KR102470287B1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

(식 [2] 중, Z¹ 은 하기의 식 [2a] ∼ 식 [2j] 에서 선택되는 적어도 1 종의 4 가의 기이다.)

(식 [2a] 중, Z² ∼ Z⁵ 는 수소 원자, 메틸기, 염소 원자 또는 벤젠 고리를 나타내고, 각각 동일하거나 상이하여도 되며, 식 [2g] 중, Z⁶ 및 Z⁷ 은 수소 원자 또는 메틸기를 나타내고, 각각 동일하거나 상이하여도 된다.)A polyimide precursor obtained by reacting a diamine component with a tetracarboxylic acid component containing tetracarboxylic dianhydride represented by the following formula [1] and aliphatic tetracarboxylic dianhydride represented by the following formula [2], and a polyimide precursor thereof The liquid-crystal aligning agent containing the at least 1 sort(s) of polymer chosen from the polyimide obtained by imidating a polyimide precursor.

(In formula [2], Z ¹ is at least one kind of tetravalent group selected from the following formula [2a] to formula [2j].)

(In the formula [2a], 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 in the formula [2g], Z ⁶ and Z ⁷ are a hydrogen atom or a methyl group , which may be the same or different.)

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}

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

Currently, as a liquid crystal alignment film of a liquid crystal display element, a so-called polyimide-based liquid crystal alignment film obtained by applying and firing a liquid crystal aligning agent containing a polyimide precursor such as polyamic acid or a soluble polyimide solution as a main component is mainly used.

A liquid crystal alignment film is used for the purpose of controlling the alignment state of liquid crystals. However, with the high definition of the liquid crystal display element, from the viewpoint of suppression of the decrease in contrast of the liquid crystal display element and reduction of the afterimage phenomenon, the voltage retention is high also in the liquid crystal aligning film used therein, and when a direct current voltage is applied The characteristics of having little accumulated charge or quick relaxation of the accumulated charge by direct current voltage have become increasingly important.

In the polyimide-based liquid crystal alignment film, the time until the afterimage generated by the DC voltage disappears is short, and a liquid crystal aligning agent containing a tertiary amine of a specific structure in addition to polyamic acid or imide group-containing polyamic acid What was used (for example, refer to Patent Literature 1), and what used a liquid crystal aligning agent containing a soluble polyimide in which a specific diamine having a pyridine skeleton or the like was used as a raw material (see, for example, Patent Literature 2) are known. have. In addition, the voltage retention is high and the time until the afterimage generated by the DC voltage disappears is short, and in addition to polyamic acid or its imidized polymer, a compound containing one carboxylic acid group in the molecule, one in the molecule It is known that a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing a carboxylic acid anhydride group and a compound containing one tertiary amino group in a molecule is used (see Patent Document 3, for example).

Japanese Unexamined Patent Publication No. 9-316200 Japanese Unexamined Patent Publication No. 10-104633 Japanese Unexamined Patent Publication No. 8-076128

BACKGROUND ART With recent high performance of liquid crystal display elements, liquid crystal display elements are used for large-screen, high-definition liquid crystal televisions and in-vehicle applications, such as car navigation systems and meter panels. In such applications, a backlight having a large calorific value is sometimes used to obtain high luminance. For this reason, high reliability from another viewpoint, ie, high stability with respect to the light from a backlight, was requested|required of the liquid crystal aligning film. In particular, when the voltage retention, which is one of the electrical characteristics of the liquid crystal display element, is lowered by light irradiation from the backlight, the problem of burn-in defect (also referred to as line burn-in), which is one of the display defects of the liquid crystal display element, occurs. there is

Therefore, in a liquid crystal aligning film, it is calculated|required that voltage retention does not fall easily, for example, even after being exposed to irradiation of light for a long time in addition to having good initial stage characteristics.

Then, this invention can suppress the fall of voltage retention even after long-time light irradiation, and is an object of providing the liquid crystal aligning agent for obtaining the liquid crystal aligning film excellent in light resistance, the liquid crystal aligning film, and the liquid crystal display element which has this liquid crystal aligning film. do.

As a result of intensive research, the present inventors have imidized a polyimide precursor obtained by reacting a diamine component and a tetracarboxylic acid component containing two types of tetracarboxylic dianhydride having a specific structure, and the polyimide precursor, In order to achieve the said objective, the liquid-crystal aligning agent containing the at least 1 sort(s) of polymer chosen from the polyimide obtained discovers that it is very effective, and came to complete this invention.

That is, this invention has the following summary.

(1) A polyimide precursor obtained by reacting a diamine component with a tetracarboxylic acid component containing tetracarboxylic dianhydride represented by the following formula [1] and tetracarboxylic dianhydride represented by the following formula [2] And the liquid-crystal aligning agent characterized by containing at least 1 sort(s) of polymer chosen from the polyimide obtained by imidating the polyimide precursor.

[Formula 1]

[Formula 2]

(In formula [2], Z ¹ is at least one kind of tetravalent group selected from the following formula [2a] to formula [2j].)

[Formula 3]

(In the formula [2a], 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 in the formula [2g], Z ⁶ and Z ⁷ are a hydrogen atom or a methyl group , which may be the same or different.)

(2) The liquid crystal alignment described in the above (1) characterized by containing N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone as a solvent in the liquid crystal aligning agent. treatment agent.

(3) The liquid-crystal aligning agent as described in (1) or (2) above, characterized by containing a solvent selected from the following formula [D-1] to formula [D-3] as a solvent in the liquid-crystal aligning agent .

[Formula 4]

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

(4) The liquid crystal aligning film characterized by being obtained using the liquid-crystal aligning agent as described in said (1) - said (3).

(5) The liquid crystal aligning film characterized by being obtained by an inkjet method using the liquid-crystal aligning agent as described in said (1) - said (3).

(6) The liquid crystal display element characterized by having the liquid crystal aligning film as described in said (4) or said (5).

According to the liquid-crystal aligning agent of this invention, even if it exposes to irradiation of light for a long time, the fall of voltage retention can be suppressed, and the liquid crystal aligning film excellent in light resistance can be obtained. Therefore, the liquid crystal display element which has a liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention becomes a thing excellent in reliability, and can be used suitably for a large-screen, high-definition liquid crystal television etc..

The liquid-crystal aligning agent of this invention is tetracarboxylic dianhydride (it is also mentioned specific tetracarboxylic dianhydride) represented by following formula [1], and aliphatic tetracarboxylic dianhydride represented by following formula [2] ( It is also referred to as specific aliphatic tetracarboxylic dianhydride) and a polyimide precursor obtained by reacting a diamine component with a tetracarboxylic acid component, and at least one polymer selected from a polyimide obtained by imidizing the polyimide precursor. (also referred to as a specific polymer) is contained.

Here, a diamine component is a diamine compound which has two primary or secondary amino groups in a molecule|numerator. The polyimide precursor refers to polyamic acid or polyamic acid alkyl ester.

<Specific tetracarboxylic dianhydride>

The tetracarboxylic acid component which is the raw material of the specific polymer which the liquid-crystal aligning agent of this invention contains contains two types of tetracarboxylic dianhydride. One type of tetracarboxylic dianhydride is specific tetracarboxylic dianhydride represented by the following formula [1].

[Formula 5]

The specific tetracarboxylic dianhydride represented by formula [1] is a tetracarboxylic acid derivative, tetracarboxylic acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester compound, or tetracarboxylic acid dialkyl ester dihalide. Compounds (all collectively referred to as specific tetracarboxylic acid components) can also be used.

It is preferable that specific tetracarboxylic dianhydride represented by Formula [1] is 20 mol% - 80 mol% in all tetracarboxylic-acid components. Especially, it is preferable that they are 20 mol% - 60 mol%. Particularly preferred are 20 mol% to 50 mol%.

<Specific aliphatic tetracarboxylic dianhydride>

The tetracarboxylic acid component which is the raw material of the specific polymer which the liquid-crystal aligning agent of this invention contains contains two types of tetracarboxylic dianhydride. The other kind of tetracarboxylic dianhydride is a specific aliphatic tetracarboxylic dianhydride represented by the following formula [2].

[Formula 6]

In formula [2], Z< ¹ > is at least 1 sort(s) of tetravalent groups chosen from following formula [2a] - formula [2j].

[Formula 7]

^In formula [2a], Z2 ^- Z5 represent a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, and may be the same or different, respectively.

In formula [2g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and may be the same or different, respectively.

