine ring is substituted. -30 (above, manufactured by Sanwa Chemical) or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamine, Cymel 235, 236, 238, 212, 253 , Methoxymethylated butoxymethylated melamine such as 254, butoxymethylated melamine such as Cymel 506, 508, methoxymethylated isobutoxymethylated melamine containing carboxyl groups such as Cymel 1141, methoxymethylated ethoxymethylated such as Cymel 1123 Benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, and methoxymethylated ethoxymethylated benzoguanamine containing carboxyl groups such as Cymel 1125-80 Namin (above, manufactured by Mitsui cyanamide) is mentioned. Further, examples of the glycoluril include butoxymethylolated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powder Link 1174.

As a benzene or phenolic compound having a hydroxyl group or an alkoxyl group, for example, 1,3,5-tris(methoxymethyl)benzene, 1,2,4-tris(isopropoxymethyl)benzene, 1,4-bis(sec-butoxymethyl)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, etc. are mentioned.

More specifically, crosslinkable compounds represented by formulas [6-1] to [6-48] published on pages 62 to 66 of WO2011/132751 (published on October 27, 2011) can be mentioned.

As a crosslinkable compound having a polymerizable unsaturated bond, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, tri(meth)acrylate ) Crosslinkable compounds having three polymerizable unsaturated groups in a molecule such as acryloyloxyethoxytrimethylolpropane and glycerin polyglycidyl ether poly(meth)acrylate; Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol Di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, glycerindi(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol digly Crosslinkable compounds having two polymerizable unsaturated groups in the molecule, such as cidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, and hydroxypivalate neopentyl glycol di(meth)acrylate ; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2 -(Meth)acryloyloxy-2-hydroxypropylphthalate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono(meth)acrylate, 2-(meth)acryloyloxyethylphosphoric acid Crosslinkable compounds having one polymerizable unsaturated group in a molecule such as ester or N-methylol (meth)acrylamide; And the like.

Moreover, a compound represented by the following formula [7] can also be used.

[Formula 51]

(E ₁ represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring, and E ₂ is Represents a group selected from formula [7a] and formula [7b], and n represents an integer of 1 to 4)

[Formula 52]

The compound is an example of a crosslinkable compound, and is not limited thereto. Moreover, the crosslinkable compound used for the liquid crystal aligning agent of this invention may be 1 type, and may combine 2 or more types.

It is preferable that content of a crosslinkable compound in a liquid-crystal aligning agent is 0.1-150 mass parts with respect to 100 mass parts of all polymer components. In order to allow the crosslinking reaction to proceed to exhibit the desired effect, 0.1 to 100 parts by mass is more preferable, and in particular, 1 to 50 parts by mass is most preferable based on 100 parts by mass of all polymer components.

The liquid crystal aligning agent can use a compound which improves the uniformity of the film thickness and the surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied, as long as the effect of the present invention is not impaired.

As a compound which improves the uniformity of the film thickness and surface smoothness of a liquid crystal aligning film, a fluorine-type surfactant, a silicone-type surfactant, a nonionic surfactant, etc. are mentioned.

More specifically, for example, Ftop EF301, EF303, EF352 (above, manufactured by Tochem Products), Megapac F171, F173, R-30 (above, manufactured by Dai Nippon Ink), Florade FC430, FC431 ( As described above, Sumitomo 3M), Asahigard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass), and the like are mentioned. The ratio of use of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all polymer components contained in the liquid crystal aligning agent.

In addition, in the liquid crystal aligning agent, as a compound which promotes charge transfer in the liquid crystal aligning film to accelerate charge dropout of the device, the formula [M1] published on pages 69 to 73 of WO2011/132751 (published on October 27, 2011) You can also add a nitrogen-containing heterocyclic amine compound represented by-Formula [M156]. Although this amine compound may be added directly to a liquid crystal aligning agent, it is preferable to add after setting it as a solution of concentration 0.1-10 mass %, Preferably it is 1-7 mass% with a suitable solvent. The solvent to be used is not particularly limited as long as it is an organic solvent in which the specific polymer described above is dissolved.

In addition to the above poor solvent, a crosslinkable compound, a compound that improves the uniformity or surface smoothness of the film thickness of a resin film or a liquid crystal alignment film, and a compound that promotes charge dropout, the effect of the present invention is not impaired. Within the range, a dielectric material or a conductive material for the purpose of changing electrical properties such as dielectric constant and conductivity of the liquid crystal alignment film may be added.

<Liquid crystal alignment film/liquid crystal display element>

The liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film by performing alignment treatment by rubbing treatment or light irradiation after applying and firing on a substrate. Moreover, in the case of a vertical alignment use etc., it can be used as a liquid crystal aligning film without alignment treatment. The substrate used at this time is not particularly limited as long as it is a substrate having high transparency, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate and a polycarbonate substrate may be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed. In addition, in a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used as long as only one substrate is used, and a material that reflects light such as aluminum can also be used as an electrode in this case.

The application method of the liquid crystal aligning agent is not particularly limited, but industrially, screen printing, offset printing, flexo printing, ink jet method, and the like are common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, a spray method, and the like, and may be used depending on the purpose.

