KR102609036B1 - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

A liquid crystal aligning agent containing the following (A) component and (B) component.
(A) Component: At least one type of polymer selected from a polyimide precursor having a side chain that vertically aligns the liquid crystal and a side chain having a radical generation site, and a polyimide obtained by imidizing the same.
(B) Component: a polymer selected from a polyimide precursor obtained using at least one type of diamine selected below and a polyimide obtained by imidizing it, or at least one type of tetracarboxylic dianhydride selected below. A polymer selected from polyimide precursors obtained by using them and polyimides obtained by imidizing them.
The definitions of symbols in the formula are the same as those described in the specification.

Description

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

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display device that can be used in a vertically aligned liquid crystal display device manufactured by irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules.

A liquid crystal display element in which liquid crystal molecules aligned perpendicularly to the substrate are responded to by an electric field (also referred to as vertical alignment (VA) method) involves a process of irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules during the manufacturing process. There is something that includes .

In such a vertically aligned liquid crystal display device, a photopolymerizable compound is added to the liquid crystal composition in advance, a vertical alignment film such as a polyimide type is used, and ultraviolet rays are irradiated while applying a voltage to the liquid crystal cell to change the response of the liquid crystal. Technology for increasing the speed (PSA (Polymer Sustained Alignment) type device, for example, see Patent Document 1 and Non-Patent Document 1) is known.

In such a PSA type device, the direction in which the liquid crystal molecules in response to the electric field are tilted is usually controlled by protrusions formed on the substrate or slits formed in the display electrode, but the liquid crystal cell is formed by adding a photopolymerizable compound to the liquid crystal composition. By irradiating ultraviolet rays while applying a voltage, a polymer structure that remembers the direction in which the liquid crystal molecules are tilted is formed on the liquid crystal alignment film, so the response of the liquid crystal display device is better than the method of controlling the tilt direction of the liquid crystal molecules with only protrusions or slits. It is said that the speed is increasing.

On the other hand, in this PSA type liquid crystal display device, there is also a problem that unreacted polymerizable compounds remaining in the liquid crystal become impurities (contamination) in the liquid crystal, thereby lowering the reliability of the liquid crystal display device. In addition, if the UV irradiation treatment required for the PSA method is large, the components in the liquid crystal decompose, causing a decrease in reliability.

In addition, it has been reported that the response speed of a liquid crystal display element increases by adding a photopolymerizable compound not to the liquid crystal composition but to the liquid crystal alignment film (SC-PVA type liquid crystal display, see, for example, Non-Patent Document 2). .

Japanese Patent Publication No. 2003-307720

K. Hanaoka, SID 04 DIGEST, P.1200-1202 K.H Y.-J. Lee, SID 09 DIGEST, P.666-668

Recently, as the quality of liquid crystal display elements has improved, there has been a demand to further speed up the response speed of the liquid crystal to voltage application. To achieve this, it is necessary for the polymerizable compound to react efficiently with long-wavelength ultraviolet irradiation that does not decompose the components in the liquid crystal, thereby demonstrating the ability to fix the orientation. In addition, there is a need for no unreacted polymerizable compound to remain after ultraviolet irradiation, so as not to adversely affect the reliability of the liquid crystal display device.

In addition, it is also desired to improve the electrical characteristics of the resulting liquid crystal display element, especially to improve the direct current charge accumulation characteristics.

The object of the present invention is to solve the problems of the prior art described above, and the response speed of the vertically aligned liquid crystal display device can be improved by efficiently reacting the polymerizable compound even with long-wavelength ultraviolet irradiation, Furthermore, the object is to provide a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display device, and a method for manufacturing a liquid crystal display device that can improve the electrical properties of the obtained liquid crystal display device, especially the direct current charge accumulation characteristics.

As a result of intensive examination, the present inventors found that the above-described subject could be achieved by introducing a specific structure that generates a radical by ultraviolet irradiation into the polymer constituting the liquid crystal aligning agent, and completed this invention.

That is, the present invention has the following gist.

1. A liquid crystal aligning agent characterized by containing the following (A) component, (B) component, and organic solvent.

(A) Component: A polyimide precursor having a side chain that vertically aligns the liquid crystal and a side chain that has a site that generates radicals upon ultraviolet irradiation represented by the formula (I) below, and this polyimide precursor is imidized. At least one type of polymer selected from the polyimide obtained.

[Formula 1]

R ₁ and R ₂ are each independently an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and T ₁ and T ₂ are each independently a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, -N(CH ₃ )CO-, and S is a single bond or unsubstituted or It is an alkylene group having 1 to 20 carbon atoms substituted by a fluorine atom, and Ar is naphthylene, biphenylene, or phenylene, and the naphthylene, biphenylene, or phenylene is an alkyl group, a hydroxyl group, or an alkoxy group. and may be substituted with at least one substituent selected from the group consisting of amino groups. However, -CH ₂ - or -CF ₂ - of the alkylene group may be optionally substituted with -CH=CH-, and may be substituted with any of the groups illustrated below in the case where they are not adjacent to each other; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbon ring, a divalent heterocycle, and Q represents a structure selected from the following.

[Formula 2]

R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

(B) Component: A polyimide precursor obtained by using a diamine component containing at least one type of diamine selected from the following formulas (B-1) to (B-5) as a raw material, and a polyimide precursor obtained by imidizing the polyimide precursor. A polyimide precursor obtained using a polymer selected from polyimides or a tetracarboxylic dianhydride component containing at least one tetracarboxylic dianhydride selected from the following formulas (3) and (4) as a raw material, and A polymer selected from polyimides obtained by imidizing this polyimide precursor.

[Formula 3]

Y ₁ is a secondary amine, a tertiary amine, or a monovalent organic group having a heterocyclic structure, and Y ₂ is a secondary amine, a tertiary amine, or a divalent organic group having a heterocyclic structure.

[Formula 4]

n, m are 0 or 1, and X, y are a single bond, carbonyl, ester, phenylene, or sulfonyl group.

2. A liquid crystal alignment film obtained by applying the liquid crystal aligning agent described in 1 to a substrate and baking it.

3. A liquid crystal display characterized by applying the liquid crystal aligning agent described in 1 to a substrate, contacting it with a liquid crystal alignment film obtained by baking, forming a liquid crystal layer, and providing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to this liquid crystal layer. device.

4. A liquid crystal display characterized by applying the liquid crystal aligning agent described in 1 to a substrate, contacting it with a liquid crystal alignment film obtained by baking, forming a liquid crystal layer, and producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to this liquid crystal layer. Method of manufacturing the device.

According to the present invention, the response speed of the liquid crystal can be increased even when irradiated with long-wavelength ultraviolet rays, and a vertically aligned liquid crystal display device with less accumulation of direct current charges can be provided.

The liquid crystal aligning agent of this invention contains the following (A) component, (B) component, and an organic solvent.

(A) Component: A polyimide precursor having a side chain that vertically aligns the liquid crystal and a side chain that has a site that generates radicals upon ultraviolet irradiation represented by the formula (I) below, and this polyimide precursor is imidized. At least one type of polymer selected from the polyimide obtained.

[Formula 5]

(B) Component: selected from the group consisting of a polyimide precursor obtained using at least one diamine selected from the following formulas (B-1) to (B-5) as a raw material, and a polyimide obtained by imidizing this polyimide precursor. A polymer selected from a polymer or a polyimide precursor obtained using at least one tetracarboxylic dianhydride selected from the following formulas (3) and (4) as a raw material, and a polyimide obtained by imidizing this polyimide precursor. .

[Formula 6]

[Formula 7]

A liquid crystal aligning film is a solution for forming a liquid crystal aligning film, and a liquid crystal aligning film is a film for aligning a liquid crystal in a predetermined direction.

Below, each configuration requirement is described in detail.

＜(A) Ingredient＞

The liquid crystal aligning agent of the present invention is a polyimide precursor having a side chain that vertically aligns the liquid crystal and a side chain that has a site that generates radicals by ultraviolet irradiation represented by the formula (1) above, and this polyimide precursor. It is at least one type of polymer selected from polyimides obtained by imidization.

Here, the polyimide precursor refers to polyamic acid and polyamic acid ester.

＜Side chains that generate radicals when irradiated with ultraviolet rays＞

(A) component contained in the liquid crystal aligning agent of this invention has the site|part where a radical generate|occur|produces as a side chain by ultraviolet irradiation. The site where radicals are generated by ultraviolet irradiation can be represented by the following formula (I).

[Formula 8]

In the above formula (I), Ar to which the carbonyl is bonded is involved in the absorption wavelength of ultraviolet rays, so when increasing the wavelength, a structure with a long conjugate length such as naphthylene or biphenylene is preferable. Additionally, Ar may be substituted with a substituent, and such substituent is preferably an electron-donating organic group such as an alkyl group, hydroxyl group, alkoxy group, or amino group.

If Ar has a structure like naphthylene or biphenylene, the solubility deteriorates and the difficulty of synthesis also increases. If the wavelength of ultraviolet rays is in the range of 250 nm to 380 nm, the phenyl group is most preferable because sufficient properties can be obtained even with the phenyl group.