Among the structures shown in formula [2], Z ¹ represents formula [2a], formula [2c], formula [2d], or formula [2e] from the viewpoint of ease of synthesis and ease of polymerization reactivity when producing a polymer. , the structure represented by formula [2f] or formula [2g] is preferable. A more preferable thing is a structure represented by a formula [2a], a formula [2e], a formula [2f], or a formula [2g], and a formula [2e], a formula [2f], or a formula [2g] is especially preferable.

The specific aliphatic tetracarboxylic dianhydride represented by formula [2] is a tetracarboxylic acid derivative such as tetracarboxylic acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester compound, or tetracarboxylic acid dialkyl ester di Halide compounds (all collectively referred to as specific aliphatic tetracarboxylic acid components) can also be used.

It is preferable that specific aliphatic tetracarboxylic dianhydride represented by Formula [2] is 20 mol% - 80 mol% in all tetracarboxylic-acid components. Particularly preferred are 20 mol% to 60 mol%.

Moreover, specific aliphatic tetracarboxylic dianhydride is solubility to the solvent of the specific polymer which the liquid-crystal aligning agent of this invention contains, the applicability|paintability of a liquid-crystal aligning agent, the orientation of the liquid crystal in the case where it is set as a liquid crystal aligning film, and voltage retention Depending on characteristics such as , accumulated charge, etc., one type or a mixture of two or more types may be used.

<Other tetracarboxylic acid compounds>

The tetracarboxylic acid component in the specific polymer contained in the liquid-crystal aligning agent of the present invention is other than specific tetracarboxylic dianhydride and specific aliphatic tetracarboxylic dianhydride unless the effect of the present invention is impaired. A tetracarboxylic acid compound of (also referred to as other tetracarboxylic acid compounds) can also be used.

Specific examples thereof include tetracarboxylic dianhydride, tetracarboxylic acid compound, and dicarboxylic acid dihalide compound shown below.

Namely, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-anthracentetracarboxylic acid, 1,2,5,6-anthracentetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic 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-pyridinetetracarboxyl 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.

As for other tetracarboxylic compounds, the solubility to the solvent of the specific polymer contained in the liquid crystal aligning agent of the present invention, the applicability of the liquid crystal aligning agent, the orientation of liquid crystal when used as a liquid crystal aligning film, voltage retention, accumulated charge, etc. Depending on the characteristics of , one type or a mixture of two or more types may be used.

<diamine component>

A well-known diamine compound can be used as a diamine component for manufacturing the specific polymer which the liquid-crystal aligning agent of this invention contains.

Especially, it is preferable to use the diamine compound which has a structure represented by following formula [3].

[Formula 8]

In formula [3], Y is the following formula [3-1], formula [3-2], formula [3-3], formula [3-4], formula [3-5] or formula [3-6] ], m represents an integer of 1 to 4, and -(Y) _m represents that there are m substituents Y.

[Formula 9]

In formula [3-1], a 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 [3-2], 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 [3-3], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- indicate Among them, from the viewpoint of the 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 single bonds, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In formula [3-3], Y2 represents ^a single bond or _- (CH2) _b- (b is an integer of 1-15). Especially, a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) is preferable.

In formula [3-3], Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- indicate Especially, from the point of synthetic|combination easiness, a single bond, -(CH2) _c- (c is an integer _of 1-15), -O-, -CH2O- _, or -COO- are preferable. More preferable ones are a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In formula [3-3], Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group of 1 to 3 carbon atoms or a carbon atom of 1 to 3 carbon atoms. may be substituted with an alkoxyl group, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine atom. Further, Y ⁴ may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a steroid skeleton. Especially, from the viewpoint of ease of synthesis, an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable.

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

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

In formula [3-3], Y< ⁶ > represents a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group. Especially, 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. Especially preferably, it is 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 [3-3] for constituting the substituent Y in the formula [3], International Publication WO2011/ The same combinations as (2-1) to (2-629) listed in Tables 6 to 47 of 132751 to 34 are exemplified. In addition, in each table|surface of international publication gazette, Y1 ^- Y6 in this invention is shown as Y1 ^- Y6, but Y1 ^- Y6 shall read it as Y1 ^- Y6. In addition, an organic group having 12 to 25 carbon atoms having a steroid skeleton is read interchangeably with an organic group having 17 to 51 carbon atoms having a steroid skeleton.

In formula [3-4], Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-. Especially, -O-, -CH ₂ O-, -COO-, or -CONH- is preferable. More preferably -O-, -COO- or -CONH-.

In formula [3-4], Y< ⁸ > represents a C8-C22 alkyl group.

In formula [3-5], Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group having 1 to 12 carbon atoms.

In formula [3-6], Y< ¹¹ > represents a C1-C5 alkyl group.

Although the method of manufacturing the diamine compound represented by said Formula [3] is not specifically limited, As a preferable method, what is shown below is mentioned. As an example, the diamine compound represented by formula [3] is obtained by synthesizing a dinitro compound represented by the following formula [3-A], further reducing the nitro group and converting it into an amino group.

[Formula 10]

(In formula [3-A], Y is the formula [3-1], formula [3-2], formula [3-3], formula [3-4], formula [3-5] or formula [3 -6] represents at least one substituent selected from, and m represents an integer of 1 to 4.)

The method for reducing the dinitro group of the dinitro compound represented by the formula [3-A] is not particularly limited, and is usually palladium- There is a method of reacting under hydrogen gas, hydrazine or hydrogen chloride using carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina or platinum carbon sulfide as a catalyst.

Below, although the specific structure of the diamine compound represented by said Formula [3] is given, it is not limited to these examples.

That is, as a diamine compound represented by Formula [3], 2, 4- dimethyl- m - phenylenediamine, 2, 6- diamino toluene, 2, 4- diamino benzoic acid, 3, 5- diamino benzoic acid, 2 , 4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, as well as the following formula [3- 7] - the diamine compound of the structure shown by [3-47] is mentioned.

[Formula 11]

(In the formula [3-7] to the formula [3-10], A ¹ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.)

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

(In formula [3-35] to formula [3-37], R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or CH ₂ OCO-, and R ² represents carbon number An alkyl group of 1 to 22, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group is shown.)

[Formula 24]

(In formula [3-38] to formula [3-40], R ³ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or - represents CH ₂ -, and R ⁴ represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.)

[Formula 25]

(In formulas [3-41] and [3-42], 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, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.)

[Formula 26]

(In formula [3-43] and formula [3-44], R ⁷ represents an alkyl group having 3 to 12 carbon atoms. In addition, the cis-trans isomer of 1,4-cyclohexylene is each preferably a trans isomer. )

[Formula 27]

(In formula [3-45] and formula [3-46], 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 28]

(In the formula [3-47], 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-* (provided that the bond attached with "*" binds to B ³ ), and B ¹ represents an oxygen atom or -COO-* (provided that the bond attached with "*" is ( CH ₂ ) bonded to 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.)

When the liquid-crystal aligning agent obtained from the specific polymer using the diamine compound of the structure in which the substituent Y in formula [3] is represented by formula [3-3] among the diamine compounds represented by said formula [3] is set as a liquid crystal aligning film, liquid crystal The pretilt angle of can be increased. At that time, for the purpose of enhancing these effects, among the above diamine compounds, formula [3-25] to formula [3-40] or formula [3-43] to use diamine compounds represented by formula [3-47] it is desirable A more preferable thing is a diamine compound represented by formula [3-29] - formula [3-40] or formula [3-43] - formula [3-47]. Moreover, in order to enhance these effects more, it is preferable that these diamine compounds are 5 mol% or more and 80 mol% or less of the whole diamine component. More preferably, these diamine compounds are 5 mol% or more and 60 mol% or less of the whole diamine component from the point of the electrical property as the coating property of a composition and a liquid-crystal aligning agent, or a liquid crystal aligning film.

The diamine compound represented by the said Formula [3] is solubility and applicability to the solvent of the specific polymer which the liquid-crystal aligning agent of this invention contains, orientation of the liquid crystal in the case of setting it as a liquid crystal aligning film, voltage retention, accumulated charge, etc. Depending on the characteristics, one type or a mixture of two or more types may be used.

As a diamine component for producing the specific polymer which the liquid-crystal aligning agent of this invention contains, diamine compounds (it is also mentioned other diamine compounds) other than the diamine compound represented by said Formula [3] can be used. Below, although specific examples of other diamine compounds are 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'-diaminobiphenyl, 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'-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3' -sulfonyldianiline, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'- Thiodyaniline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2' -Diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl (3,4'-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' -Diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6- Diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3- Bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane Rophane, 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-phenyl Lenbis[(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 -phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4 -Aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenyl Len)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3- aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)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-amino Phenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2, 2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2' -bis(3-amino-4-methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-amino Phenoxy)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-aminophenoxy) 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; and the like. have.