After applying the liquid crystal aligning agent on the substrate, by a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared ray) type oven, depending on the solvent used for the liquid crystal aligning agent, 30 to 300° C., preferably Can be set as a liquid crystal aligning film by evaporating the solvent at a temperature of 30 to 250°C. If the thickness of the liquid crystal aligning film after firing is too thick, it becomes 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 be lowered. Therefore, preferably 5 to 300 nm, more preferably 10 It is-100 nm. When the liquid crystal is horizontally aligned or obliquely aligned, the sintered liquid crystal alignment film is subjected to rubbing, polarized ultraviolet irradiation, or the like.

In the liquid crystal display device of the present invention, after obtaining a substrate with a liquid crystal aligning film from the liquid crystal aligning agent of the present invention by the above-described method, a liquid crystal cell is produced by a known method to obtain a liquid crystal display device.

As a manufacturing method of a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film was formed is prepared, a spacer is scattered on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inner side, and the other substrate is bonded together (貼合), and a method of sealing by injecting a liquid crystal under reduced pressure, or a method of attaching and sealing a substrate after dropping the liquid crystal on the liquid crystal alignment film surface scattered with spacers.

Further, the liquid crystal aligning agent of the present invention comprises a liquid crystal layer between a pair of substrates with electrodes, and contains a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured by polymerizing a polymerizable compound by at least one of irradiation and heating of an active energy ray while disposing a liquid crystal composition to be formed and applying a voltage between the electrodes. Here, as the active energy ray, ultraviolet rays are preferable. As ultraviolet rays, the wavelength is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120°C, preferably 60 to 80°C. In addition, ultraviolet rays and heating may be performed simultaneously.

The above-described liquid crystal display device controls the pretilt angle of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA system, a small amount of a photopolymerizable compound, such as a photopolymerizable monomer, is mixed in a liquid crystal material, and after assembling a liquid crystal cell, UV light is applied to the photopolymerizable compound while a predetermined voltage is applied to the liquid crystal layer. Etc. are irradiated, and the pretilt angle of the liquid crystal molecules is controlled by the resulting polymer. That is, since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after removing the voltage, the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. Moreover, since the PSA system does not require rubbing treatment, it is suitable for formation of a vertically aligned liquid crystal layer in which it is difficult to control the pretilt angle by rubbing treatment.

In the liquid crystal display device of the present invention, after obtaining a substrate with a liquid crystal aligning film from a liquid crystal aligning agent by the above-described method, a liquid crystal cell is prepared, and a polymerizable compound is polymerized by at least one of irradiation with ultraviolet rays and heating. , It is possible to control the alignment of liquid crystal molecules.

To give an example of manufacturing a PSA type liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is inside, and the other substrate is A method of bonding and sealing by injecting a liquid crystal under reduced pressure, and a method of bonding and sealing a substrate after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacers are scattered are mentioned.

The liquid crystal is mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation. Examples of the polymerizable compound include compounds having one or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in a molecule. In that case, the polymerizable compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component. If the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize and the orientation of the liquid crystal cannot be controlled. Is lowered.

After manufacturing the liquid crystal cell, the polymerizable compound is polymerized by irradiation with heat or ultraviolet rays while applying an alternating current or direct current voltage to the liquid crystal cell. Thereby, the orientation of liquid crystal molecules can be controlled.

In addition, the liquid crystal aligning agent of the present invention comprises a liquid crystal layer between a pair of substrates with electrodes, and contains a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured through a step of disposing a liquid crystal aligning film and applying a voltage between the electrodes. Here, as the active energy ray, ultraviolet rays are preferable. As ultraviolet rays, the wavelength is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120°C, preferably 60 to 80°C. In addition, ultraviolet rays and heating may be performed simultaneously.

In order to obtain a liquid crystal aligning film containing a polymerizable group polymerized by at least one of active energy rays and heat, a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent, or a method of using a polymer component containing a polymerizable group Can be mentioned.

Since the liquid crystal aligning agent of the present invention contains a specific compound having a double bonding site that reacts by irradiation with heat or ultraviolet rays, the orientation of the liquid crystal molecules can be controlled by at least one of irradiation and heating with ultraviolet rays. have.

The production of a liquid crystal cell having a liquid crystal alignment film containing such a polymerizable group, and control of the alignment of the liquid crystal molecules after production of the liquid crystal cell are performed in the same manner as in the above-described PSA liquid crystal cell.

A liquid crystal display element having a liquid crystal aligning film produced by using the liquid crystal aligning agent of the present invention is excellent in reliability, and can be preferably used for a large-screen and high-definition liquid crystal television.

Example

Hereinafter, although an Example is given and this invention is demonstrated in more detail, it is limited to these and is not interpreted.