In addition, R ₁ and R ₂ are each independently an alkyl group, an alkoxy group, a benzyl group, or a phenethyl group having 1 to 10 carbon atoms, and in the case of an alkyl group or an alkoxy group, R ₁ and R ₂ may form a ring. .

Q is preferably an electron-donating organic group, and is preferably as follows.

[Formula 9]

(R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ represents -CH ₂ -, -NR-, -O-, or -S-.)

When Q is represented by -OR, R is preferably an alkyl group having 1 to 4 carbon atoms for the purpose of increasing the surface abundance of component (A) after application. This is because by setting Q to alkyl, the polarity is lowered and it is easier to transfer to the surface. Also, considering the difficulty of synthesis, etc., 1 to 2 are more preferable, and 1 is most preferable.

When Q is an amino derivative, problems such as the carboxylic acid group and amino group forming a salt may occur during polymerization of polyamic acid, which is the precursor of polyimide, so it is more preferable to use a hydroxyl group or an alkoxy group. It's a practical skill.

As a polymer containing a liquid crystal aligning agent, when using a polyimide precursor and or polyimide and trying to introduce the structure of the said formula (I) into a side chain, setting it as the side chain structure of this formula (I) is of a raw material. It is preferable in terms of handling properties and ease of polymer synthesis.

The site that generates radicals by ultraviolet irradiation in the formula (I) is specifically preferably as follows. In particular, (b), (c) or (d) is preferable from the point of reliability of the resulting liquid crystal display element, and (d) is more preferable from the point of the surface layer abundance of the radical generation site on the surface of the liquid crystal alignment film.

[Formula 10]

In addition, -T ₁ -ST ₂ - serves as a linking group connecting diaminobenzene and the site where radicals are generated by ultraviolet irradiation. T ₁ and T ₂ are each independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-. S is a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom (however, -CH ₂ - or -CF ₂ - of the alkylene group may be optionally substituted with -CH=CH- , if any of the following groups are not adjacent to each other, they may be substituted with these groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbon ring or heterocycle) am. In particular, -O- is most preferable for T ₂ in terms of difficulty in synthesis. Moreover, S is preferably an alkylene group with 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, from the viewpoint of difficulty in synthesis and solubility.

＜Side chains that orient the liquid crystal vertically＞

It is preferable that the polymer contained in the liquid crystal aligning agent of this invention has a side chain which aligns a liquid crystal perpendicularly other than the side chain represented by said formula (I). The side chain that vertically aligns the liquid crystal is represented by the following formula [II-1] or formula [II-2].

[Formula 11]

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and n in formula [II-1] are as defined above.

Among them, X ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO- is preferable, and more preferable is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O-, or -COO-. Among them, X ² is preferably a single bond or (CH ₂ ) _b - (b is an integer of 1 to 10). X ³ is, among others, preferably a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO- from the viewpoint of ease of synthesis. , more preferable ones are single bonds, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

Among them, X ⁴ is preferably an organic group of 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton from the viewpoint of ease of synthesis. X ⁵ is especially preferably a benzene ring or a cyclohexane ring. Among these, n is preferably 0 to 3, and more preferably 0 to 2, from the viewpoint of availability of raw materials and ease of synthesis.

Among these, X ⁶ is preferably an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 10 carbon atoms, an alkoxyl group with 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group with 1 to 10 carbon atoms. More preferably, it is an alkyl group with 1 to 12 carbon atoms or an alkoxyl group with 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

^A preferable combination of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , The same combinations as (2-1) to (2-629) shown in Tables 6 to 47 on pages 34 to 34 can be used. In addition, in each table of the international publication, X ¹ to X ⁶ in the present invention are shown as Y1 to Y6, but Y1 to ^Y6 are read as X ¹ to

In addition, in (2-605) to (2-629) published in each table of the International Publication Publication, the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention is a group having 12 to 25 carbon atoms having a steroid skeleton. Although shown as an organic group, an organic group having 12 to 25 carbon atoms having a steroid skeleton is read as an organic group having 17 to 51 carbon atoms having a steroid skeleton. Among them, (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483) or (2-603) to (2-615) is preferable. Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).

[Formula 12]

In formula [II-2], X ⁷ and X ⁸ are as defined above. _Among ^them _, CONH- or -COO-. X ⁸ Among them, an alkyl group having 8 to 18 carbon atoms is preferable.

As the side chain for vertically aligning the liquid crystal, it is preferable to use the structure represented by the formula [II-1] because high and stable vertical alignment of the liquid crystal can be obtained.

In addition, the ability of a polymer having a side chain to vertically align the liquid crystal varies depending on the structure of the side chain to vertically align the liquid crystal, but generally, the amount of side chains to vertically align the liquid crystal As this increases, the ability to vertically align the liquid crystal increases, and as it decreases, it decreases. Additionally, when it has a cyclic structure, the ability to vertically align the liquid crystal tends to be higher compared to when it does not have a cyclic structure.

＜Photo-reactive side chain＞

The (A) component contained in the liquid crystal aligning agent of this invention may have a photoreactive side chain other than the side chain represented by said formula (I). The photoreactive side chain has a functional group (hereinafter also referred to as a photoreactive group) that can react with irradiation of light such as ultraviolet rays (UV) to form a covalent bond.

The photoreactive side chain may be directly bonded to the main chain of the polymer, or may be bonded through a linking group. The photoreactive side chain is represented by the following formula (III), for example.

[Formula 13]

In formula (III), R ⁸ , R ⁹ , and R ¹⁰ are as defined above. Among them, R ⁸ is preferably a single bond, -O-, -COO-, -NHCO-, or -CONH-. R ⁹ can be formed by conventional organic synthesis methods, but from the viewpoint of ease of synthesis, a single bond or an alkylene group having 1 to 12 carbon atoms is preferable.

In addition, the divalent carbon ring or heterocycle that substitutes any -CH ₂ - of R ⁹ is specifically exemplified by the following.

[Formula 14]

R ¹⁰ is preferably a methacryl group, an acrylic group, a vinyl group, or a styryl group from the viewpoint of photoreactivity.

The amount of the photoreactive side chain is preferably in a range that can speed up the response speed of the liquid crystal by reacting with irradiation of ultraviolet rays to form a covalent bond. In order to speed up the response speed of the liquid crystal, other characteristics It is desirable to have as much as possible without affecting it.

＜Specific diamine＞

The diamine (hereinafter also referred to as specific diamine) used for production of the polymer that forms the liquid crystal aligning agent of the present invention has as a side chain a site that is decomposed by ultraviolet ray irradiation and generates radicals.

[Formula 15]

Ar, R ₁ , R ₂ , T ₁ , T ₂ , and Sn in the above formula (1) are as defined above.

Diaminobenzene in formula (1) may have any structure of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine, but is m-phenylenediamine in terms of reactivity with acid dianhydride. , or p-phenylenediamine is preferred.

As a specific diamine, the structure represented by the following formula is most preferable from the viewpoint of ease of synthesis, high versatility, and properties. In addition, in the formula, n is an integer of 2 to 8.

[Formula 16]

<Synthesis of specific diamine>

In the present invention, the specific diamine is synthesized through each step to form a dinitro form, or a mononitro form or diamine having an amino group with a protective group that can be removed in the reduction step, and convert the nitro group into an amino group or a protecting group by a commonly used reduction reaction. It can be obtained by deprotecting .

There are various methods for synthesizing diamine precursors. For example, a method of synthesizing a site where a radical is generated by irradiation with ultraviolet rays, introducing a spacer site, and then combining it with dinitrobenzene is shown below. In addition, in the formula, n is an integer of 2 to 8.

[Formula 17]

In the case of the above reaction, one having two hydroxyl groups is used, but selective synthesis can be achieved by optimizing the type and injection ratio of the base (catalyst).

The base used is not particularly limited, but inorganic bases such as potassium carbonate, sodium carbonate, and cesium carbonate, and organic bases such as pyridine, dimethylaminopyridine, trimethylamine, triethylamine, and tributylamine are preferable.

There is no particular limitation on the method of reducing the dinitro compound, which is a diamine precursor, and usually palladium carbon, platinum oxide, Raney nickel, platinum carbon, rhodium-alumina, platinum sulfide carbon, etc. are used as catalysts, and ethyl acetate, toluene, and tetrahydrate are used as catalysts. Among solvents such as hydrofuran, dioxane, and alcohol, there is a method of performing reduction using hydrogen gas, hydrazine, hydrogen chloride, etc. If necessary, an autoclave, etc. may be used.

On the other hand, when the structure contains an unsaturated bonding site, if palladium carbon, platinum carbon, etc. are used, the unsaturated bonding site may be reduced and become a saturated bond. Therefore, preferred conditions include reduced iron, tin, tin chloride, etc. Reduction conditions using a transition metal, poisoned palladium carbon, platinum carbon, iron-doped platinum carbon, etc. as a catalyst are preferable.

Additionally, the diamine of the present invention can be obtained from diaminobenzene derivatives protected with a benzyl group or the like by similarly deprotecting them in the above reduction step.

As for specific diamine, it is preferable to use 10-80 mol% of the diamine component used for the synthesis|combination of a polyamic acid, More preferably, it is 20-60 mol%, Especially preferably, it is 30-50 mol%.