Moreover, as another diamine compound, those which have an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, or a heterocyclic ring in the diamine side chain, and those which have a macrocyclic substituent composed of these can also be cited. Specifically, diamine compounds represented by the following formulas [DA1] to [DA7] can be exemplified.

[Formula 29]

[Formula 30]

[Formula 31]

(In formula [DA1] to formula [DA6], A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.)

[Formula 32]

(In the formula [DA7], p represents an integer of 1 to 10.)

Moreover, the diamine compound represented by the following formula [DA8] - formula [DA13] can also be used as another diamine compound, unless the effect of this invention is impaired.

[Formula 33]

[Formula 34]

(In the formula [DA10], m represents an integer of 0 to 3, and in the formula [DA13], n represents an integer of 1 to 5.)

Moreover, the diamine compound represented by the following formula [DA14] - formula [DA17] can also be used as another diamine compound, unless the effect of this invention is impaired.

[Formula 35]

(In the formula [DA14], 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(CH ₃ )CO-, m ¹ and m ² each represent an integer of 0 to 4, and m ¹ +m ² represents an integer of 1 to 4, and in the formula [DA15], m ³ and m ⁴ represent an integer of 1 to 5, respectively, in the 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; ], A ³ 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 - represents N(CH ₃ )CO-, and m ⁶ represents an integer of 1 to 4.)

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

[Formula 36]

The other diamine compounds exemplified above have properties such as the solubility to the solvent of the specific polymer contained in the liquid crystal aligning agent of the present invention, the applicability of the composition, the orientation of the liquid crystal when used as a liquid crystal aligning film, voltage retention, accumulated charge, etc. Depending on the characteristics, one type or a mixture of two or more types may be used.

<specific polymer>

The specific polymer which the liquid-crystal aligning agent of this invention contains is the specific tetracarboxylic acid component containing the specific tetracarboxylic dianhydride represented by said formula [1], and the specific aliphatic tetracarboxylic represented by said formula [2] It is at least 1 sort(s) of polymer chosen from the polyimide precursor obtained by making the specific aliphatic tetracarboxylic acid component containing acid dianhydride and the said diamine component react, and the polyimide obtained by imidating this polyimide precursor.

Moreover, the polyimide precursor obtained by making the said specific aliphatic tetracarboxylic acid component and the said diamine component react is a structure shown by following formula [A], for example.

[Formula 37]

(In formula [A], R ¹ is a tetravalent organic group derived from a specific aliphatic tetracarboxylic acid component, R ² is a divalent organic group derived from a diamine component, and A ¹ and A ² are hydrogen atoms or carbon atoms represents an alkyl group of 1 to 8, each may be the same or different, A ³ and A ⁴ represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or an acetyl group, may be the same or different, respectively, and n is a positive integer; indicate.)

The specific polymer which the liquid-crystal aligning agent of this invention contains is the specific tetracarboxylic dianhydride represented by said formula [1], the specific aliphatic tetracarboxylic dianhydride represented by following formula [B], and the following formula For the reason that it can be obtained relatively simply by using the diamine compound represented by [C] as a raw material, a polyamic acid having a structural formula of a repeating unit represented by the following formula [D] or a polyimide obtained by imidizing the polyamic acid is preferred. In addition, the specific tetracarboxylic dianhydride represented by formula [B] is the same as the specific aliphatic tetracarboxylic dianhydride represented by said formula [2]. In this case, R ¹ in formula [B] is the same tetravalent group as Z ¹ in formula [2].

[Formula 38]

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

[Formula 39]

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

Moreover, by a normal synthesis method, the C1-C8 alkyl group of A1 and A2 represented by formula [ ^{A ]} , and ^A3 and A4 represented by formula [ ^A ] were added to the polymer of formula [D] obtained above An alkyl group having 1 to 5 carbon atoms or an acetyl group may be introduced.

<Method for producing specific polymer>

In this invention, the tetracarboxylic acid component containing the specific tetracarboxylic dianhydride and the specific aliphatic tetracarboxylic dianhydride represented by the specific tetracarboxylic dianhydride and the specific tetracarboxylic dianhydride represented by the said formula [2], and diamine which a specific polymer is represented by said formula [1], It is obtained by reacting the components. Specifically, a method of polycondensing a specific tetracarboxylic dianhydride, a specific aliphatic tetracarboxylic dianhydride, and a diamine component to obtain a polyamic acid, dehydration polycondensation or polycondensation of a tetracarboxylic acid component and a diamine component. A method of obtaining a polyamic acid by combining them is used.

To obtain polyamic acid alkyl ester, polycondensation of tetracarboxylic acid obtained by dialkyl esterification of carboxylic acid group with diamine component, and polycondensation of tetracarboxylic acid dihalide obtained by dialkyl esterification of carboxylic acid group with diamine component are performed. A method of converting the carboxyl group of polyamic acid into an ester is used.

In order to obtain polyimide, the method of making a polyimide by ring-closing the said polyamic acid or polyamic-acid alkylester is used.

Reaction of a diamine component and a tetracarboxylic acid component normally performs a diamine component and a tetracarboxylic acid component in an organic solvent. The organic solvent used in that case is not particularly limited as long as the produced polyimide precursor dissolves therein. 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, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D-1] to formula [D- 3], etc. are mentioned.

[Formula 40]

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

These may be used independently or may be used in mixture. Moreover, even if it is a solvent which does not dissolve a polyimide precursor, you may mix with the said solvent and use it within the range in which the produced|generated polyimide precursor does not precipitate. Further, since moisture in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the resulting polyimide precursor, it is preferable to use a dehydrated and dried organic solvent.

When reacting the diamine component and the tetracarboxylic acid component in an organic solvent, a method in which a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid component is added as it is or after being dispersed or dissolved in an organic solvent. , Conversely, a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent, a method of adding a diamine component and a tetracarboxylic acid component alternately, and the like, using any of these methods can also Moreover, when reacting using multiple types of diamine component or tetracarboxylic acid component, respectively, they may be reacted in a state mixed beforehand, or they may be reacted sequentially individually, or a mixture reaction of low molecular weight substances reacted separately to form a polymer can be done with The polymerization temperature at that time can be selected from any temperature in the range of -20°C to 150°C, but is preferably in the range of -5°C to 100°C. In addition, although the reaction can be carried out at an arbitrary concentration, when the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and when 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 stage of the reaction can be performed at a high concentration, and then an organic solvent can be added.

In the polymerization reaction of the polyimide precursor, it is preferable that the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is 0.8 to 1.2. Similar to a normal polycondensation reaction, the closer this molar ratio is to 1.0, the larger the molecular weight of the polyimide precursor to be produced.

The polyimide constituting the specific polymer contained in the liquid-crystal aligning agent of the present invention is a polyimide obtained by ring-closing the above polyimide precursor, and in this polyimide, the amide acid group closure rate (also referred to as imidation rate) is necessarily It does not have to be 100%, and can be arbitrarily adjusted depending on the use or purpose.

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

The temperature in the case of thermal imidization of the polyimide precursor in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction to the outside of the system. .

Catalytic imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to a 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 the amount of the amide acid group, and the amount of the acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times the amount of the amide acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among these, pyridine is preferable because it has appropriate basicity for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, and among these, acetic anhydride is preferable because purification after completion of the reaction becomes easy. The imidation rate by catalyst imidation is controllable by adjusting the catalyst amount, reaction temperature, and reaction time.

What is necessary is just to throw in the reaction solution into a solvent and just to precipitate it, when collect|recovering the produced|generated polyimide precursor or polyimide from the polyimide precursor or the reaction solution of a polyimide. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, or water. The polymer precipitated by being put into a solvent can be collected by filtration and then dried by heating or at room temperature under normal pressure or reduced pressure. In addition, the impurities in the polymer can be reduced by re-dissolving the polymer recovered by precipitation in an organic solvent and repeating the operation of re-precipitation and recovery 2 to 10 times. Examples of the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more types of solvents selected from among these, since the purification efficiency is further increased.

The molecular weight of the specific polymer contained in the liquid crystal aligning agent of the present invention is a weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method when the strength of the liquid crystal aligning film obtained therefrom, workability at the time of film formation, and coating film properties are considered. It is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<liquid crystal aligning agent>

The liquid-crystal aligning agent of this invention is a coating solution for forming a liquid crystal aligning film, and contains a polymer component and a solvent, and is a coating solution for forming a polymer film.