"Abbreviations of compounds used in Synthesis Examples, Examples and Comparative Examples"

<Specific compound>

P1: compound represented by the following formula [P1]

P2: compound represented by the following formula [P2]

P3: Compound represented by the following formula [P3]

[Formula 53]

<Monomer for producing polyimide polymer (specific polymer)>

(Specific diamine compound)

A1: 3,5-diaminobenzoic acid

A2: Diamine compound represented by the following formula [A2]

A3: 1,3-diamino-4-octadecyloxybenzene

A4: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene

A5: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxymethyl]benzene

A6: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene

A7: Diamine compound represented by the following formula [A7]

[Chemical Formula 54]

[Chemical Formula 55]

[Formula 56]

(Other diamine compounds)

B1: p-phenylenediamine

B2: m-phenylenediamine

[Chemical Formula 57]

(Specific tetracarboxylic acid component)

C1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

C2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

C3: Tetracarboxylic dianhydride represented by the following formula [C3]

C4: Tetracarboxylic dianhydride represented by the following formula [C4]

[Chemical Formula 58]

<solvent>

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

ECS: Ethylene glycol monoethyl ether

EC: Diethylene glycol monoethyl ether

BCS: Ethylene glycol monobutyl ether

PB: Propylene glycol monobutyl ether

"Measurement method of molecular weight of polyimide polymer"

The molecular weight of the polyimide precursor and the polyimide is determined by using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (made by Showa Electric Corporation) and a column (KD-803, KD-805) (manufactured by Shodex). , Was measured as follows.

Column temperature: 50 °C

Eluent: N,N'-dimethylformamide (as additive, lithium bromide-hydrate (LiBrH ₂ O) is 30 mmol/L (liter), phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L , Tetrahydrofuran (THF) is 10 ml/ℓ)

Flow rate: 1.0 ml/min

Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratories).

"Measurement method of imidation ratio of polyimide"

20 mg of the polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific)), and deuterated dimethylsulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) was mixed Product) (0.53 ml) was added, and ultrasonic waves were added to dissolve completely. The 500 MHz proton NMR was measured for this solution with an NMR analyzer (JNW-ECA500) (made by Nippon Electronics Datum). For the imidation rate, the proton derived from a structure that does not change before and after imidation is determined as a reference proton, and the integrated peak value of this proton and the integrated value of the proton peak derived from the NH group of the amic acid appearing around 9.5 to 10.0 ppm It was calculated|required by the following formula using.

Imidation rate (%) = (1-α·x/y) × 100

In the above formula, x is the integrated value of the proton peak derived from the NH group of the amic acid, y is the integrated value of the peak of the reference proton, and α is the NH of the amic acid in the case of polyamic acid (imidation ratio is 0%). It is the ratio of the number of reference protons to 1 group proton.

<Synthesis Example 1>

C1 (3.45 g, 17.6 mmol), A2 (0.73 g, 3.57 mmol) and B1 (1.54 g, 14.3 mmol) were mixed in NMP (17.2 g), reacted at 40° C. for 8 hours, and resin solid content concentration A 25 mass% polyamic acid solution (1) was obtained. The number average molecular weight of this polyamic acid was 26,600, and the weight average molecular weight was 85,200.

<Synthesis Example 2>

C2 (3.83 g, 15.3 mmol), A2 (0.93 g, 4.59 mmol) and B2 (2.81 g, 26.0 mmol) were mixed in NEP (21.0 g), and reacted at 50° C. for 2 hours. Then, C1 (2.91 g, 14.8 mmol) and NEP (10.5 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25% by mass. The number average molecular weight of this polyamic acid was 24,500, and the weight average molecular weight was 71,100.

<Synthesis Example 3>

To the polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 2, NEP was added and diluted to 6% by mass, and then acetic anhydride (3.95 g) and pyridine (2.45 g) were added as an imidation catalyst, It was made to react at 70 degreeC for 3 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (3). The imidation ratio of this polyimide was 70 %, the number average molecular weight was 22,100 and the weight average molecular weight was 60,100.

<Synthesis Example 4>

C2 (4.47 g, 17.9 mmol), A1 (1.95 g, 12.8 mmol) and A4 (4.85 g, 12.8 mmol) were mixed in NEP (25.4 g), and reacted at 80°C for 5 hours. Then, C1 (1.43 g, 7.30 mmol) and NEP (12.7 g) were added and reacted at 40° C. for 8 hours to obtain a polyamic acid solution (4) having a resin solid content concentration of 25% by mass. The number average molecular weight of this polyamic acid was 23,500, and the weight average molecular weight was 68,600.

<Synthesis Example 5>

To the polyamic acid solution (4) (30.2 g) obtained in Synthesis Example 4, NEP was added and diluted to 6% by mass, and then acetic anhydride (3.80 g) and pyridine (2.40 g) were added as an imidation catalyst. It was made to react at 70 degreeC for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (5). The imidation ratio of this polyimide was 61 %, the number average molecular weight was 19,900 and the weight average molecular weight was 57,100.

<Synthesis Example 6>

C2 (5.10 g, 20.4 mmol), A1 (1.94 g, 12.8 mmol), A2 (0.52 g, 2.55 mmol) and A5 (4.02 g, 10.2 mmol) were mixed in NMP (25.0 g), and 80 It was made to react at degreeC for 5 hours. Then, C1 (0.93 g, 4.80 mmol) and NMP (12.5 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NMP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (4.54 g) and pyridine (3.33 g) were added as an imidation catalyst, and reacted at 80°C for 3.5 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (6). The imidation ratio of this polyimide was 85 %, the number average molecular weight was 16,800 and the weight average molecular weight was 50,100.