<Diamine having a side chain that vertically orients the liquid crystal>

In the method of introducing a side chain that vertically aligns the liquid crystal into a polyimide polymer, it is preferable to use a diamine having a specific side chain structure as part of the diamine component. In particular, it is preferable to use the diamine (also referred to as a specific side chain type diamine compound) represented by the following formula [2].

[Formula 18]

In formula [2],

As the specific side chain type diamine, it is preferable to use the diamine represented by the following formula [2-1] from the point that high and stable vertical alignment of the liquid crystal can be obtained.

[Formula 19]

X ¹ , X ^{2 ,} X ³ , X ⁴ , Preferred ones are also the same as those defined in each of the above formulas [II-1].

In addition, in formula [2-1], m is an integer of 1 to 4. Preferably it is an integer of 1.

Specific side chain type diamine specifically includes structures represented by the following formula [2a-1] to formula [2a-31].

[Formula 20]

(R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and R ² is a straight-chain or branched alkyl group having 1 to 22 carbon atoms, 1 carbon atom A straight-chain or branched alkoxyl group with ∼22 carbon atoms, a straight-chain or branched fluorine-containing alkyl group or a fluorine-containing alkoxyl group with 1 to 22 carbon atoms.)

[Formula 21]

(R ³ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or -CH ₂ -, R ⁴ is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group or a fluorine-containing alkoxyl group having 1 to 22 carbon atoms. It is a practical skill).

[Formula 22]

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

[Formula 23]

(R ⁷ is a straight-chain or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of 1,4-cyclohexylene are each trans isomers).

[Formula 24]

(R ⁸ is a straight-chain or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of 1,4-cyclohexylene are each trans isomers).

[Formula 25]

(A ₄ is a straight-chain or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₃ is a 1,4-cyclohexylene group or 1,4-phenylene group, and A ₂ is an oxygen atom or COO-* (however, the bond to which “*” is attached combines with A ₃ ), and A ₁ is an oxygen atom or COO-* (however, the bond to which “*” is attached is (CH ₂ )a ₂ ). combine). Moreover, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1).

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

Among the above formulas [2a-1] to [2a-31], particularly preferred ones are formula [2a-1] to formula [2a-6], formula [2a-9] to formula [2a-13] or formula [2a- 22] ~ Formula [2a-31].

Moreover, as diamine which has a specific side chain structure represented by said formula [II-2], diamine represented by the following formula [2b-1] - [2b-10] is mentioned.

[Formula 31]

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

[Formula 32]

[Formula 33]

[Formula 34]

In the above formulas [2b-5] to [2b-10], A ¹ is -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH - represents, and 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.

The said diamine can also be used 1 type or in mixture of 2 or more types depending on characteristics, such as liquid crystal orientation when used as a liquid crystal alignment film, a pretilt angle, a voltage maintenance characteristic, and an accumulated charge.

The diamine having a side chain that vertically aligns the liquid crystal is preferably used in an amount of 5 to 50 mol% of the diamine component used in the synthesis of polyamic acid, more preferably in an amount of 10 to 40 mol% of the diamine component, especially Preferably it is 15 to 30 mol%.

The use of a diamine having a side chain that vertically aligns the liquid crystal is particularly excellent in terms of improvement in response speed and the ability to fix the orientation of the liquid crystal.

<Diamine containing photoreactive side chains>

Examples of diamines having a photoreactive side chain include diamines having a side chain represented by formula (3), and specifically include diamines represented by the following general formula (3), but are not limited to this. .

[Formula 35]

(The definitions of R ⁸ , R ⁹ and R ¹⁰ in formula (3) are the same as in formula (III) above.)

The bonding position of two amino groups (-NH ₂ ) in formula (3) is not limited. Specifically, with respect to the linking group in the side chain, the positions 2,3, 2,4, 2,5, 2,6, 3,4, and 3,5 on the benzene ring. I can hear it. Among them, the 2,4 position, 2,5 position, or 3,5 position is preferable from the viewpoint of reactivity when synthesizing polyamic acid. Considering the ease of synthesizing diamine, the 2,4 position or the 3,5 position is more preferable.

Diamines having photoreactive side chains specifically include the following.

[Formula 36]

(X ^{9 and} .)

Moreover, as diamine which has a photoreactive side chain, the diamine which has in the side chain the group which causes a photo dimerization reaction represented by the following formula, and the group which causes a photopolymerization reaction are also mentioned.

[Formula 37]

In the above formula, Y ₁ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, or -CO-. Y ₂ is an alkylene group having 1 to 30 carbon atoms, a divalent carbon ring, or a heterocycle, and one or more hydrogen atoms of the alkylene group, a divalent carbon ring, or a heterocycle may be substituted with a fluorine atom or an organic group. do. In Y ₂ , -CH ₂ - may be substituted with the following groups if they are not adjacent to each other; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. Y ₃ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, or a single bond. Y ₄ represents Cinnamo Diary. Y ₅ is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbon ring, or a heterocyclic ring, and one or more hydrogen atoms of the alkylene group, a divalent carbon ring, or heterocycle are substituted with a fluorine atom or an organic group. It can be done. Y ₅ may have -CH ₂ - substituted with the following groups if they are not adjacent to each other; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. Y ₆ represents a photopolymerizable group that is an acrylic group or a methacryl group.

The diamine having a group that causes a photodimerization reaction and a group that causes a photopolymerization reaction in the side chain specifically includes the following, but is not limited to these.

[Formula 38]

The above diamine can be used one type or in a mixture of two or more types depending on characteristics such as liquid crystal orientation, pretilt angle, voltage holding characteristic, and accumulated charge when used as a liquid crystal alignment film, and the response speed of the liquid crystal when used as a liquid crystal display element. You can.

Moreover, as for the diamine which has a photoreactive side chain, it is preferable to use 10-70 mol% of the diamine component used for synthesis of a polyamic acid, More preferably, it is 20-60 mol%, Especially preferably, it is 30-70 mol%. It is 50 mol%.

＜Other diamines＞

In addition, when producing a polyimide precursor and/or polyimide, diamines other than the above-mentioned diamines can be used together as a diamine component, as long as the effects of the present invention are not impaired. Specifically, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2, 4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy- 4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4 '-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3, 3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane Phenyl ether, 3,3'-diaminodiphenyl 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'-thiodianiline, 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, 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-amino) Phenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]dianiline, 4,4'-[1,3-phenylenebis(methylene)]dianiline, 3,4'- [1,4-phenylenebis(methylene)]dianiline, 3,4'-[1,3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis(methylene) )]dianiline, 3,3'-[1,3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis [(3-aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl)methanone], 1,4 -Phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-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-phenylene)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-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexa Fluoropropane, 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, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis(4-aminophenoxy)propane, 1 ,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-amino) Phenoxy)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, Aromatic diamines such as 12-(3-aminophenoxy)dodecane, alicyclic diamines such as bis(4-aminocyclohexyl)methane and bis(4-amino-3-methylcyclohexyl)methane, and 1,3-dia Minopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminoctane, 1,9-diamino and aliphatic diamines such as orchid, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminodecane.

The above-mentioned other diamines can also be used one type or in mixture of two or more types depending on characteristics such as liquid crystal orientation when used as a liquid crystal alignment film, pretilt angle, voltage holding characteristic, and accumulated charge.

＜Tetracarboxylic dianhydride＞

The tetracarboxylic dianhydride component reacted with the diamine component is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 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-pyridinetetracar Boxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxyl Acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxydiphthalatetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2 ,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid Boxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3 ,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid , 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid, bicyclo [4,3,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic acid, bicyclo[4 ,4,0]decane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic acid, 1, 2,3,4-Butanetetracarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid , bicyclo[2,2,2]oct-7-en-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclo Hexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0,2,7]dodeca-4,5,9,10-tetracarboxylic acid, 3,5,6- and tetracarboxylic dianhydride obtained from tricarboxynorbornane-2:3, 5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc. Of course, tetracarboxylic dianhydride may also be used one type or in combination of two or more types depending on characteristics such as liquid crystal orientation when used as a liquid crystal alignment film, voltage holding characteristics, and accumulated charge.

＜(B) Ingredient＞

The liquid crystal aligning agent of the present invention is a polyimide precursor obtained by using as a raw material a diamine component containing at least one type of diamine selected from the following formulas (B-1) to (B-5) as the (B) component, and this A tetracarboxylic dianhydride component containing a polymer selected from polyimides obtained by imidizing a polyimide precursor, or at least one type of tetracarboxylic dianhydride selected from the following formulas (3) and (4), It contains a polymer selected from a polyimide precursor obtained by reaction of diamine, and a polyimide obtained by imidizing this polyimide precursor.

[Formula 39]

[Formula 40]

When at least one tetracarboxylic dianhydride selected from the above formulas (3) and (4) is used as a raw material, the accumulated charge characteristics are improved due to interaction between [liquid crystal-alignment film] by light irradiation. It can be improved. Examples of the tetracarboxylic dianhydride represented by a formula selected from the above formulas (3) and (4) include, but are not limited to, the following compounds.