And as above-mentioned, the liquid-crystal aligning agent of this invention is the said specific polymer, ie, the specific tetracarboxylic dianhydride represented by the above-mentioned formula [1] as a polymer component, and the above-mentioned formula [2 ] A polyimide precursor obtained by reacting a tetracarboxylic acid component (a specific tetracarboxylic acid component and a specific aliphatic tetracarboxylic acid component) containing a specific aliphatic tetracarboxylic dianhydride represented by and a diamine component, and a polyimide thereof It contains at least 1 sort(s) of polymer chosen from the polyimide obtained by imidating a precursor. By using the liquid-crystal aligning agent containing such a specific polymer, it is excellent in light tolerance and the liquid crystal aligning film excellent in voltage retention characteristic (voltage retention) can be obtained. This reason is explained below.

Specific tetracarboxylic dianhydride has a structure in which two dicarboxylic acid dianhydrides are bonded with a methylene group. Since the methylene group is flexible (flexible), the polyimide precursor or polyimide obtained by reacting the specific tetracarboxylic dianhydride having such a methylene group, the specific aliphatic tetracarboxylic dianhydride and the diamine component has the flexibility of the methylene group. It is thought that intramolecular and intramolecular pseudo-crosslinking is achieved by As a result, a specific polymer polymerizes and becomes high in density. The liquid crystal aligning film which has a specific polymer with a high density turns into a precise|minute film|membrane, and as shown in the Example mentioned later, the fall of voltage retention is suppressed even after irradiation of strong ultraviolet-ray, and it becomes a thing excellent in light tolerance.

In general, aromatic acid anhydrides are weak in light resistance, but since specific tetracarboxylic dianhydride has a flexible methylene group as described above, the light resistance of a liquid crystal aligning film having a specific polymer does not decrease, and voltage The retention rate can be maintained at a high level.

Such excellent voltage retention characteristics can be further enhanced by using a specific non-aromatic tetracarboxylic dianhydride together with a specific tetracarboxylic dianhydride having a methylene group as a raw material for a specific polymer.

As a result of the above, by using two types of tetracarboxylic dianhydride of specific tetracarboxylic dianhydride and specific aliphatic tetracarboxylic dianhydride as a raw material of the specific polymer contained in the liquid-crystal aligning agent of the present invention, light resistance This is excellent, and the liquid crystal aligning film excellent in voltage retention characteristic can be obtained.

As for all the polymer components in the liquid-crystal aligning agent of this invention, all may be a specific polymer, and another polymer other than that may be mixed. In that case, content of other polymers other than that is 0.5 mass % - 15 mass % of a specific polymer, Preferably they are 1 mass % - 10 mass %. As another polymer other than that, the polyimide precursor or polyimide which does not use the specific tetracarboxylic dianhydride represented by said formula [1] and the specific aliphatic tetracarboxylic dianhydride represented by said formula [2] can be heard Furthermore, an acrylic polymer, a methacryl polymer, polystyrene, polyamide, or polysiloxane etc. are mentioned.

Although solid content concentration in the liquid-crystal aligning agent of this invention can be changed suitably according to setting of the thickness of the liquid crystal aligning film to form, it is preferable to set it as 0.5-10 mass %, and it is more preferable to set it as 1-8 mass %. If the solid content concentration is less than 0.5% by mass, it becomes difficult to form a uniform and defect-free coating film, and if it is more than 10% by mass, the storage stability of the solution may deteriorate. Solid content here means the component which removed the solvent from the liquid-crystal aligning agent, and means the above-mentioned specific polymer, another polymer other than that, and the various additives mentioned later.

It is preferable that content of the solvent in a liquid-crystal aligning agent is 70-99.9 mass % from a viewpoint that the solvent in the liquid-crystal aligning agent of this invention forms a uniform liquid crystal aligning film by application|coating. This content can be suitably changed according to the film thickness of the liquid crystal aligning film made into the objective.

The solvent used for the liquid-crystal aligning agent of this invention will not be specifically limited if it is a solvent (it is also mentioned a good solvent) in which a specific polymer is dissolved. Below, although the 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, dimethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, or 4-hydroxy-4-methyl-2-pentanone. Among them, solvents represented by N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone or the above-described formula [D-1] to formula [D-3], etc. can be heard These may be used independently or may be used in mixture.

Especially, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and (gamma)-butyrolactone. Furthermore, when the solubility to the solvent of a specific polymer is high, it is preferable to use the solvent represented by the said formula [D-1] - formula [D-3].

It is preferable that the good solvent in the liquid-crystal aligning agent of this invention is 10-100 mass % of the whole solvent contained in the liquid-crystal aligning agent. Especially, 20-90 mass % is preferable. More preferably, it is 30-80 mass %.

The liquid-crystal aligning agent of this invention can use the solvent (it is also mentioned a poor solvent) which improves the coating film property and surface smoothness of the liquid crystal aligning film at the time of apply|coating a liquid-crystal aligning agent, unless the effect of this invention is impaired. Below, although the 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 Monoethyl ether acetate, diethylene glycol monobutyl ether Acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxy Propionic acid, 3-methoxypropylpropionate, 3-methoxybutylpropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate or the above formula [D-1] to The solvent etc. represented by formula [D-3] are mentioned.

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

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

In the liquid crystal aligning agent of the present invention, in the group consisting of a crosslinkable 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, unless the effect of the present invention is impaired. A crosslinkable compound having at least one selected substituent or a crosslinkable compound having a polymerizable unsaturated bond may be contained. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in a crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, and tetraglycidylaminodiphenylene. , tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroaceto 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 or 1,3-bis(4-(1-(4-(2,3-epoxypro) Poxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol and the like.

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

[Formula 41]

The crosslinking|crosslinking compound specifically, represented by formula [4a] - formula [4k] published in the 58th term|claim of international publication WO2011/132751 - 59th term|claim is mentioned.

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].

[Formula 42]

The crosslinking|crosslinked compound specifically, represented by the formula [5-1] - which is published in international publication WO2011/132751 76 term - 82 term - formula [5-42] is 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 amino resins having a hydroxyl group or an alkoxyl group, such as melamine resins, urea resins, and guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, or ethyleneurea-formaldehyde resin. 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 thereof can be used. This melamine derivative or benzoguanamine derivative can also exist as a dimer or a trimer. It is preferable that these have an average of 3 or more and 6 or less methylol groups or alkoxymethyl groups per triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 methoxymethyl groups per triazine ring, and MW, which has an average of 5.8 methoxymethyl groups per triazine ring. -30 (above, manufactured by Sanwa Chemical Co., Ltd.), methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 238, 212, 253 . Benzoguanamines, methoxymethylated butoxymethylated benzoguanamines such as Cymel 1123-10, butoxymethylated benzoguanamines such as Cymel 1128, methoxymethylated ethoxymethylated benzoguas containing carboxyl groups such as Cymel 1125-80 Namine (above, manufactured by Mitsui Cyanamide Co., Ltd.) is exemplified. Moreover, as an example of a glycoluril, butoxymethylation glycoluril like Cymel 1170, methylolation glycoluril like Cymel 1172, etc., a methoxymethylolation glycoluril like Powder Link 1174, etc. are mentioned.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris(methoxymethyl)benzene, 1,2,4-tris(isopropoxymethyl)benzene, 1 ,4-bis(sec-butoxymethyl)benzene or 2,6-dihydroxymethyl-p-tert-butylphenol; and the like.

More specifically, the crosslinkable compound shown by formula [6-1] - formula [6-48] published on page 62 of international publication WO2011/132751 - page 66 is mentioned.

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tri(meth)acrylate. ) A crosslinkable compound having three polymerizable unsaturated groups in the molecule, such as acryloyloxyethoxytrimethylolpropane or glycerin polyglycidyl ether poly(meth)acrylate, furthermore, ethylene glycol di(meth)acrylate, di Ethylene 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, neopentylglycoldi(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanedioldi(meth) Acrylates, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, A crosslinkable compound having two polymerizable unsaturated groups in the molecule, such as phthalic acid diglycidyl ester di(meth)acrylate or hydroxypivalic acid neopentyl glycol di(meth)acrylate, and furthermore, 2-hydroxyethyl (meth)acrylate ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy Cy-2-hydroxypropylphthalate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono(meth)acrylate, 2-(meth)acryloyloxyethyl phosphate or N-methylol ( and crosslinkable compounds having one polymerizable unsaturated group in the molecule, such as meth)acrylamide.

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

[Formula 43]

(In formula [7], E ₁ is 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, or a phenanthrene ring. E ₂ represents a group selected from the following formula [7a] or formula [7b], and n represents an integer of 1 to 4.)

[Formula 44]

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

It is preferable that content of the crosslinkable compound in the liquid-crystal aligning agent of this invention is 0.1-150 mass parts with respect to 100 mass parts of all polymer components. In order for the crosslinking reaction to proceed and the desired effect to be expressed, 0.1 to 100 parts by mass is more preferred, and particularly 1 to 50 parts by mass is most preferred, based on 100 parts by mass of all the polymer components.