<Synthesis Example 7>

C2 (2.42 g, 9.69 mmol), A1 (2.58 g, 17.0 mmol) and A6 (3.14 g, 7.27 mmol) were mixed in NEP (21.9 g), reacted at 80° C. for 5 hours, and then C1 ( 2.79 g, 14.2 mmol) and NEP (10.9 g) were added and reacted at 40°C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NEP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (4.40 g) and pyridine (3.25 g) were added as an imidation catalyst, and reacted at 80°C for 3 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (7). The imidation ratio of this polyimide was 81 %, the number average molecular weight was 17,400 and the weight average molecular weight was 52,800.

<Synthesis Example 8>

C2 (4.32 g, 17.3 mmol), A1 (3.00 g, 19.7 mmol) and A7 (2.43 g, 4.93 mmol) were mixed in NMP (22.2 g), and reacted at 80°C for 5 hours. Then, C1 (1.37 g, 7.00 mmol) and NMP (11.1 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NMP was added to the obtained polyamic acid solution (30.5 g) and diluted to 6% by mass, acetic anhydride (3.90 g) and pyridine (2.55 g) were added as an imidation catalyst, and reacted at 60°C for 3 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (8). The imidation ratio of this polyimide was 53 %, the number average molecular weight was 16,500 and the weight average molecular weight was 51,800.

<Synthesis Example 9>

C3 (5.40 g, 24.1 mmol), A1 (2.43 g, 15.9 mmol), A2 (0.50 g, 2.45 mmol) and A7 (3.02 g, 6.13 mmol) were mixed in NMP (34.1 g), and 40 The reaction was carried out at°C for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NMP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (4.05 g) and pyridine (2.50 g) were added as an imidation catalyst, and reacted at 60°C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (9). The imidation ratio of this polyimide was 55 %, the number average molecular weight was 16,100 and the weight average molecular weight was 48,100.

<Synthesis Example 10>

C3 (5.38 g, 24.0 mmol), A1 (2.22 g, 14.6 mmol) and A5 (3.84 g, 9.72 mmol) were mixed in NMP (34.3 g), reacted at 40° C. for 8 hours, and resin solid content concentration A polyamic acid solution of 25% by mass was obtained.

After NMP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (4.00 g) and pyridine (2.50 g) were added as an imidation catalyst, and reacted at 70°C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (10). The imidation ratio of this polyimide was 61 %, the number average molecular weight was 17,300 and the weight average molecular weight was 51,100.

<Synthesis Example 11>

C4 (3.48 g, 11.6 mmol), A1 (1.06 g, 6.95 mmol), A2 (0.94 g, 4.63 mmol) and A3 (4.36 g, 11.6 mmol) were mixed in NEP (24.1 g), and 40 It was made to react at degreeC for 6 hours. Then, C1 (2.20 g, 11.2 mmol) and NEP (12.0 g) were added and reacted at 25° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NEP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (7.20 g) and pyridine (2.30 g) were added as an imidation catalyst, followed by reaction at 40°C for 1.5 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (11). The imidation ratio of this polyimide was 70 %, the number average molecular weight was 17,500 and the weight average molecular weight was 40,100.

The polyimide polymer is put together and shown in Table 1.

"Evaluation of inkjet coating properties of liquid crystal orientation treatment agent"

The liquid crystal aligning agent was pressure-filtered with a membrane filter having a pore diameter of 1 µm, and the inkjet coatability was evaluated. HIS-200 (manufactured by Hitachi Plant Technology) was used for the inkjet applicator. Coating was performed on an ITO (indium tin oxide) evaporated substrate washed with pure water and IPA (isopropyl alcohol), with a coating area of 70 × 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, and a coating speed of 40. Mm/sec, time from application to pre-drying was 60 seconds, and pre-drying was performed on a hot plate at 70°C for 5 minutes.

The film properties of the substrate with the obtained liquid crystal alignment film were confirmed. Specifically, the coating film was visually observed under a sodium lamp to confirm the presence or absence of pinholes. As a result, in the liquid crystal alignment films obtained in all examples, no pinhole was observed on the coating film, and a liquid crystal alignment film excellent in coating properties was obtained.

"Evaluation of display non-uniformity characteristics near the frame of a liquid crystal cell after storage at high temperature and humidity (normal cell)"

The liquid crystal aligning agent was pressure-filtered with a membrane filter having a pore diameter of 1 µm, and production (normal cell) of a liquid crystal cell was performed. This solution was spin-coated on the ITO side of a substrate (100 mm long × 100 mm wide, 0.7 mm thick) with a 100 × 100 mm ITO electrode washed with pure water and IPA, and then on a hot plate at 100° C. for 5 minutes, It heat-processed at 230 degreeC for 30 minutes in a heat circulation type clean oven, and the ITO board|substrate with the polyimide liquid crystal aligning film of 100 nm thickness was obtained. The coated surface of this ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm, with a roll rotation speed of 1000 rpm, a roll advance speed of 50 mm/sec, and a press fit of 0.1 mm.

Two ITO substrates with the obtained liquid crystal alignment film were prepared, and a 6 µm spacer was scattered on the surface of the liquid crystal alignment film of the substrate with one liquid crystal alignment film. Thereafter, an ultraviolet curable sealing agent was drawn around the substrate, and a liquid crystal was injected by the ODF (One Drop Filling) method to obtain a liquid crystal cell. Thereafter, in order to cure the UV-curable sealing agent, a metal halide lamp having an illuminance of 60 mW was used in this liquid crystal cell, and a wavelength of 310 nm or less was cut, and UV rays of 5 J/cm 2 were irradiated in terms of 365 nm. I did. Then, it heat-processed for 60 minutes at 120 degreeC in a heat circulation type clean oven, and the liquid crystal cell (normal cell) was obtained.