[Formula 41]

At least one tetracarboxylic dianhydride selected from the above formulas (1-1) to (1-4) is the tetracarboxylic dianhydride component used in the synthesis of component (B), which is a polyamic acid. It is preferable to use an amount of 10 to 100%. More preferably, it is good to use 10 to 60%.

Moreover, as long as the effect of the present invention is not impaired, tetracarboxylic dianhydrides other than those of the above formulas (1-1) to (1-4) may be used as a raw material for component (B). Specific examples include, but are not limited to, tetracarboxylic dianhydride described as component (A).

For example, when tetracarboxylic dianhydride having an aliphatic group or alicyclic group is also used as a raw material, the amount is 0 to 90% of the tetracarboxylic dianhydride component used in the synthesis of component (B), which is a polyamic acid. It is desirable to use .

When using at least one tetracarboxylic dianhydride selected from the above formulas (1-1) to (1-4) as the component (B), the diamine component to be reacted is not particularly limited, and specific examples thereof Examples of the diamines exemplified by component (A) include, but it is preferable to use at least one diamine selected from the above formulas (B-1) to (B-5) from the viewpoint of stored charge characteristics.

In addition, the polymer as component (B) is a polyimide precursor obtained using a diamine component containing at least one type of diamine selected from the following formulas (B-1) to (B-5) as a raw material, and this polyimide precursor A polymer selected from polyimides obtained by imidizing may be used.

[Formula 42]

(In the formula, Y ₁ represents a secondary amine, a tertiary amine, or a monovalent organic group having a heterocyclic structure, and Y ₂ represents a secondary amine, a tertiary amine, or a divalent organic group having a heterocyclic structure. )

At least one type of diamine having a highly polar specific structure selected from the above formulas (B-1) to (B-5) is used, or at least a diamine having a carboxyl group and a diamine having a nitrogen-containing aromatic heterocycle are each used. By using one or more types in combination, charge transfer is promoted through electrostatic interactions such as salt formation and hydrogen bonding, so the accumulated charge characteristics can be improved. Examples of at least one type of diamine selected from the above formulas (B-1) to (B-5) include, but are not limited to, the following diamines.

[Formula 43]

In addition, the polymer that is component (B) may also use diamine, which has a side chain that vertically aligns the liquid crystal used in component (A), as a raw material.

At least one type of diamine selected from the above formulas (B-1) to (B-5) is in an amount of 10 mol% to 80 mol% of the diamine component used in the synthesis of component (B), which is a polyamic acid. It is desirable to use .

When using at least one type of diamine selected from the above formulas (B-1) to (B-5), the tetracarboxylic dianhydride component to be reacted is not particularly limited, and specific examples thereof include (A) Although tetracarboxylic dianhydrides are exemplified as components, it is preferable to use at least one tetracarboxylic dianhydride selected from the above formulas (3) and (4) from the viewpoint of reducing accumulated charge.

＜Polymerizable compound＞

The liquid crystal aligning agent of this invention may contain the polymeric compound which has the group photopolymerized or photocrosslinked at two or more terminals as needed. These polymerizable compounds are compounds having two or more terminals having groups that are photopolymerized or photocrosslinked. Here, a polymerizable compound having a group that undergoes photopolymerization is a compound that has a functional group that undergoes polymerization by irradiating light. In addition, the compound having a photo-crosslinking group means that by irradiating light, it reacts with at least one polymer selected from the group consisting of a polymer of a polymerizable compound, a polyimide precursor, and a polyimide obtained by imidizing this polyimide precursor, thereby forming these compounds. It is a compound that has a functional group that can be cross-linked. In addition, compounds having a photo-crosslinking group also react with each other.

By using the liquid crystal aligning agent of the present invention containing the above polymerizable compound in a vertically aligned liquid crystal display element such as a SC-PVA type liquid crystal display, the side chain that vertically aligns the liquid crystal and the photoreactive side chain are formed. Compared to the case where the polymer or this polymerizable compound is used alone, the response speed can be significantly improved, and the response speed can be sufficiently improved even with a small amount of the polymerizable compound added.

The group to be photopolymerized or photocrosslinked includes a monovalent group represented by the following formula (IV).

[Formula 44]

(R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z ¹ represents a divalent aromatic ring or heterocyclic ring that may be substituted with an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Z ² represents a monovalent aromatic ring or heterocyclic ring that may be substituted with an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms.)

Specific examples of the polymerizable compound include a compound having a photopolymerizable group at each of two terminals represented by the following formula (V), a terminal having a photopolymerizable group represented by the following formula (VI), and a terminal having a photocrosslinking group. and compounds having a photocrosslinking group at each of the two terminals represented by the following formula (VII).

Additionally, in the following formulas (V) to (VII), R ¹² , Z ¹ and Z ² are the same as R ¹² , Z ¹ and Z ² in the formula (IV), and Q ¹ is a divalent organic group. am. Q ¹ has a ring structure such as a phenylene group (-C ₆ H ₄ -), a biphenylene group (-C ₆ H ₄ -C ₆ H ₄ -), and a cyclohexylene group (-C ₆ H ₁₀ -). It is desirable to have This is because interaction with the liquid crystal tends to increase.

[Formula 45]

[Formula 46]

[Formula 47]

Specific examples of the polymerizable compound represented by formula (V) include the polymerizable compound represented by the following formula (4). In the following formula (4), V and W are a single bond or -R ¹ O-, and R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably -R ¹ It is represented by O-, and R ¹ is a linear or branched alkylene group having 2 to 6 carbon atoms. Additionally, V and W may be the same or different, but if they are the same, synthesis is easy.

[Formula 48]

In addition, even if it is a polymerizable compound that has an acrylate group or a methacrylate group rather than an α-methylene-γ-butyrolactone group as a group to be photopolymerized or photocrosslinked, the acrylate group or methacrylate group may be used as a spacer such as an oxyalkylene group. A polymerizable compound having a structure bonded to a phenylene group via , can significantly improve the response speed, as can the polymerizable compound having an α-methylene-γ-butyrolactone group at both terminals. In addition, polymerizable compounds having a structure in which an acrylate group or methacrylate group is bonded to a phenylene group through a spacer such as an oxyalkylene group have improved stability against heat and can be used at high temperatures, for example, at a firing temperature of 200°C or higher. It's bearable enough.

＜Synthesis of polyamic acid＞

When obtaining a polyamic acid by reaction of a diamine component and tetracarboxylic dianhydride, a known synthesis method can be used. Generally, this is a method of reacting a diamine component and a tetracarboxylic dianhydride component in an organic solvent. The reaction between the diamine component and tetracarboxylic dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and does not generate by-products.

The organic solvent used in the above reaction is not particularly limited as long as it dissolves the produced polyamic acid. Furthermore, even if it is an organic solvent in which polyamic acid does not dissolve, it may be used by mixing with the solvent as long as the produced polyamic acid does not precipitate. Additionally, since moisture in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use a dehydrated and dried organic solvent.

Organic solvents used in the above reaction include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-methyl-2- Pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N-methylcapro Lactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone. , methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol. , ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol. Monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3 -Methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, di Oxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate Ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3 -Methoxypropionate butyl, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, etc. are mentioned. These organic solvents may be used individually or in combination.

The method of reacting the diamine component and the tetracarboxylic dianhydride component in an organic solvent is to stir a solution in which the diamine component is dispersed or dissolved in the organic solvent, and the tetracarboxylic dianhydride component is added as is or dispersed or dissolved in the organic solvent. A method of adding by dissolving, a method of adding the diamine component to a solution in which the tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, or a method of adding the tetracarboxylic dianhydride component and the diamine component alternately, etc. It can be anything. In addition, when the diamine component or the tetracarboxylic dianhydride component consists of multiple types of compounds, they may be reacted in a pre-mixed state, may be reacted individually sequentially, or the individually reacted low molecular weight substances may be mixed and reacted to form a polymer. It may be used as a monomer.

The temperature when reacting the diamine component and the tetracarboxylic dianhydride component is, for example, -20°C to 150°C, and preferably is in the range of -5°C to 100°C. Moreover, for the reaction, for example, the concentration of the total of the diamine component and the tetracarboxylic dianhydride component is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass, with respect to the reaction liquid.

The ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component in the polymerization reaction can be selected according to the molecular weight of the polyamic acid to be obtained. As in a typical polycondensation reaction, the closer this molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced is, and a preferable range is 0.8 to 1.2.

The method for synthesizing the polyamic acid used in the present invention is not limited to the above method, and like the general method for synthesizing polyamic acid, instead of the tetracarboxylic dianhydride, tetracarboxylic acid or tetracarboxylic acid of the corresponding structure is used. The corresponding polyamic acid can also be obtained by using a tetracarboxylic acid derivative such as acid dihalide and reacting it by a known method.

Methods for imidizing the above-described polyamic acid to produce a polyimide include thermal imidization in which a solution of the polyamic acid is heated as is, and catalytic imidization in which a catalyst is added to the polyamic acid solution. In addition, the imidization rate from polyamic acid to polyimide does not necessarily need to be 100%.