When it is set as a liquid crystal aligning film using the liquid-crystal aligning agent using the composition of this invention, as a compound which accelerates the charge transfer in a liquid crystal aligning film and accelerates the charge omission of the liquid crystal cell using the liquid crystal aligning film, of International Publication WO2011/132751 It is preferable to add nitrogen-containing heterocyclic amine compounds represented by formula [M1] to formula [M156] published on pages 69 to 73. Although this amine compound may be directly added to a composition, it is preferable to add it after setting it as a solution with a density|concentration of 0.1 mass % - 10 mass % in a suitable solvent, Preferably it is 1 mass % - 7 mass %. As this solvent, it will not specifically limit, if it is an organic solvent which dissolves the specific polyimide type polymer mentioned above.

The liquid-crystal aligning agent of this invention can use the compound which improves the uniformity of the film thickness and surface smoothness of the liquid crystal aligning film at the time of apply|coating a liquid-crystal aligning agent, unless the effect of this invention is impaired. Moreover, the compound etc. which improve the adhesiveness of a liquid crystal aligning film and a board|substrate can also be used.

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

More specifically, for example, Ftop EF301, EF303, EF352 (above, manufactured by Tochem Products), Megapack F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (above) The above, made by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Suplon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, made by Asahi Glass Co., Ltd.), and the like. The proportion 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 the polymer components contained in the liquid crystal aligning agent.

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, the functional silane containing compound and epoxy group containing compound shown below are mentioned.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidpropyltrimethoxysilane, 3-ureidpropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltri Ethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol di Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglyceride Cydyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclo hexane or N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane; and the like.

When using the compound made to adhere with these board|substrates, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of all the polymer components contained in a liquid-crystal aligning agent, More preferably, it is 1-20 mass parts. When the effect of an adhesive improvement cannot be expected as it is less than 0.1 mass part, and it increases more than 30 mass parts, the storage stability of a liquid-crystal aligning agent may worsen.

In the liquid-crystal aligning agent of the present invention, in addition to the poor solvent, the crosslinkable compound, the compound that promotes charge loss of the liquid crystal cell, and the compound that improves the uniformity and surface smoothness of the film thickness of the liquid crystal aligning film, the effect of the present invention is inhibited. As long as it is not a range, you may add the dielectric material or conductive material for the purpose of changing electric characteristics, such as the dielectric constant and conductivity of a liquid crystal aligning film.

<Liquid crystal alignment film/liquid crystal display element>

After apply|coating and baking the liquid-crystal aligning agent of this invention on a board|substrate, it can carry out orientation processing by a rubbing process, light irradiation, etc., and can be used as a liquid crystal aligning film. Moreover, in the case of a vertical alignment use etc., it can be used as a liquid crystal aligning film even without orientation processing. The substrate used at this time is not particularly limited as long as it is a substrate having high transparency, and plastic substrates such as acrylic substrates and polycarbonate substrates can be used in addition to glass substrates. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed. In addition, in the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used as long as it is used for only one substrate, and a material that reflects light such as aluminum can be used as an electrode in this case.

Although the coating method of a liquid-crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, offset printing, flexographic printing, an inkjet method, etc. is common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, or a spray method, and these 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, preferably 30 to 300 ° C. can evaporate a solvent at the temperature of 30-250 degreeC, and can be set as a liquid crystal aligning film. If the thickness of the liquid crystal aligning film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, it is preferably 5 to 300 nm, more preferably Preferably, it is 10 to 100 nm. When horizontally aligning or tilting a liquid crystal, the liquid crystal aligning film after baking is processed by rubbing, polarization|polarized-light ultraviolet irradiation, etc.

After the liquid crystal display element of this invention obtained the board|substrate with a liquid crystal aligning film from the liquid crystal aligning agent of this invention by the above-mentioned method, it manufactured the liquid crystal cell by a well-known method, and used it as a liquid crystal display element. As an example, a liquid crystal cell having two substrates arranged to face each other, a liquid crystal layer formed between the substrates, and the liquid crystal alignment film formed between the substrate and the liquid crystal layer and formed by the liquid crystal aligning agent of the present invention. It is a liquid crystal display element. As such a liquid crystal display element of the present invention, a vertical alignment (VA: Vertical Alignment) method, a horizontal alignment (IPS: In-Plane Switching) method, a twisted nematic (TN: Twisted Nematic) method, an OCB alignment (OCB: Optically Compensated Bend) and the like, and a PSA (Polymer Sustained Alignment) method and the like may be used. In addition, the liquid crystal aligning film should just be formed in at least one of the board|substrates of 2 sheets.

As a manufacturing method of a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are spread on the liquid crystal alignment film of one side substrate, the liquid crystal alignment film surface is turned inside, and another one side substrate is bonded ( The method of sealing by injecting a liquid crystal under reduced pressure, or the method of bonding a board|substrate together and sealing, after dripping a liquid crystal on the surface of the liquid crystal aligning film which spread|dispersed the spacer, etc. can be illustrated.

As described above, even if the liquid crystal display element manufactured using the liquid-crystal aligning agent of this invention is exposed to light irradiation for a long time, since it has a liquid crystal aligning film in which the fall of voltage retention was suppressed, it becomes a thing excellent in reliability, and it is a large screen It can be suitably used for a high-definition liquid crystal television or the like.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in more detail.

Example

The present invention will be described in more detail by way of examples below, but it is not limited thereto.

Abbreviations used in synthesis examples and examples are as follows.

<Tetracarboxylic dianhydride>

(Specific tetracarboxylic dianhydride)

A1: Tetracarboxylic dianhydride represented by the following formula [A1]

[Formula 45]

(Specific aliphatic tetracarboxylic dianhydride)

A2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [A2])

A3: Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [A3])

A4: Tetracarboxylic dianhydride represented by the following formula [A4]

A5: Tetracarboxylic dianhydride represented by the following formula [A5]

[Formula 46]

(Other tetracarboxylic dianhydrides)

A6: Pyromellitic dianhydride (tetracarboxylic dianhydride represented by the following formula [A6])

[Formula 47]

<diamine component>

B1: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene (diamine compound represented by the following formula [B1])

B2: 1,3-diamino-5-[4-(trans-4-n-heptylcyclohexyl)phenoxymethyl]benzene (diamine compound represented by the following formula [B2])

B3: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene (diamine compound represented by the following formula [B3])

B4: 1,3-diamino-5-{4-[4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxymethyl}benzene (diamine compound represented by the following formula [B4])

B5: Specific side chain type diamine compound represented by the following formula [B5]

B6: 1,3-diamino-4-octadecyloxybenzene (diamine compound represented by the following formula [B6])

B7: m-phenylenediamine (diamine compound represented by the following formula [B7])

B8: p-phenylenediamine (diamine compound represented by the following formula [B8])

B9: 3,5-diaminobenzoic acid (diamine compound represented by the following formula [B9])

B10: diamine compound represented by the following formula [B10]

[Formula 48]

[Formula 49]

[Formula 50]

[Formula 51]

<organic solvent>

(polar solvent)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

G-BL: γ-butyrolactone

(other organic solvents)

BCS: 2-butoxyethanol

PB: Propylene glycol monobutyl ether

<Molecular weight measurement of polyimide precursor and polyimide>

The molecular weight of the polyimide precursor and polyimide in the synthesis example was determined by a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko), a column (KD-803, KD-805) (Shodex) manufacture) was used and measured as follows.

Column temperature: 50 ° C

Eluent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr H ₂ O) is 30 mmol/L (liter), phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L , tetrahydrofuran (THF) at 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 Laboratory)

<Measurement of imidization rate of polyimide>

The imidation rate of the polyimide in the synthesis example was measured as follows. 20 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) mixture) ) (0.53 mL) was added and ultrasonic was applied to dissolve completely. A 500 MHz proton NMR was measured for this solution with an NMR measuring device (JNW-ECA500) (manufactured by JEOL Datum Co., Ltd.). The imidation rate was determined using a proton derived from a structure that does not change before and after imidization as a reference proton, and the peak integration value of this proton and the proton peak derived from the NH group of amic acid appearing around 9.5 ppm to 10.0 ppm It calculated|required by the following formula using the integrated value.

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

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

<Synthesis Example 1>

After mixing A1 (3.82 g, 18.0 mmol), B1 (4.11 g, 10.8 mmol), and B7 (2.75 g, 25.2 mmol) in NMP (22.8 g) and reacting at 40 ° C. for 5 hours, A2 ( 3.53 g, 18.0 mmol) and NMP (18.7 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (A) whose solid content concentration is 20.0 mass % was obtained. The number average molecular weight of this polyamic acid was 11,500, and the weight average molecular weight was 38,600.