In addition, in a liquid crystal cell using the liquid crystal aligning agents (1) to (3) obtained in Examples 1-3 and the liquid crystal aligning agents (21) to (22) obtained in Comparative Examples 1-2, as a liquid crystal, a nematic liquid crystal ( MLC-2003) (made by Merck Japan) was used.

Moreover, in the liquid crystal aligning agent (4)-(6) obtained in Examples 4-6, the liquid-crystal aligning agent (8) obtained in Example 8, the liquid-crystal aligning agent (9) obtained in Example 9, Examples 11-15 Using the obtained liquid-crystal aligning agent (11)-(15), the liquid-crystal aligning agent (17)-(20) obtained in Examples 17-20, and the liquid-crystal aligning agent (23)-(24) obtained in Comparative Examples 3-4 In the liquid crystal cell, a nematic liquid crystal (MLC-6608) (made by Merck Japan) was used as a liquid crystal.

The obtained liquid crystal cell (normal cell) was evaluated by visual observation using a polarizing plate and a backlight, and the liquid crystal alignment property in the vicinity of the sealing agent was evaluated. As a result, uniform liquid crystal alignment was shown in all the liquid crystal cells obtained in Examples and Comparative Examples.

Thereafter, the liquid crystal cell was stored in a high-temperature, high-humidity tank at a temperature of 80°C and a humidity of 90% RH for 36 hours, and the liquid crystal alignment property near the sealing agent was evaluated under the same conditions as above. Specifically, it was considered that this evaluation was excellent as the disorder of liquid crystal orientation was not observed near the sealing agent.

In Tables 5 to 7, the thing in which the disorder in liquid crystal alignment was not seen was made "○", and the thing in which the disorder in liquid crystal alignment was observed was made into "x".

``Evaluation of voltage retention after storage at high temperature and humidity (normal cell)''

The liquid crystal aligning agent was pressure-filtered with a membrane filter having a pore diameter of 1 µm, and production (normal cell) of a liquid crystal cell was performed. This solution was spin-coated on the ITO side of a substrate (40 mm in length × 30 mm in width, 0.7 mm in thickness) with a 30 × 40 mm ITO electrode washed with pure water and IPA, and then on a hot plate at 100° C. for 5 minutes, It heat-processed at 230 degreeC for 30 minutes in a heat circulation type clean oven, and the ITO board|substrate with the polyimide liquid crystal aligning film of 100 nm thickness was obtained. The coated surface of this ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm, with a roll rotation speed of 1000 rpm, a roll advance speed of 50 mm/sec, and a press fit of 0.1 mm.

Two ITO substrates with the obtained liquid crystal aligning film were prepared, the liquid crystal aligning film surface was made inside, and it combined with a 6 micrometers spacer in between, and the ultraviolet curable sealing agent was printed. Subsequently, after bonding by making the other board|substrate and the liquid crystal aligning film surface face-to-face, the process for hardening an ultraviolet-curable sealing agent was performed, and the empty cell was obtained. Specifically, using a metal halide lamp having an illuminance of 60 mW, a wavelength of 310 nm or less was cut, irradiated with ultraviolet rays of 5 J/cm 2 in terms of 365 nm, and thereafter, at 120°C in a thermal cycle clean oven Heat treatment was performed for 60 minutes to obtain an empty cell. Liquid crystal was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell (normal cell).

In addition, the liquid crystal used for the manufacture of the liquid crystal cells of each Example and the comparative example was made the same as the above-mentioned "evaluation of the display non-uniformity characteristic near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)".

To the obtained liquid crystal cell, a voltage of 1 V was applied for 60 µs at a temperature of 80°C, and the voltage after 50 ms was measured, and how much the voltage was maintained was calculated as a voltage retention rate (also referred to as VHR). In addition, measurement was performed with the setting of Voltage: ±1 V, Pulse Width: 60 μs, and Flame Period: 50 ms using a voltage retention rate measuring device (VHR-1) (manufactured by Toyo Technica).

In addition, the liquid crystal cell after the measurement of the voltage retention was stored in a high-temperature, high-humidity bath at a temperature of 80°C and a humidity of 90% RH for 48 hours, and the voltage retention was measured again under the same conditions as above.

The evaluation was made better as the value of the voltage retention rate immediately after the liquid crystal cell is manufactured is less decreased in the value of the voltage retention rate after storage in a high-temperature, high-humidity tank (Tables 5 to 7).

"Production of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)"

The liquid crystal aligning agent was pressure-filtered with a membrane filter having a pore diameter of 1 µm, and the production of a liquid crystal cell and evaluation of liquid crystal orientation (PSA cell) were performed. This solution was cleaned with pure water and IPA, and a substrate with an ITO electrode with a pattern spacing of 20 µm of 10 × 10 mm (40 mm in length × 30 mm in width, 0.7 mm in thickness) and 10 × 40 mm in ITO in the center Spin coat on the ITO surface of the electrode-attached substrate (40 mm in length x 30 mm in width, 0.7 mm in thickness), heat treatment at 100°C for 5 minutes on a hot plate, and heat treatment at 230°C for 30 minutes in a thermal cycle clean oven. A polyimide coating film having a film thickness of 100 nm was obtained.