The temperature when thermally imidizing a polyamic acid in a solution is 100°C to 400°C, preferably 120°C to 250°C, and is preferably carried out while removing water generated by the imidization reaction to the outside of the system.

Catalyst imidization of the polyamic acid can be performed by adding a basic catalyst and an acid anhydride to a solution of the polyamic acid and stirring the solution at -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.5 to 30 mole times the amic acid group, preferably 2 to 20 mole times, and the amount of the acid anhydride is 1 to 50 mole times the amic acid group, preferably 3 to 30 mole times. Basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among them, pyridine is preferable because it has an appropriate basicity to proceed with the reaction. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among these, acetic anhydride is preferred because it facilitates purification after completion of the reaction. The imidization rate by catalyst imidization can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

In addition, polyamic acid ester is prepared by reacting tetracarboxylic acid diester dichloride with a diamine similar to the synthesis of the polyamic acid above, or by reacting tetracarboxylic acid diester with the same diamine as the synthesis of the polyamic acid above in the presence of a suitable condensing agent or base. It can be produced by reacting under the following conditions. In addition, it can also be obtained by synthesizing polyamic acid in advance using the above method and esterifying the carboxylic acid in the amic acid using a polymer reaction. Specifically, for example, tetracarboxylic acid diester dichloride and diamine are reacted in the presence of a base and an organic solvent at -20°C to 150°C, preferably 0°C to 50°C, for 30 minutes to 24 hours, preferably. Polyamic acid ester can be synthesized by reacting for 1 hour to 4 hours. Polyimide can also be obtained by heating the polyamic acid ester at a high temperature to promote dealcoholization and ring closure.

When recovering polyimide precursors or polyimides such as polyamic acid and polyamic acid ester produced from the reaction solution, the reaction solution may be added to a poor solvent to cause precipitation. Poor solvents used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated by adding it to a poor solvent can be recovered by filtration and then dried under normal or reduced pressure, at room temperature, or by heating. Additionally, if the recovered polymer is re-dissolved in an organic solvent and the reprecipitation and recovery operation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of poor solvents at this time include alcohols, ketones, hydrocarbons, etc., and it is preferable to use three or more types of poor solvents selected from among these, as the efficiency of purification further increases.

＜Liquid crystal alignment agent＞

Although the liquid crystal aligning agent of this invention contains at least 1 polymer which has the structure shown by said formula (1) in a side chain, content of this polymer is preferably 1-20 mass %, More preferably, it is 3-15 mass %. %, especially preferably 3 to 10 mass %. In addition, when containing a polymerizable compound each having a photopolymerizable or photocrosslinkable group at two or more terminals, the content thereof is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, with respect to 100 parts by mass of the polymer. It is wealth.

Moreover, the liquid crystal aligning agent of this invention may contain other polymers other than the said polymer. At that time, the content of these other polymers in all polymer components is preferably 0.5 to 80 mass%, more preferably 20 to 50 mass%.

The molecular weight of the polymer of the liquid crystal aligning agent is the weight average measured by GPC (gel permeation chromatography) method when considering the strength of the liquid crystal alignment film obtained by applying the liquid crystal aligning agent, workability at the time of forming the coating film, and uniformity of the coating film. The molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

The solvent that the liquid crystal aligning agent contains is not particularly limited, and is a polymer having a structure represented by the above formula (1) in the side chain, and a polymer having a group that is photopolymerized or photocrosslinked at two or more terminals contained as necessary. Any material that can dissolve or disperse components such as chemical compounds is sufficient. For example, organic solvents as exemplified in the synthesis of polyamic acid can be mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N- Dimethylpropanamide is preferable in terms of solubility. Of course, a mixed solvent of two or more types may be used.

Moreover, it is preferable to mix and use the solvent which improves the uniformity and smoothness of a coating film with a solvent in which the component containing a liquid crystal aligning agent has high solubility. Such solvents include, for example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, and ethyl cellosolve acetate. , butylcarbitol, ethylcarbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene. Glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl Ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3- Methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, di Isobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene acetate. Glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid. Propyl, 3-methoxybutyl propionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, Propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate ester , ethyl lactic acid, n-propyl lactic acid, n-butyl lactic acid, isoamyl lactic acid, 2-ethyl-1-hexanol, etc. You may mix multiple types of these solvents. 5-80 mass % of the whole solvent contained in a liquid crystal aligning agent is preferable, and, as for these solvents, 20-60 mass % is more preferable.

The liquid crystal aligning agent may contain components other than those mentioned above. Examples include compounds that improve film thickness uniformity and surface smoothness when the liquid crystal aligning agent is applied, and compounds that improve the adhesiveness of the liquid crystal aligning film and the substrate.

Compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, Ftop EF301, EF303, EF352 (manufactured by Tochem Products), Megapak F171, F173, R-30 (manufactured by Dainippon Ink), Fluorad FC430, FC431 (manufactured by Sumitomo 3M) , Asahi Guard AG710, Suplon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.). The usage ratio 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 the total amount of the polymer contained in the liquid crystal aligning agent.

Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 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 diyl. Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl ether Cydyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane , N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3-( N,N-diglycidyl)aminopropyltrimethoxysilane, etc. are mentioned.

Additionally, in order to further increase the film strength of the liquid crystal alignment film, phenol compounds such as 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane and tetra(methoxymethyl)bisphenol may be added. 0.1-30 mass parts is preferable with respect to the total amount of 100 mass parts of polymers contained in a liquid crystal aligning agent, and 1-20 mass parts of these compounds are more preferable.

In addition, to the liquid crystal aligning agent, you may add a dielectric or a conductive substance for the purpose of changing the electrical properties such as dielectric constant and conductivity of the liquid crystal aligning film as long as it is a range in which the effect of the present invention is not impaired other than the above.

By applying this liquid crystal aligning agent on a substrate and baking it, a liquid crystal alignment film that vertically aligns the liquid crystal can be formed. By use of the liquid crystal aligning agent of this invention, the response speed of the liquid crystal display element using the liquid crystal aligning film obtained can be made fast. Moreover, the polymerizable compound which has the group which photopolymerizes or photocrosslinks at two or more terminals, which may be contained in the liquid crystal aligning agent of this invention, is not contained in a liquid crystal aligning agent, or is contained in a liquid crystal together with a liquid crystal aligning agent. , even in the so-called PSA mode, the light reaction is highly sensitive, and a tilt angle can be provided even with a small amount of ultraviolet irradiation.

For example, after apply|coating the liquid crystal aligning agent of this invention to a board|substrate, it dries as needed, and the cured film obtained by baking can also be used as a liquid crystal aligning film as it is. In addition, this cured film can be rubbed, irradiated with polarized light or light of a specific wavelength, treated with an ion beam, etc., or UV can be irradiated with a voltage applied to the liquid crystal display element after liquid crystal charging as an alignment film for PSA. . In particular, it is useful to use as an alignment film for PSA.

At this time, the substrate used is not particularly limited as long as it is a highly transparent substrate, and includes glass plates, polycarbonate, poly(meth)acrylate, polyether sulfone, polyarylate, polyurethane, polysulfone, polyether, and polyether ketone. , trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetylcellulose, diacetylcellulose, acetate butyrate cellulose, etc. can be used. In addition, it is preferable from the viewpoint of process simplification to use a substrate on which ITO electrodes for driving liquid crystal are formed. Additionally, in a reflective liquid crystal display device, even an opaque material such as a silicon wafer can be used as long as it is used for only one side of the substrate, and a light-reflecting material such as aluminum can also be used as the electrode in this case.

The application method of the liquid crystal aligning agent is not particularly limited, and includes printing methods such as screen printing, offset printing, and flexo printing, inkjet methods, spray methods, roll coat methods, dip, roll coater, slit coater, and spinner. there is. In terms of productivity, the transfer printing method is widely used industrially, and is also preferably used in the present invention.

The coating film formed by applying the liquid crystal aligning agent by the above method can be baked to form a cured film. The drying process after applying the liquid crystal aligning agent is not necessarily necessary, but it is preferable to perform the drying process when the time from application to baking is not constant for each substrate, or when baking is not performed immediately after application. This drying only requires that the solvent has been removed to the extent that the shape of the coating film is not deformed by transportation of the substrate, etc., and the drying means is not particularly limited. For example, a method of drying on a hot plate at a temperature of 40°C to 150°C, preferably 60°C to 100°C, is used for 0.5 minutes to 30 minutes, preferably for 1 minute to 5 minutes.

The baking temperature of the coating film formed by applying a liquid crystal aligning agent is not limited, and is, for example, 100 to 350°C, preferably 120 to 300°C, and more preferably 150 to 250°C. The firing time is 5 minutes to 240 minutes, preferably 10 minutes to 90 minutes, and more preferably 20 minutes to 90 minutes. Heating can be performed by a commonly known method, for example, a hot plate, a hot air circulation furnace, an infrared furnace, etc.

Moreover, the thickness of the liquid crystal aligning film obtained by baking is not specifically limited, but is preferably 5 to 300 nm, and more preferably 10 to 100 nm.