<Synthesis Example 2>

After mixing A1 (3.81 g, 18.0 mmol), B2 (4.25 g, 10.8 mmol), and B8 (2.72 g, 25.1 mmol) in NMP (23.1 g) and reacting at 40 ° C. for 5 hours, A2 ( 3.52 g, 18.0 mmol) and NMP (18.9 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution whose solid content concentration is 20.0 mass % was obtained.

After adding NMP to the obtained polyamic acid solution (15.0 g) and diluting to 6 mass %, acetic anhydride (2.01 g) and pyridine (1.02 g) were added as an imidation catalyst, and it was made to react at 40 degreeC for 4 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (B). The imidation rate of this polyimide was 50%, the number average molecular weight was 12,500, and the weight average molecular weight was 38,200.

<Synthesis Example 3>

After mixing A1 (2.83 g, 13.3 mmol), B6 (3.76 g, 10.0 mmol), and B10 (2.72 g, 23.3 mmol) in NMP (16.9 g) and reacting at 40 ° C. for 5 hours, A2 ( 3.92 g, 20.0 mmol) and NMP (13.8 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution whose solid content concentration is 20.0 mass % was obtained.

After adding NMP to the obtained polyamic acid solution (15.1 g) and diluting to 6 mass %, acetic anhydride (2.28 g) and pyridine (1.18 g) were added as an imidation catalyst, and it was made to react at 40 degreeC for 3 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (C). The imidation rate of this polyimide was 70%, the number average molecular weight was 11,500, and the weight average molecular weight was 31,400.

<Synthesis Example 4>

After mixing A1 (4.50 g, 21.2 mmol) and B7 (4.59 g, 42.4 mmol) in NMP (21.8 g) and reacting at 40 ° C. for 5 hours, A3 (5.31 g, 21.2 mmol) and NMP ( 17.8 g) was added, and it was made to react at 50 degreeC for 6 hours, and the polyamic acid solution whose solid content concentration is 20.0 mass % was obtained.

After adding NMP to the obtained polyamic acid solution (15.0g) and diluting to 6 mass %, acetic anhydride (2.73g) and pyridine (1.60g) were added as an imidation catalyst, and it was made to react at 40 degreeC for 3.5 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (D). The imidation rate of this polyimide was 53%, the number average molecular weight was 13,100, and the weight average molecular weight was 35,000.

<Synthesis Example 5>

After mixing A1 (1.10 g, 5.19 mmol), B1 (3.95 g, 10.4 mmol), and B9 (2.37 g, 15.6 mmol) in NMP (22.9 g) and reacting at 40 ° C. for 5 hours, A2 ( 4.07 g, 20.8 mmol) and NMP (18.7 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution whose solid content concentration is 20.0 mass % was obtained.

After adding NMP to the obtained polyamic acid solution (15.0g) and diluting to 6 mass %, acetic anhydride (2.12g) and pyridine (1.15g) were added as an imidation catalyst, and it was made to react at 40 degreeC for 3 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (E). The imidation rate of this polyimide was 52%, the number average molecular weight was 12,600, and the weight average molecular weight was 36,200.

<Synthesis Example 6>

After mixing A1 (7.80 g, 36.7 mmol) and B8 (6.11 g, 56.5 mmol) in NMP (22.0 g) and reacting at 40 ° C. for 5 hours, A2 (3.88 g, 19.8 mmol) and NMP ( 18.0 g) was added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (F) whose solid content concentration is 20.0 mass % was obtained. The number average molecular weight of this polyamic acid was 11,200, and the weight average molecular weight was 38,500.

<Synthesis Example 7>

After mixing A1 (1.41 g, 6.65 mmol), B5 (2.62 g, 5.32 mmol), and B9 (3.24 g, 21.3 mmol) in NMP (23.9 g) and reacting at 40 ° C. for 5 hours, A3 ( 4.99 g, 19.9 mmol) and NMP (19.5 g) were added, and it was made to react at 50 degreeC for 6 hours, and the polyamic acid solution (G) whose solid content concentration is 20.0 mass % was obtained. The number average molecular weight of this polyamic acid was 13,500, and the weight average molecular weight was 35,600.

<Synthesis Example 8>

After mixing A1 (3.06 g, 14.4 mmol), B3 (3.74 g, 8.65 mmol), and B10 (2.47 g, 20.2 mmol) in NMP (1.53 g) and reacting at 40 ° C. for 5 hours, A4 ( 3.23 g, 14.4 mmol) and NMP (12.6 g) were added, and it was made to react at 50 degreeC for 6 hours, and the solid content concentration obtained the polyamic acid solution of 20.0 mass %.

After adding NMP to the obtained polyamic acid solution (15.0g) and diluting to 6 mass %, acetic anhydride (1.89g) and pyridine (0.90g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (H). The imidation ratio of this polyimide was 70%, the number average molecular weight was 11,800, and the weight average molecular weight was 30,400.

<Synthesis Example 9>

A1 (2.25 g, 10.6 mmol), B4 (2.71 g, 6.06 mmol), B7 (1.64 g, 15.2 mmol), B9 (1.38 g, 9.09 mmol) were mixed in NMP (2.23 g) and 40 After making it react at degreeC for 5 hours, A4 (4.42g, 19.7 mmol) and NMP (18.3g) were added, it was made to react at 50 degreeC for 6 hours, and the solid content concentration obtained the polyamic acid solution of 20.0 mass %.

After adding NMP to the obtained polyamic acid solution (15.0 g) and diluting to 6 mass %, acetic anhydride (2.20 g) and pyridine (1.12 g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (I). The imidation ratio of this polyimide was 51%, the number average molecular weight was 11,000, and the weight average molecular weight was 30,100.

<Synthesis Example 10>

After mixing A1 (2.02 g, 9.52 mmol) and B8 (3.43 g, 31.7 mmol) in NMP (22.2 g) and reacting at 40 ° C. for 5 hours, A5 (6.67 g, 22.2 mmol) and NMP ( 18.2 g) was added, and it was made to react at 25 degreeC for 12 hours, and the polyamic acid solution (J) whose solid content concentration is 20.0 mass % was obtained. The number average molecular weight of this polyamic acid was 11,800, and the weight average molecular weight was 36,300.

<Synthesis Example 11>

A1 (11.2 g, 52.9 mmol), B1 (6.04 g, 15.9 mmol), and B7 (4.01 g, 37.1 mmol) were mixed in NMP (40.2 g) and reacted at 40°C for 24 hours to obtain a solid content concentration of A 20.0% by mass polyamic acid solution (K) was obtained. The number average molecular weight of this polyamic acid was 7,100, and the weight average molecular weight was 29,800.

<Synthesis Example 12>

A2 (5.10 g, 26.0 mmol), B6 (2.94 g, 7.80 mmol), and B10 (2.22 g, 18.2 mmol) were mixed in NMP (32.2 g) and reacted at 40°C for 8 hours to obtain a solid content concentration of A 20.0% by mass polyamic acid solution was obtained.

After adding NMP to the obtained polyamic acid solution (15.0 g) and diluting to 6 mass %, acetic anhydride (2.00 g) and pyridine (1.01 g) were added as an imidation catalyst, and it was made to react at 40 degreeC for 3 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (L). The imidation rate of this polyimide was 70%, the number average molecular weight was 13,800, and the weight average molecular weight was 35,600.

<Synthesis Example 13>

After mixing A3 (3.80 g, 15.2 mmol) and B7 (3.29 g, 30.4 mmol) in NMP (22.2 g) and reacting at 50 ° C. for 3 hours, A2 (2.98 g, 15.2 mmol) and NMP ( 18.1 g) was added, and it was made to react at 40 degreeC for 6 hours, and the solid content concentration obtained the polyamic acid solution of 20.0 mass %.

After adding NMP to the obtained polyamic acid solution (15.0 g) and diluting to 6 mass %, acetic anhydride (3.10 g) and pyridine (1.52 g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3.5 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (M). The imidation rate of this polyimide was 50%, the number average molecular weight was 14,700, and the weight average molecular weight was 37,100.

<Synthesis Example 14>

After mixing A1 (1.03 g, 4.85 mmol), B1 (3.70 g, 9.71 mmol), and B9 (2.22 g, 14.6 mmol) in NMP (22.3 g) and reacting at 40 ° C. for 5 hours, A6 ( 4.24 g, 19.4 mmol) and NMP (18.3 g) were added, and it was made to react at 40 degreeC for 6 hours, and the solid content concentration obtained the polyamic acid solution of 20.0 mass %.