The substrate to which the liquid crystal alignment film was attached was combined with the liquid crystal alignment film surface as the inner side, sandwiched between 6 µm spacers, and bonded to the periphery with a sealing agent to produce an empty cell. A liquid crystal mixture obtained by mixing 0.3% by mass of a polymerizable compound (1) represented by the following formula into this empty cell by a vacuum injection method with respect to 100% by mass of nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) Was injected, the injection port was sealed, and a liquid crystal cell was obtained.

[Chemical Formula 59]

To the obtained liquid crystal cell, using a metal halide lamp having an illuminance of 60 mW while applying a voltage of 5 V of alternating current, a wavelength of 350 nm or less was cut, and irradiation with UV rays of 20 J/cm 2 in terms of 365 nm was performed, and liquid crystal The liquid crystal cell (PSA cell) in which the orientation direction of was controlled was obtained. When the liquid crystal cell was irradiated with ultraviolet rays, the temperature in the irradiation device was 50°C.

The response speed of the liquid crystal before ultraviolet irradiation of this liquid crystal cell and after ultraviolet irradiation was measured. The response speed measured T90 → T10 from 90% transmittance to 10% transmittance.

In the PSA cell obtained in Examples, it was confirmed that the orientation direction of the liquid crystal was controlled because the response speed of the liquid crystal cell after ultraviolet irradiation became faster than the liquid crystal cell before ultraviolet irradiation. In addition, in all liquid crystal cells, it was confirmed that the liquid crystal was uniformly oriented by observation with a polarization microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation).

<Example 1>

NMP (19.9 g) and BCS (11.8 g) were added to the polyamic acid solution (1) (10.0 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1, followed by stirring at 25°C for 2 hours. After that, P2 (0.25 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (1). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (1), "evaluation of the display non-uniformity characteristic near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (usual cell)" were performed. .

<Example 2>

NEP (18.9 g) and PB (14.4 g) were added to the polyamic acid solution (2) (10.5 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2, followed by stirring at 25°C for 2 hours. Then, P2 (0.18 g) was added, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (2). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (2), "evaluation of the display non-uniformity characteristic near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" were performed. .

<Example 3>

To the polyimide powder (3) (1.55 g) obtained in Synthesis Example 3, NEP (17.0 g) and PB (7.30 g) were added, followed by stirring at 70°C for 24 hours to dissolve. After that, P2 (0.11 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (3). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (3), "evaluation of the display non-uniformity characteristic near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (usual cell)" were performed. .

<Example 4>

To the polyamic acid solution (4) (11.0 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 4, NEP (19.8 g) and PB (15.1 g) were added, followed by stirring at 25°C for 2 hours. Then, P2 (0.19 g) was added, and it stirred at 60 degreeC for 6 hours, and the liquid-crystal aligning agent (4) was obtained. Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (4), "evaluation of the display non-uniformity characteristic near the frame of a liquid crystal cell after high temperature high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature high humidity storage (normal cell)" were performed. .

<Example 5>

To the polyamic acid solution (4) (11.0 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 4, NEP (17.6 g), EC (4.30 g) and PB (12.9 g) were added, and 2 at 25°C. Stirred for hours. Then, P1 (0.41 g) was added, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (5). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (5), "evaluation of display non-uniformity characteristics near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" were performed. .

<Example 6>

To the polyimide powder (5) (1.50 g) obtained in Synthesis Example 5, NEP (15.3 g) and PB (8.20 g) were added, followed by stirring at 70°C for 24 hours to dissolve. After that, P2 (0.11 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (6). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid crystal aligning agent (6), "evaluation of display non-uniformity characteristics near the frame of liquid crystal cell after high temperature and high humidity storage (normal cell)", "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" and "liquid crystal Production of a cell and evaluation of liquid crystal orientation (PSA cell)" were performed.

<Example 7>

To the polyimide powder (5) (1.10 g) obtained in Synthesis Example 5, NEP (23.1 g) and PB (12.4 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, P2 (0.077 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (7). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

"Evaluation of inkjet coatability of a liquid crystal aligning agent" was performed using the obtained liquid-crystal aligning agent (7).

<Example 8>

To the polyimide powder (5) (1.55 g) obtained in Synthesis Example 5, NMP (13.4 g), EC (2.40 g) and BCS (8.50 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, P3 (0.23 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (8). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (8), "evaluation of the display non-uniformity characteristic near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" were performed. .

<Example 9>

To the polyimide powder (6) (1.52 g) obtained in Synthesis Example 6, NEP (15.5 g) and PB (8.30 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, P1 (0.26 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (9). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid crystal aligning agent (9), ``evaluation of display non-uniformity characteristics near the frame of a liquid crystal cell after storage at high temperature and high humidity (normal cell)'', ``evaluation of voltage retention after storage at high temperature and humidity (normal cell)'' and ``liquid crystal Production of a cell and evaluation of liquid crystal orientation (PSA cell)" were performed.