＜Liquid crystal display device＞

The liquid crystal display element of this invention can produce a liquid crystal cell by a well-known method after forming a liquid crystal alignment film on a board|substrate by the said method. A specific example of the liquid crystal display element is 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 with the liquid crystal aligning agent of the present invention. It is a vertically aligned liquid crystal display device equipped with a. Specifically, a liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention onto two substrates and baking them, the two substrates are arranged so that the liquid crystal alignment films face each other, and a liquid crystal layer composed of liquid crystal is formed between the two substrates. It is a liquid crystal display element of a vertical alignment type including a liquid crystal cell produced by sandwiching, that is, contacting a liquid crystal alignment film to form a liquid crystal layer, and irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer.

Using a liquid crystal aligning film formed with the liquid crystal aligning agent of the present invention, ultraviolet rays are irradiated while applying a voltage to the liquid crystal aligning film and the liquid crystal layer to polymerize the polymerizable compound, and the photoreactive side chains that the polymer has, By reacting the photoreactive side chain of the polymer with the polymerizable compound, the orientation of the liquid crystal is fixed more efficiently, resulting in a liquid crystal display element with significantly excellent response speed.

The substrate used in the liquid crystal display device of the present invention is not particularly limited as long as it is a substrate with high transparency, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed. Specific examples include the same substrate as the liquid crystal alignment film described above. A substrate on which a conventional electrode pattern or a protrusion pattern is formed may be used, but in the liquid crystal display device of the present invention, since the liquid crystal aligning agent of the present invention is used, for example, a line/slit of 1 to 10 μm is formed on one side of the substrate. It is possible to operate even with a structure in which an electrode pattern is formed and no slit pattern or protrusion pattern is formed on the opposing substrate. By using a liquid crystal display device with this structure, the manufacturing process can be simplified and high transmittance can be obtained. .

Additionally, in high-performance devices such as TFT-type devices, devices such as transistors formed between an electrode for driving liquid crystal and a substrate are used.

In the case of a transmissive liquid crystal display element, it is common to use a substrate as described above, but in a reflective liquid crystal display element, it is possible to use an opaque substrate such as a silicon wafer as long as it is only on one side. At that time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display device of the present invention is not particularly limited, and includes negative type liquid crystal materials such as liquid crystal materials used in the conventional vertical alignment method, such as MLC-6608 and MLC-6609 manufactured by Merck & Co., Ltd. Liquid crystal can be used. In addition, in PSA mode, for example, a liquid crystal containing a polymerizable compound represented by the following formula can be used.

[Formula 49]

In the present invention, known methods can be used as a method of sandwiching the liquid crystal layer between two substrates. For example, prepare a pair of substrates on which a liquid crystal alignment film is formed, spacers such as beads are spread on the liquid crystal alignment film of one substrate, and the other substrate is bonded so that the surface on the side on which the liquid crystal alignment film is formed is inside. and a method of injecting liquid crystal under reduced pressure and sealing it. In addition, a pair of substrates on which a liquid crystal alignment film was formed was prepared, and spacers such as beads were spread on the liquid crystal alignment film of one of the substrates, and then the liquid crystal was dropped so that the surface on the side on which the liquid crystal alignment film was formed was inside, and the other substrate was placed on the liquid crystal alignment film. A liquid crystal cell can also be produced by bonding one side of the substrate and sealing it. The thickness of the spacer is preferably 1 to 30 μm, more preferably 2 to 10 μm.

The process of manufacturing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field to the liquid crystal alignment film and the liquid crystal layer by applying a voltage between electrodes provided on a substrate, and One example is a method of irradiating ultraviolet rays while maintaining an electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The amount of ultraviolet irradiation is, for example, 1 to 60 J, preferably 40 J or less. A smaller amount of ultraviolet irradiation can suppress the decrease in reliability caused by destruction of the members constituting the liquid crystal display element, and can also suppress the irradiation of ultraviolet rays. This is desirable because manufacturing efficiency increases by reducing time.

As described above, when ultraviolet rays are irradiated while applying voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is remembered by this polymer, resulting in a response of the liquid crystal display element. The speed can be increased. Moreover, when ultraviolet rays are irradiated while applying voltage to the liquid crystal alignment film and the liquid crystal layer, a polyimide precursor having a side chain that vertically aligns the liquid crystal and a photoreactive side chain, and a polyimide obtained by imidizing this polyimide precursor Since the photoreactive side chains of at least one type of polymer selected from the above or the photoreactive side chains of the polymer react with the polymerizable compound, the response speed of the resulting liquid crystal display element can be increased.

Example

Hereinafter, it will be described in more detail based on examples, but the present invention is not limited by these examples at all.

＜Synthesis of liquid crystal aligning agent＞

The symbols used in preparation of the following liquid crystal aligning agent are as follows.

(acid dianhydride)

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

CBDA: 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride

PMDA: Pyromellitic dianhydride

TCA: 2,3,5-tricarboxycyclopentylacetic acid-1,4,2,3-2 anhydride

(diamine)

p-PDA: p-phenylenediamine

DBA: 3,5-diaminobenzoic acid

3AMPDA: 3,5-diamino-N-(pyridin-3-ylmethyl)benzamide

Photosensitive diamine represented by the following formulas DA-1 to DA-3

[Formula 50]

Polymerizable diamine represented by the following formula DA-4

[Formula 51]

Vertically oriented side chain diamine represented by the following formulas DA-5 to DA-7

[Formula 52]

Diamine represented by the following formula DA-8 to 9

[Formula 53]

＜Solvent＞

NMP: N-methyl-2-pyrrolidone

BCS: Butylcellosolve

＜Additives＞

3AMP: 3-picolylamine

＜Polymerizable compound＞

Polymerizable compound represented by the following formula RM1

[Formula 54]

In addition, the conditions for measuring the molecular weight of polyimide are as follows.

Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Science Co., Ltd.

Column: Column manufactured by Shodex (KD-803, KD-805)

Column temperature: 50℃

Eluent: N,N'-dimethylformamide (as additives, lithium bromide-hydrate (LiBr·H ₂ O) is 30 mmol/l, phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/l, tetrahydrofuran (THF) ) this 10 ㎖/ℓ)

Flow rate: 1.0 mL/min

Standard samples for creating a calibration curve: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight approximately 9,000,000, 150,000, 100,000, 30,000), and polyethylene glycol manufactured by Polymer Laboratories (molecular weight approximately 12,000, 4,000, 1,000).

In addition, the imidation rate of polyimide was measured as follows. Put 20 mg of polyimide powder into an NMR sample tube (NMR sampling tube standard ϕ5 manufactured by Kusano Science Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture), and apply ultrasound to completely dissolve. I ordered it. Proton NMR of this solution was measured at 500 MHz using an NMR measuring instrument (JNW-ECA500) manufactured by Nippon Electronics Datum Co., Ltd. The imidization rate is determined by determining a proton derived from a structure that does not change before and after imidization as a reference proton, and calculating the peak integration value of this proton and the peak integration value of the proton derived from the NH group of amic acid appearing around 9.5 to 10.0 ppm. The value was used to obtain the value using the formula below. In the formula below, 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 rate is 0%). It is the ratio of the number of standard protons to one basic proton.

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

(Synthesis Example 1)

BODA (10.01 g, 40.0 mmol), 3AMPDA (4.85 g, 20.0 mmol), DA-2 (13.22 g, 40.0 mmol), DA-5 (15.22 g, 40.0 mmol) were dissolved in NMP (164.6 g), 60 After reacting at ℃ for 5 hours, CBDA (11.57 g, 59.0 mmol) and NMP (54.9 g) were added and reacted at 40℃ for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (250 g) and diluting it to 6.5% by mass, acetic anhydride (46.4 g) and pyridine (14.4 g) were added as imidization catalysts, and reaction was performed at 70°C for 3 hours. This reaction solution was added to methanol (3300 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, dried under reduced pressure at 100°C, and polyimide powder (A) was obtained. The imidation rate of this polyimide was 72%, the number average molecular weight was 14000, and the weight average molecular weight was 38000.

NMP (44.0 g) was added to the obtained polyimide powder (A) (6.0 g), and stirred at 70°C for 20 hours to dissolve. 6.0 g of 3AMP (1% by mass NMP solution), NMP (4.0 g), and BCS (40.0 g) were added to this solution, and the liquid crystal aligning agent (U1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 2)

BODA (10.01 g, 40.0 mmol), 3AMPDA (4.85 g, 20.0 mmol), DA-1 (14.34 g, 40.0 mmol), DA-5 (15.22 g, 40.0 mmol) were dissolved in NMP (168.0 g), 60 After reacting at ℃ for 5 hours, CBDA (11.57 g, 59.0 mmol) and NMP (55.98 g) were added and reacted at 40℃ for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (250 g) and diluting it to 6.5 mass%, acetic anhydride (45.4 g) and pyridine (14.0 g) were added as imidization catalysts, and the reaction was allowed to proceed at 70°C for 3 hours. This reaction solution was added to methanol (3300 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, dried under reduced pressure at 100°C, and polyimide powder (B) was obtained. The imidization rate of this polyimide was 73%, the number average molecular weight was 18,000, and the weight average molecular weight was 37,000.