After adding NMP to the obtained polyamic acid solution (15.0 g) and diluting to 6 mass %, acetic anhydride (1.86 g) and pyridine (0.98 g) were added as an imidation catalyst, and it was made to react at 40 degreeC for 3 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (N). The imidation ratio of this polyimide was 52%, the number average molecular weight was 13,800, and the weight average molecular weight was 34,700.

<Synthesis Example 15>

After mixing A6 (4.52 g, 20.7 mmol) and B8 (3.45 g, 31.9 mmol) in NMP (22.4 g) and reacting at 40 ° C. for 5 hours, A2 (2.19 g, 11.2 mmol) and NMP ( 18.3 g) was added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution (O) whose solid content concentration is 20.0 mass % was obtained. The number average molecular weight of this polyamic acid was 16,100, and the weight average molecular weight was 42,000.

Table 1 shows polyamic acids and polyimides obtained in Synthesis Examples 1 to 15.

<Example 1>

A polyamic acid solution (A) (9.03g), NMP (8.90g), and BCS (12.0g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 1 were mixed at 25°C for 8 hours, and the liquid-crystal aligning agent (1) got Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (1), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the above-mentioned conditions.

<Example 2>

The polyimide powder (B) (1.80g), NMP (9.02g), NEP (7.51g), and BCS (13.5g) obtained in Synthesis Example 2 were mixed at 25°C for 8 hours, and the liquid-crystal aligning agent (2) got it Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (2), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the conditions mentioned above.

<Example 3>

The polyimide powder (B) (1.50g), NMP (12.4g), NEP (10.3g), and BCS (18.6g) obtained in Synthesis Example 2 were mixed at 25°C for 8 hours, and the liquid crystal aligning agent (3) was prepared. got it Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

"Evaluation of the inkjet coatability of the liquid crystal aligning agent" was performed on the conditions mentioned above using the obtained liquid-crystal aligning agent (3).

<Example 4>

The polyimide powder (C) (1.80g), NMP (9.01g), G-BL (9.02g) and BCS (12.0g) obtained in Synthesis Example 3 were mixed at 25°C for 8 hours, and the liquid crystal aligning agent (4 ) was obtained. Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (4), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the conditions mentioned above.

<Example 5>

The polyimide powder (D) (1.80 g), NMP (7.53 g), NEP (12.1 g), G-BL (1.53 g) and PB (9.11 g) obtained in Synthesis Example 4 were mixed at 25°C for 8 hours. , The liquid-crystal aligning agent (5) was obtained. Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (5), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the above-mentioned conditions.

<Example 6>

Polyimide powder (E) (1.79g), NMP (9.00g), NEP (14.5g), BCS (3.02g) and PB (3.00g) obtained in Synthesis Example 5 were mixed at 25°C for 8 hours, and the liquid crystal An orientation treatment agent (6) was obtained. Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (6), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the conditions mentioned above.

<Example 7>

The polyimide powder (E) (1.50g), NMP (8.27g), NEP (16.5g), and PB (16.5g) obtained in Synthesis Example 5 were mixed at 25°C for 8 hours, and the liquid-crystal aligning agent (7) got it Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

"Evaluation of the inkjet coatability of the liquid-crystal aligning agent" was performed on the conditions mentioned above using the obtained liquid-crystal aligning agent (7).

<Example 8>

Polyamic acid solution (F) (9.00 g) having a solid content concentration of 20.0 mass% obtained in Synthesis Example 6, NMP (3.00 g), G-BL (9.06 g) and BCS (9.01 g) were mixed at 25°C for 8 hours. Thus, a liquid-crystal aligning agent (8) was obtained. Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (8), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the above-mentioned conditions.

<Example 9>

Polyamic acid solution (G) (9.01 g), NEP (9.02 g), G-BL (9.02 g), BCS (6.01 g) and PB (6.00 g) having a solid content concentration of 20.0 mass% obtained in Synthesis Example 7, It mixed at 25 degreeC for 8 hours and obtained the liquid-crystal aligning agent (9). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (9), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the conditions mentioned above.

<Example 10>

The polyimide powder (H) (1.80 g), NMP (6.00 g), NEP (6.05 g), BCS (6.04 g) and PB (3.01 g) obtained in Synthesis Example 8 were mixed at 25°C for 8 hours, and the liquid crystal An orientation treatment agent (10) was obtained. Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (10), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the above-mentioned conditions.

<Example 11>

Polyimide powder (I) (1.80g), NMP (12.0g), NEP (9.00g), and BCS (9.05g) obtained in Synthesis Example 9 were mixed at 25°C for 8 hours, and the liquid-crystal aligning agent (11) got it Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (11), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the above-mentioned conditions.

<Example 12>

The polyamic acid solution (J) (9.04 g), NMP (16.5 g), NEP (9.02 g) and PB (4.50 g) having a solid content concentration of 20.0 mass% obtained in Synthesis Example 10 were mixed at 25 ° C. for 8 hours, A liquid-crystal aligning agent (12) was obtained. Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (12), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the above-mentioned conditions.

<Comparative Example 1>

A polyamic acid solution (K) (9.03g), NMP (9.31g), and BCS (12.2g) having a solid content concentration of 20.0 mass% obtained in Synthesis Example 11 were mixed at 25°C for 8 hours, and the liquid-crystal aligning agent (13) got Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (13), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the above-mentioned conditions.

<Comparative Example 2>

The polyimide powder (L) (1.80 g), NMP (9.00 g), G-BL (9.02 g), and BCS (12.0 g) obtained in Synthesis Example 12 were mixed at 25°C for 8 hours, and the liquid crystal aligning agent (14 ) was obtained. Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

"Preparation of a liquid crystal cell and evaluation of electrical characteristics" were implemented on the conditions mentioned above using the obtained liquid-crystal aligning agent (14).

<Comparative Example 3>

Polyimide powder (M) (1.80 g), NMP (7.50 g), NEP (12.0 g), G-BL (1.50 g) and PB (9.00 g) obtained in Synthesis Example 13 were mixed at 25°C for 8 hours, , The liquid-crystal aligning agent (15) was obtained. Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (15), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the above-mentioned conditions.

<Comparative Example 4>

The polyimide powder (N) (1.80 g), NMP (9.00 g), NEP (15.0 g), BCS (3.06 g) and PB (3.03 g) obtained in Synthesis Example 14 were mixed at 25°C for 8 hours, and the liquid crystal An orientation treatment agent (16) was obtained. Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (16), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the above-mentioned conditions.

<Comparative Example 5>

A polyamic acid solution (O) (9.05 g) having a solid content concentration of 20.0 mass% obtained in Synthesis Example 15, NMP (3.00 g), G-BL (9.02 g) and BCS (9.00 g) were mixed at 25°C for 8 hours. Thus, a liquid-crystal aligning agent (17) was obtained. Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Using the obtained liquid-crystal aligning agent (17), "preparation of a liquid crystal cell and evaluation of electrical characteristics" were performed on the above-mentioned conditions.

"Preparation of a liquid crystal cell", "evaluation of electrical characteristics (voltage retention)" and "evaluation of the inkjet coating property of a liquid crystal aligning agent" were performed using the liquid-crystal aligning agent obtained by each Example of this invention and each comparative example. . The conditions are as follows.

In Table 1 and Table 2, the raw material (tetracarboxylic dianhydride and diamine component) of the specific polymer which the liquid-crystal aligning agent obtained by Examples 1-12 and Comparative Examples 1-5 contains is shown.

<Manufacture of liquid crystal cell and evaluation of electrical characteristics>

The liquid-crystal aligning agent obtained in Examples 1, 2, 4-6, 8-12 and Comparative Examples 1-5 was filtered under pressure with a membrane filter having a pore diameter of 1 μm, and a liquid crystal cell was manufactured. This solution was spin-coated on the ITO surface of a substrate with 30 × 40 mm ITO electrodes (40 mm in length × 30 mm in width, 0.7 mm in thickness) washed with pure water and IPA, and then on a hot plate at 80 ° C. for 5 minutes, The heat treatment was performed at 230°C for 30 minutes in a heat circulation type clean oven to obtain an ITO substrate with a polyimide liquid crystal aligning film having a film thickness of 100 nm. The coating film surface of this ITO substrate was rubbed using a rayon cloth with a rubbing device having a roll diameter of 120 mm under conditions of a roll rotation speed of 1000 rpm, a roll travel speed of 50 mm/sec, and a press-in amount of 0.1 mm.