<Example 10>

To the polyimide powder (6) (1.05 g) obtained in Synthesis Example 6, NEP (22.1 g) and PB (11.9 g) were added, followed by stirring at 70°C for 24 hours to dissolve. After that, P1 (0.18 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (10). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

"Evaluation of inkjet coatability of a liquid crystal aligning agent" was performed using the obtained liquid crystal aligning agent (10).

<Example 11>

To the polyimide powder (7) (1.50 g) obtained in Synthesis Example 7, NEP (9.40 g), γ-BL (4.70 g) and BCS (9.40 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, P2 (0.075 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (11). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (11), "evaluation of the display non-uniformity characteristic near the frame of a liquid crystal cell after high temperature high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature high humidity storage (normal cell)" were performed. .

<Example 12>

To the polyimide powder (7) (1.50 g) obtained in Synthesis Example 7, NMP (14.1 g), ECS (2.40 g) and BCS (7.10 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, to this solution, P1 (0.075 g) and P2 (0.15 g) were added, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (12). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (12), "evaluation of the display non-uniformity characteristic near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (usual cell)" were performed. .

<Example 13>

To the polyimide powder (8) (1.52 g) obtained in Synthesis Example 8, NEP (15.5 g) and PB (8.30 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, P2 (0.15 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (13). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (13), "evaluation of display non-uniformity characteristics near the frame of liquid crystal cell after high temperature and high humidity storage (normal cell)", "evaluation of voltage retention after high temperature and high humidity storage (normal cell)", and "liquid crystal Production of a cell and evaluation of liquid crystal orientation (PSA cell)" were performed.

<Example 14>

To the polyimide powder (8) (1.50 g) obtained in Synthesis Example 8, NEP (15.3 g) and PB (8.20 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, P1 (0.045 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (14). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (14), "evaluation of display non-uniformity characteristics near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" were performed. .

<Example 15>

To the polyimide powder (9) (1.50 g) obtained in Synthesis Example 9, NEP (11.8 g), γ-BL (2.40 g) and PB (9.40 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, P3 (0.15 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (15). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (15), "evaluation of display non-uniformity characteristics near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" were performed. .

<Example 16>

To the polyimide powder (9) (1.00 g) obtained in Synthesis Example 9, NEP (16.2 g), γ-BL (3.20 g) and PB (12.9 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, P3 (0.10 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (16). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

"Evaluation of the inkjet coatability of the liquid crystal aligning agent" was performed using the obtained liquid crystal aligning agent (16).

<Example 17>

To the polyimide powder (10) (1.55 g) obtained in Synthesis Example 10, NMP (15.8 g) and PB (8.50 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, P1 (0.23 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (17). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (17), "evaluation of display non-uniformity characteristics near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" were performed. .

<Example 18>

To the polyimide powder (10) (1.55 g) obtained in Synthesis Example 10, NEP (15.8 g) and PB (8.50 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, P1 (0.11 g) and P2 (0.11 g) were added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (18). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (18), "evaluation of display non-uniformity characteristics near the frame of liquid crystal cell after high temperature and high humidity storage (normal cell)", "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" and "liquid crystal Production of a cell and evaluation of liquid crystal orientation (PSA cell)" were performed.

<Example 19>

To the polyimide powder (11) (1.50 g) obtained in Synthesis Example 11, γ-BL (12.9 g), EC (2.40 g) and BCS (8.20 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, P3 (0.15 g) was added to this solution, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (19). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (19), "evaluation of display non-uniformity characteristics near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" were performed. .

<Example 20>

To the polyimide powder 11 (1.50 g) obtained in Synthesis Example 11, NMP (14.1 g), ECS (2.40 g), and BCS (7.10 g) were added, followed by stirring at 70°C for 24 hours to dissolve. Then, to this solution, P1 (0.075 g) and P2 (0.075 g) were added, and it stirred at 60 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (20). Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (20), "evaluation of the display non-uniformity characteristic near the frame of a liquid crystal cell after high temperature high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature high humidity storage (normal cell)" were performed. .

<Comparative Example 1>

To the polyamic acid solution (2) (10.5 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 2, NEP (18.9 g) and PB (14.4 g) were added, followed by stirring at 25°C for 2 hours, and liquid crystal alignment The treatment agent (21) was obtained. Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (21), "evaluation of the display non-uniformity characteristic near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" were performed. .

<Comparative Example 2>

To the polyimide powder (3) (1.55 g) obtained in Synthesis Example 3, NEP (17.0 g) and PB (7.30 g) were added, stirred at 70° C. for 24 hours and dissolved, thereby obtaining a liquid crystal aligning agent (22). . Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (22), "evaluation of display non-uniformity characteristics near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" were performed. .

<Comparative Example 3>

To the polyamic acid solution (4) (11.0 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 4, NEP (19.8 g) and PB (15.1 g) were added, followed by stirring at 25°C for 2 hours, and liquid crystal alignment The treatment agent (23) was obtained. Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (23), "evaluation of display non-uniformity characteristics near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" were performed. .

<Comparative Example 4>

To the polyimide powder (5) (1.50 g) obtained in Synthesis Example 5, NEP (15.3 g) and PB (8.20 g) were added, stirred at 70°C for 24 hours to dissolve, and a liquid crystal aligning agent (24) was obtained. . Abnormalities such as turbidity and precipitation were not seen in the liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

Using the obtained liquid-crystal aligning agent (24), "evaluation of the display non-uniformity characteristic near the frame of a liquid crystal cell after high temperature and high humidity storage (normal cell)" and "evaluation of voltage retention after high temperature and high humidity storage (normal cell)" were performed. .