NMP (44.0 g) was added to the obtained polyimide powder (B) (6.0 g), and stirred at 70°C for 20 hours to dissolve. A liquid crystal aligning agent (U2) was obtained by adding 6.0 g of 3AMP (1 mass % NMP solution), NMP (4.0 g), and BCS (40.0 g) to this solution and stirring it at room temperature for 5 hours.

(Synthesis Example 3)

BODA (10.01 g, 40.0 mmol), 3AMPDA (4.85 g, 20.0 mmol), DA-3 (13.78 g, 40.0 mmol), DA-5 (15.22 g, 40.0 mmol) were dissolved in NMP (166.2 g), 60 After reacting at ℃ for 5 hours, CBDA (11.57 g, 59.0 mmol) and NMP (55.42 g) were added and reacted at 40℃ for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (250 g) and diluting it to 6.5% by mass, acetic anhydride (45.49 g) and pyridine (14.3 g) were added as imidization catalysts, and reaction was performed at 70°C for 3 hours. This reaction solution was added to methanol (3300 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, dried under reduced pressure at 100°C, and polyimide powder (C) was obtained. The imidization rate of this polyimide was 72%, the number average molecular weight was 21000, and the weight average molecular weight was 82000.

NMP (44.0 g) was added to the obtained polyimide powder (C) (6.0 g), and stirred at 70°C for 20 hours to dissolve. 6.0 g of 3AMP (1% by mass NMP solution), NMP (4.0 g), and BCS (40.0 g) were added to this solution, and the liquid crystal aligning agent (U3) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 4)

TCA (11.21 g, 50.0 mmol), p-PDA (4.33 g, 40.0 mmol), DA-3 (6.89 g, 20.0 mmol), DA-5 (7.61 g, 20.0 mmol), DA-7 (9.90 g, 20.0 mmol) mmol) was dissolved in NMP (148.6 g) and reacted at 80°C for 5 hours, then CBDA (9.61 g, 49.0 mmol) and NMP (49.54 g) were added and reacted at 40°C for 10 hours to prepare a polyamic acid solution. got it

After adding NMP to this polyamic acid solution (220 g) and diluting it to 6.5% by mass, acetic anhydride (35.1 g) and pyridine (10.9 g) were added as imidization catalysts, and reaction was performed at 50°C for 3 hours. This reaction solution was added to methanol (2900 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (D). The imidation rate of this polyimide was 51%, the number average molecular weight was 11000, and the weight average molecular weight was 25000.

NMP (44.0 g) was added to the obtained polyimide powder (D) (6.0 g), and stirred at 70°C for 20 hours to dissolve. 6.0 g of 3AMP (1% by mass NMP solution), NMP (4.0 g), and BCS (40.0 g) were added to this solution, and the liquid crystal aligning agent (U4) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 5)

BODA (10.01 g, 40.0 mmol), DA-4 (7.93 g, 30.0 mmol), DA-3 (10.33 g, 30.0 mmol), DA-5 (7.61 g, 20.0 mmol), DA-6 (8.69 g, 20.0 mmol) was dissolved in NMP (168.4 g) and reacted at 80°C for 5 hours, then CBDA (11.57 g, 49.0 mmol) and NMP (56.14 g) were added and reacted at 40°C for 10 hours to prepare a polyamic acid solution. got it

After adding NMP to this polyamic acid solution (250 g) and diluting it to 6.5 mass%, acetic anhydride (27.2 g) and pyridine (70.2 g) were added as imidization catalysts, and the reaction was allowed to proceed at 50°C for 3 hours. This reaction solution was added to methanol (3500 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, dried under reduced pressure at 100°C, and polyimide powder (E) was obtained. The imidization rate of this polyimide was 59%, the number average molecular weight was 14000, and the weight average molecular weight was 51000.

NMP (44.0 g) was added to the obtained polyimide powder (E) (6.0 g), and stirred at 70°C for 20 hours to dissolve. 6.0 g of 3AMP (1% by mass NMP solution), NMP (4.0 g), and BCS (40.0 g) were added to this solution, and the liquid crystal aligning agent (U5) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 6)

BODA (18.77 g, 75.0 mmol), DBA (3.04 g, 20.0 mmol), DA-8 (9.96 g, 50.0 mmol), DA-5 (11.42 g, 30.0 mmol) were dissolved in NMP (143.7 g), 60 After reacting at ℃ for 5 hours, CBDA (4.12 g, 21.0 mmol) and NMP (47.89 g) were added and reacted at 40℃ for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (180 g) and diluting it to 6.5 mass%, acetic anhydride (19.1 g) and pyridine (14.8 g) were added as imidization catalysts, and the reaction was allowed to proceed at 80°C for 4 hours. This reaction solution was added to methanol (2200 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, dried under reduced pressure at 100°C, and polyimide powder (E) was obtained. The imidization rate of this polyimide was 57%, the number average molecular weight was 12000, and the weight average molecular weight was 39000.

NMP (44.0 g) was added to the obtained polyimide powder (E) (6.0 g), and stirred at 70°C for 20 hours to dissolve. 6.0 g of 3AMP (1% by mass NMP solution), NMP (4.0 g), and BCS (40.0 g) were added to this solution, and the liquid crystal aligning agent (L1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 7)

BODA (12.51 g, 50.0 mmol), DBA (12.93 g, 85.0 mmol), and DA-9 (6.16 g, 15.0 mmol) were dissolved in NMP (123.3 g), reacted at 60°C for 3 hours, and then CBDA (9.51 g, 48.5 mmol) and NMP (41.11 g) were added and reacted at 40°C for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (180 g) and diluting it to 6.5% by mass, acetic anhydride (44.4 g) and pyridine (13.8 g) were added as imidization catalysts, and reaction was performed at 80°C for 2 hours. This reaction solution was added to methanol (2400 ml), and the obtained precipitate was separated by filtration. This deposit was washed with methanol, dried under reduced pressure at 100°C, and polyimide powder (F) was obtained. The imidization rate of this polyimide was 70%, the number average molecular weight was 12000, and the weight average molecular weight was 31000.

NMP (44.0 g) was added to the obtained polyimide powder (F) (6.0 g), and stirred at 70°C for 20 hours to dissolve. A liquid crystal aligning agent (L2) was obtained by adding 6.0 g of 3AMP (1 mass % NMP solution), NMP (4.0 g), and BCS (40.0 g) to this solution and stirring it at room temperature for 5 hours.

(Synthesis Example 8)

BODA (5.00 g, 20.0 mmol), DBA (6.09 g, 40.0 mmol), 3AMPDA (7.27 g, 30.0 mmol), DA-5 (11.42 g, 30.0 mmol) were dissolved in NMP (136.5 g) and incubated at 60°C. After reacting for 3 hours, PMDA (4.36 g, 48.5 mmol), CBDA (11.37 g, 58.0 mmol), and NMP (45.51 g) were added and reacted at 40°C for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (180 g) and diluting it to 6.5 mass%, acetic anhydride (40.0 g) and pyridine (12.4 g) were added as imidization catalysts, and the reaction was allowed to proceed at 50°C for 3 hours. This reaction solution was added to methanol (2300 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (G). The imidization rate of this polyimide was 78%, the number average molecular weight was 9000, and the weight average molecular weight was 20000.

NMP (44.0 g) was added to the obtained polyimide powder (G) (6.0 g), and stirred at 70°C for 20 hours to dissolve. A liquid crystal aligning agent (L3) was obtained by adding 6.0 g of 3AMP (1 mass % NMP solution), NMP (4.0 g), and BCS (40.0 g) to this solution and stirring it at room temperature for 5 hours.

(Example 1)

By mixing 3.0 g of the liquid crystal aligning agent (U1) obtained in Synthesis Example 1 as a first component and 7.0 g of the liquid crystal aligning agent (L1) obtained in Example 5 as a second component, and stirring for 1 hour, a liquid crystal aligning agent (A1) is obtained. ) was prepared.

＜Production of liquid crystal cell＞

The liquid crystal cell was produced in the procedures as shown below using the liquid crystal aligning agent (A1) obtained in Example 1. The liquid crystal aligning agent (A1) obtained in Example 1 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern with a pixel size of 100 μm × 300 μm and a line/space of 5 μm was formed, and the mixture was heated at 80°C. After drying for 90 seconds with a hot plate, baking was performed for 30 minutes in a hot air circulation oven at 200°C to form a liquid crystal alignment film with a film thickness of 100 nm.

In addition, the liquid crystal aligning agent (A1) is spin-coated on the ITO surface on which the electrode pattern is not formed, dried for 90 seconds on a hot plate at 80°C, and then baked in a hot air circulation oven at 200°C for 30 minutes. A liquid crystal alignment film with a film thickness of 100 nm was formed.

For the above two substrates, a 4 µm bead spacer was spread on the liquid crystal alignment film of one of the substrates, and then a sealant (solvent-type thermosetting type epoxy resin) was printed from thereon. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was turned inward and bonded to the previous substrate, and then the sealant was cured to produce an empty cell. Liquid crystal MLC-3023 (trade name manufactured by Merck & Co., Ltd.) containing a polymerizable compound for PSA was injected into this empty cell by a reduced-pressure injection method to produce a liquid crystal cell.