Two obtained ITO substrates with a liquid crystal aligning film were prepared, the liquid crystal aligning film surface was turned inside, and a 6 µm spacer was pinched and combined, and a sealing compound (XN-1500T) (manufactured by Mitsui Chemicals, Inc.) was printed. Then, after bonding together with the other substrate and the liquid crystal aligning film surface facing each other, the sealing compound was cured by heat-processing at 150°C for 90 minutes in a heat circulation type clean oven to prepare an empty cell. A 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.

Furthermore, the liquid-crystal aligning agent obtained in Example 1 (1), the liquid-crystal aligning agent obtained in Example 2 (2), the liquid-crystal aligning agent obtained in Example 4 (4), the liquid-crystal aligning agent obtained in Example 6 (6), Liquid-crystal aligning agent (9) - liquid-crystal aligning agent (11) obtained in Example 9 - Example 11, liquid-crystal aligning agent (13) obtained in Comparative Example 1, liquid-crystal aligning agent (14) obtained in Comparative Example 2, and Comparative Example 4 In the liquid crystal cell using the liquid-crystal aligning agent (16) obtained in , a nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Co., Ltd.) was used for the liquid crystal.

Moreover, the liquid-crystal aligning agent (5) obtained in Example 5, the liquid-crystal aligning agent (8) obtained in Example 8, the liquid-crystal aligning agent (12) obtained in Example 12, the liquid-crystal aligning agent (15) obtained in Comparative Example 3, and In the liquid crystal cell using the liquid-crystal aligning agent (17) obtained by the comparative example 5, the nematic liquid crystal (MLC-2041) (made by Merck Japan) was used for the liquid crystal.

The liquid-crystal orientation was evaluated using the liquid crystal cell obtained above. The liquid crystal orientation observed the liquid crystal cell with a polarization microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation), and confirmed the presence or absence of an orientation defect. As a result, no alignment defect was observed in the liquid crystal cells obtained in any of Examples and Comparative Examples, and uniform orientation was exhibited.

In addition, a voltage of 1 V of 60 μm was applied to the liquid crystal cell prepared above at a temperature of 80 ° C., the voltages after 16.67 ms and after 50 ms were measured, and how much voltage could be maintained was determined by voltage retention (VHR). was calculated as In addition, the measurement was performed using a VHR-1 voltage holding ratio measuring device (manufactured by Toyo Technica) under the settings of Voltage: ±1 V, Pulse Width: 60 μs, and Flame Period: 16.67 ms or 50 ms. Moreover, after irradiating the liquid crystal cell which the measurement of voltage retention was complete|finished with the ultraviolet-ray of 50 J/cm<2> in conversion of 365 nm, the voltage retention was measured under the same conditions as the above. In addition, ultraviolet irradiation was performed using a tabletop UV curing apparatus (HCT3B28HEX-1) (manufactured by Senlight Corporation).

In Table 3, the measurement result of voltage retention is shown. In addition, since voltage retention depends on the kind of diamine component, it is necessary to compare things using the same diamine component.

Compared with the liquid crystal aligning film obtained from the liquid-crystal aligning agent of each comparative example, even if the liquid crystal aligning film obtained from the liquid-crystal aligning agent of each Example was exposed to irradiation of an ultraviolet-ray, the fall of voltage retention decreased.

Specifically, in Example 1, two types of tetracarboxylic dianhydride, specific tetracarboxylic dianhydride and specific aliphatic tetracarboxylic dianhydride, were used, but in Comparative Example 1, one specific tetracarboxylic dianhydride was used. Only acid dianhydride is used. In addition, the diamine component (B1 and B7) is the same. As a result, the voltage holding ratio of Comparative Example 1 was greatly reduced by irradiation with ultraviolet rays.

Similarly, in Example 4, two types of tetracarboxylic dianhydride are used, but in Comparative Example 2, only the other specific aliphatic tetracarboxylic dianhydride is used. In addition, the diamine components (B6 and B10) are the same. As a result, the voltage holding ratio of Comparative Example 2 was further greatly reduced by irradiation with ultraviolet rays.

The comparison between Example 5 and Comparative Example 3 also yielded the same results.

In addition, in the comparison between Example 6 and Comparative Example 4 and Example 8 and Comparative Example 5, either one of the two types of tetracarboxylic dianhydride and the other tetracarboxylic dianhydride were used in Comparative Examples 4 and 5. However, the voltage holding ratios of Comparative Examples 4 and 5 were greatly reduced by irradiation with ultraviolet rays.

As a result, as a raw material of the specific polymer which the liquid-crystal aligning agent of this invention contains, by using two types of tetracarboxylic dianhydride of specific tetracarboxylic dianhydride and specific aliphatic tetracarboxylic dianhydride, voltage retention It turned out that the fall of is suppressed and the liquid crystal aligning film which has excellent light tolerance can be manufactured. Even if the liquid crystal display element which has such a liquid crystal aligning film is exposed to light irradiation for a long time, it has light tolerance and becomes a thing excellent in reliability, without a voltage retention falling.

<Evaluation of the inkjet coating property of the liquid crystal aligning agent>

The liquid-crystal aligning agent (3) obtained in Example 3 of the present invention and the liquid-crystal aligning agent (7) obtained in Example 7 were filtered under pressure with a membrane filter having a pore diameter of 1 μm, and inkjet coating properties were evaluated. For the inkjet coating machine, HIS-200 (manufactured by Hitachi Plant Technology Co., Ltd.) was used. The application was performed on an indium tin oxide (ITO) deposited substrate cleaned 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, the time from application to pre-drying was 60 seconds, and pre-drying was carried out on a hot plate at 70°C for 5 minutes.

In any Example, on the obtained liquid crystal aligning film, repelling and a pinhole were not seen, but the liquid crystal aligning film apply|coated uniformly was obtained.

Here, the liquid-crystal aligning agent (3) obtained in Example 3 and the liquid-crystal aligning agent (7) obtained in Example 7 are two types of tetracarboxylic dianhydride specific tetracarboxylic dianhydride and specific aliphatic tetracarboxylic dianhydride. It contains the specific polymer obtained by making acid dianhydride and a diamine component react. Specifically, the liquid-crystal aligning agent (3) of Example 3 is the same structure as the liquid-crystal aligning agent (2) of Example 2, and the liquid-crystal aligning agent (7) of Example 7 is the liquid-crystal aligning agent of Example 6 It is the same configuration as (6).

For this reason, the liquid crystal aligning film obtained by the inkjet method using the liquid-crystal aligning agent (3) of Example 3 and the liquid-crystal aligning agent (7) of Example 7 measured the voltage retention mentioned above (Examples 2 and 6 ), it is estimated that the decrease in voltage retention is suppressed and it has excellent light tolerance. Therefore, even if it exposes to irradiation of light for a long time similarly about the liquid crystal display element which has a liquid crystal aligning film obtained by the inkjet method, it becomes a thing excellent in reliability, without voltage retention falling.

Claims (10)

Having a tetracarboxylic acid component containing tetracarboxylic dianhydride represented by the following formula [1] and aliphatic tetracarboxylic dianhydride represented by the following formula [2] and a structure represented by the following formula [3] Contains at least one polymer selected from a polyimide precursor obtained by reacting a diamine component containing a diamine compound and a polyimide obtained by imidizing the polyimide precursor,
The liquid-crystal aligning agent characterized by the diamine compound which has a structure represented by said Formula [3] being 5 mol% or more and 80 mol% or less of the whole diamine component.

(In formula [2], Z ¹ is at least one kind of tetravalent group selected from the following formula [2a] to formula [2j].)

(In formula [2a], 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 in formula [2g], Z ⁶ and Z ⁷ are a hydrogen atom or a methyl group , which may be the same or different.)

(In formula [3], Y represents at least one monovalent group selected from the following formula [3-1] or formula [3-5], m represents an integer of 1 to 4, -(Y) _m indicates that there are m substituents Y.)

(In formula [3-1], a represents an integer of 0 to 4.
In formula [3-5], Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group having 1 to 12 carbon atoms.) According to claim 1,
The liquid-crystal aligning agent whose said polymer is a polyimide. According to claim 1,
A liquid-crystal aligning agent characterized by containing N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone as a solvent in the liquid-crystal aligning agent. According to claim 1,
As a solvent in a liquid-crystal aligning agent, the liquid-crystal aligning agent characterized by containing the solvent chosen from the solvent represented by the following formula [D-1] - formula [D-3].

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms.) It is obtained using the liquid-crystal aligning agent in any one of Claims 1-4, The liquid crystal aligning film characterized by the above-mentioned. The liquid crystal aligning film characterized by being obtained by an inkjet method using the liquid-crystal aligning agent in any one of Claims 1-4. The liquid crystal display element characterized by having the liquid crystal aligning film of Claim 5. delete delete delete