As can be seen from the above results, compared to the liquid crystal aligning agent of the comparative example, the liquid crystal aligning agent of the embodiment does not disturb the liquid crystal alignment of the liquid crystal cell near the sealing agent even if the liquid crystal cell is stored in a high temperature and high humidity tank for a long period of time. A liquid crystal aligning film was obtained. Furthermore, even if the liquid crystal cell was stored in a high-temperature, high-humidity bath for a long period of time, a liquid crystal alignment film capable of suppressing a decrease in voltage retention was obtained. That is, the liquid crystal aligning agent of the present invention becomes a liquid crystal aligning film capable of suppressing the occurrence of display unevenness in the vicinity of the frame of a liquid crystal display element and a decrease in voltage retention under high temperature and high humidity conditions.

Specifically, it is a comparison between Example 2 and Comparative Example 1, Example 3 and Comparative Example 2, Example 4 and Comparative Example 3, and Example 6 and Comparative Example 4, and the same component (B) as the Example It is a comparison with the comparative example which uses a specific polymer and does not contain the specific compound which is (A) component. In the case of using the liquid crystal aligning agent of the comparative example, when the liquid crystal cell is stored in a high-temperature, high-humidity tank for a long period of time, disturbance of the liquid crystal aligning property occurred in the vicinity of the sealing agent of the liquid crystal cell, and the voltage retention rate was greatly reduced.

Industrial availability

The liquid crystal display element having a liquid crystal aligning film formed by using the liquid crystal aligning agent of the present invention is excellent in reliability and can be preferably used for a large-screen and high-definition liquid crystal television, etc., and TN element, STN element, TFT liquid crystal element, especially It is useful as a vertically aligned liquid crystal display device.

In addition, the entire contents of the Japanese Patent Application No. 2013-96470, the claims, and the abstract for which it applied on May 1, 2013 are cited here, and taken as an indication of the specification of the present invention.

Claims (14)

The liquid-crystal aligning agent characterized by containing the following (A) component and (B) component.
(A) Component: A compound represented by the following formula [1].
Component (B): At least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

(X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring, and X ² is the following formula [1-1] to Represents a structure selected from formula [1-5])

(W ¹ represents a hydrogen atom or a benzene ring) The method of claim 1,
The liquid crystal aligning agent in which X ¹ of said formula [1] is a C1-C10 alkylene group. The method of claim 1,
The liquid crystal aligning agent which is a structure in which X ² of said Formula [1] is a structure chosen from Formula [1-1], Formula [1-2], and Formula [1-4]. The method of claim 1,
The liquid crystal aligning agent in which the diamine component in the polymer of the component (B) contains at least one or more diamine compounds having a structure represented by the following formula [2].

(Y represents a substituent of the structure selected from the following formulas [2-1] to [2-6], and m represents an integer of 1 to 4)

(a represents the integer of 0-4, b represents the integer of 0-4.
Y ¹ represents a single bond, -(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, and Y ² is a single bond or -(CH ₂ ) _b- (b is an integer of 1 to 15), Y ³ is a single bond, -(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ represents O-, -COO- or -OCO-, and Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, Any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom. , Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, and 1 It may be substituted with a fluorine-containing alkyl group of to 3, a fluorine-containing alkoxyl group of 1 to 3 carbons, or a fluorine atom, n represents an integer of 0 to 4, Y ⁶ is an alkyl group of 1 to 18 carbons, fluorine of 1 to 18 carbons A containing alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group,
Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH-, or -NHCO-, and Y ⁸ represents an alkyl group having 8 to 22 carbon atoms.
Y ⁹ and Y ¹⁰ each independently represents a hydrocarbon group having a carbon number of 1 to 12, Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms.) The method of claim 1,
A liquid crystal aligning agent containing a compound represented by the following formula [3] in the tetracarboxylic acid component in the polymer of the said (B) component.

(Z ¹ is a group having a structure selected from the following formulas [3a] to [3j])

(Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, respectively, and Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and may be the same or different, respectively) The method of claim 1,
The liquid crystal aligning agent which is a polyimide obtained by dehydrating and cyclizing a polyamic acid in the polymer of the said (B) component. The method of claim 1,
The liquid crystal aligning agent in which the component (A) is 0.1 to 30 parts by mass per 100 parts by mass of the component (B). A liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-7. A liquid crystal aligning film obtained by an inkjet method using the liquid crystal aligning agent in any one of Claims 1-7. A liquid crystal display device having the liquid crystal alignment film according to claim 8. The method of claim 8,
It has a liquid crystal layer between a pair of substrates with electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and between the electrodes A liquid crystal alignment layer used in a liquid crystal display device manufactured by polymerizing the polymerizable compound while applying a voltage. A liquid crystal display element comprising the liquid crystal alignment film according to claim 11. The method of claim 8,
It has a liquid crystal layer between a pair of substrates with electrodes, a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and a voltage between the electrodes A liquid crystal alignment layer used in a liquid crystal display device manufactured by polymerizing the polymerizable group while applying. A liquid crystal display element comprising the liquid crystal alignment film according to claim 13.