The response speed of the obtained liquid crystal cell was measured by the following method. After that, in the state where a DC voltage of 15 V was applied to this liquid crystal cell, 10 J/cm 2 of UV was irradiated from the outside of this liquid crystal cell through a 365 nm band-pass filter. In addition, the UV illuminance was measured using UV-MO3A manufactured by ORC. Afterwards, for the purpose of deactivating unreacted polymerizable compounds remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32/A- 1) was irradiated for 30 minutes. Afterwards, the response speed was measured again and the response speed before and after UV irradiation was compared. Additionally, the pretilt angle of the pixel portion of the cell after UV irradiation was measured.

Additionally, the residual DC voltage of each cell was measured. The results are shown in the table.

“Method for measuring response speed”

First, in a measuring device consisting of a backlight, a set of polarizers in a cross-Nicol state, and a light quantity detector, a liquid crystal cell was placed between the sets of polarizers. At this time, the pattern of the ITO electrode with lines/spaces was formed at an angle of 45° with respect to the cross nicol. Then, a square wave with a voltage of ±7 V and a frequency of 1 kHz is applied to the liquid crystal cell, the change in luminance observed by the light quantity detector until saturation is acquired with an oscilloscope, and the luminance when no voltage is applied is obtained. A voltage of 0%, ±6 V was applied, the saturated luminance value was set as 100%, and the time taken for the luminance to change from 10% to 90% was taken as the response speed.

“Measurement of pretilt angle”

An LCD analyzer LCA-LUV42A manufactured by Mayo Technica was used.

“Evaluation of residual DC voltage”

To the liquid crystal cell manufactured above, a square wave of 30 Hz and 7.8 Vpp superimposed on 2 V direct current was applied at 23°C for 100 hours, and the voltage remaining in the liquid crystal cell immediately after the direct current voltage was cut off (residual DC voltage) was measured as flicker. Obtained by elimination method. This value is an indicator of afterimages generated by DC accumulation, and when this value is approximately 30 mV or less, afterimage characteristics are judged to be excellent.

(Example 2)

Except that the liquid crystal aligning agent (L1) was changed to the liquid crystal aligning agent (L2), the same operation as in Example 1 was performed to prepare the liquid crystal aligning agent (A2). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 3)

Except that liquid crystal aligning agent (L1) was used as liquid crystal aligning agent (L3), the same operation as in Example 1 was performed to prepare liquid crystal aligning agent (A3). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 4)

Except that the liquid crystal aligning agent (U1) was changed to the liquid crystal aligning agent (U2), the same operation as in Example 1 was performed to prepare the liquid crystal aligning agent (A4). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 5)

Except that the liquid crystal aligning agent (L1) was changed to the liquid crystal aligning agent (L2), the same operation as in Example 4 was performed to prepare a liquid crystal aligning agent (A5). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 6)

Except that the liquid crystal aligning agent (L1) was changed to the liquid crystal aligning agent (L3), the same operation as in Example 4 was performed to prepare the liquid crystal aligning agent (A6). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 7)

Except that the liquid crystal aligning agent (U1) was changed to the liquid crystal aligning agent (U3), the same operation as in Example 1 was performed to prepare the liquid crystal aligning agent (A7). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 8)

Except that the liquid crystal aligning agent (L1) was changed to the liquid crystal aligning agent (L2), the same operation as in Example 7 was performed to prepare a liquid crystal aligning agent (A8). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 9)

Except that the liquid crystal aligning agent (L1) was changed to the liquid crystal aligning agent (L3), the same operation as in Example 7 was performed to prepare the liquid crystal aligning agent (A9). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 10)

Except that the liquid crystal aligning agent (U1) was changed to the liquid crystal aligning agent (U4), the same operation as in Example 1 was performed to prepare the liquid crystal aligning agent (A10). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 11)

Except that the liquid crystal aligning agent (L1) was changed to the liquid crystal aligning agent (L2), the same operation as in Example 10 was performed to prepare a liquid crystal aligning agent (A11). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 12)

Except that liquid crystal aligning agent (L1) was used as liquid crystal aligning agent (L3), the same operation as Example 10 was performed to prepare liquid crystal aligning agent (A12). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 13)

Except that the liquid crystal aligning agent (U1) was changed to the liquid crystal aligning agent (U5), the same operation as in Example 1 was performed to prepare the liquid crystal aligning agent (A13). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 14)

Except that the liquid crystal aligning agent (L1) was changed to the liquid crystal aligning agent (L2), the same operation as in Example 13 was performed to prepare a liquid crystal aligning agent (A14). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 15)

Except that liquid crystal aligning agent (L1) was used as liquid crystal aligning agent (L3), the same operation as in Example 13 was performed to prepare liquid crystal aligning agent (A15). Additionally, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Example 16)

5.0 g of liquid crystal aligning agent (U5) as a first component, 5.0 g of liquid crystal aligning agent (L1) as a second component, and 0.06 g (10% by mass with respect to the solid content of the liquid crystal aligning agent) as a polymerizable compound are mixed. The liquid crystal aligning agent (A16) was prepared by stirring for 1 hour. Additionally, the same operation as in Example 1 was performed except that MLC-6608 was used as a liquid crystal containing no polymerizable compound for PSA, and the response speed, pretilt angle, and residual DC voltage were measured.

(Comparative Example 1)

Except for using the liquid crystal aligning agent (U1) as the liquid crystal aligning agent, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Comparative Example 2)

Except that the liquid crystal aligning agent (U2) was used as the liquid crystal aligning agent, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Comparative Example 3)

Except that the liquid crystal aligning agent (U3) was used as the liquid crystal aligning agent, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Comparative Example 4)

Except that the liquid crystal aligning agent (U4) was used as the liquid crystal aligning agent, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

(Comparative Example 5)

Except that the liquid crystal aligning agent (U5) was used as the liquid crystal aligning agent, the same operation as in Example 1 was performed to measure the response speed, pretilt angle, and residual DC voltage.

As shown in the above results, it can be seen that in Examples 1 to 12, by introducing component 1 having a radical generating structure, a tilt angle is provided by UV irradiation and the response speed is improved. In addition, the residual DC voltage characteristics are also good, and it can be seen that there is almost no accumulation of residual DC voltage even after long-term DC application.

On the other hand, since component 2 was not introduced in the comparative example, it was confirmed that residual DC voltage was accumulated due to long-term DC application.

As described above, by combining the first component with a radical generating structure and the second component effective in suppressing residual DC voltage, the response speed is improved even when irradiated with long-wavelength ultraviolet rays (e.g., 365 nm), and the afterimage characteristics are also improved. It becomes possible to provide this excellent liquid crystal display element.

Claims (4)

A liquid crystal aligning agent characterized by containing the following (A) component, (B) component, and organic solvent.
(A) Component: a polyimide precursor having a side chain that vertically aligns the liquid crystal and a side chain that has a site that generates radicals upon ultraviolet irradiation represented by the following formula (1), and this polyimide precursor is imidized. At least one type of polymer selected from the polyimide obtained.
[Formula 1]

R ₁ and R ₂ are each independently an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and T ₁ and T ₂ are each independently a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, -N(CH ₃ )CO-, and S is a single bond or unsubstituted or It is an alkylene group having 1 to 20 carbon atoms substituted by a fluorine atom, and Ar is naphthylene, biphenylene, or phenylene, and the naphthylene, biphenylene, or phenylene is an alkyl group, a hydroxyl group, or an alkoxy group. and may be substituted with at least one substituent selected from the group consisting of amino groups. However, -CH ₂ - or -CF ₂ - of the alkylene group may be optionally substituted with -CH=CH-, and may be substituted with any of the following groups when they are not adjacent to each other; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbon ring, a divalent heterocycle, and Q represents a structure selected from the group below.
[Formula 2]

R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
(B) Component: A polyimide precursor obtained by using a diamine component containing at least one type of diamine selected from the following formulas (B-1) to (B-5) as a raw material, and a polyimide precursor obtained by imidizing the polyimide precursor. A polyimide precursor obtained by using a polymer selected from polyimides or a tetracarboxylic dianhydride component containing at least one tetracarboxylic dianhydride selected from the following formulas (3) and (4), and A polymer selected from polyimides obtained by imidizing this polyimide precursor.
[Formula 3]

Y ₁ is a secondary amine, a tertiary amine, or a monovalent organic group having a heterocyclic structure, and Y ₂ is a secondary amine, a tertiary amine, or a divalent organic group having a heterocyclic structure.
[Formula 4]

n, m are 0 or 1, and X, y are a single bond, carbonyl, ester, phenylene, or sulfonyl group. A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to claim 1 to a substrate and baking it. A liquid crystal display comprising applying the liquid crystal aligning agent according to claim 1 to a substrate, contacting it with a liquid crystal alignment film obtained by baking, forming a liquid crystal layer, and irradiating ultraviolet rays while applying a voltage to this liquid crystal layer, thereby providing a liquid crystal cell. device. A liquid crystal display characterized by forming a liquid crystal layer by applying the liquid crystal aligning agent according to claim 1 to a substrate and contacting it with a liquid crystal alignment film obtained by baking, and producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal layer. Method of manufacturing the device.