KR102609041B1 - Manufacturing method of liquid crystal display device and substrate for liquid crystal display device and liquid crystal display device assembly - Google Patents

Abstract

A liquid crystal aligning film forming step of forming a liquid crystal aligning film on each surface of a pair of substrates with a liquid crystal aligning agent of the same composition containing a polymer having a radical generating structure that generates radicals by light irradiation, and the pair of substrates A liquid crystal alignment film light irradiation step in which at least one side is irradiated with light to set the light irradiation amounts to both liquid crystal alignment films in different states, and thereafter, a liquid crystal layer is formed between the pair of substrates and a liquid crystal compound. Including a layer forming process.

Description

Manufacturing method of liquid crystal display device and substrate for liquid crystal display device and liquid crystal display device assembly

The present invention relates to a method of manufacturing a liquid crystal display device, a substrate for a liquid crystal display device, and a liquid crystal display device assembly, and in particular, to a vertically aligned liquid crystal display device manufactured by irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules. It relates to a manufacturing method, a substrate for a liquid crystal display device, and a liquid crystal display device assembly.

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 element, a photopolymerizable compound is added in advance to the liquid crystal composition, and a vertical alignment film such as a polyimide-based film is used to irradiate ultraviolet rays 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 inclined is usually controlled by protrusions formed on the substrate or slits formed in the display electrode. However, by adding a photopolymerizable compound to the liquid crystal composition, the liquid crystal cell 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 compared to a method of controlling the tilt direction of the liquid crystal molecules with only protrusions or slits, the response of the liquid crystal display element is improved. It is said that the speed is increasing.

Recently, as the quality of liquid crystal display elements has improved, there has been a demand for a faster response speed of the liquid crystal to voltage application and further improvement in reliability. For that purpose, it is necessary that the polymerizable compound reacts 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, it is necessary that no unreacted polymerizable compound remains after ultraviolet irradiation and that it does not adversely affect the reliability of the liquid crystal display device.

Therefore, a specific structure that generates radicals is introduced into the polymer constituting the liquid crystal aligning agent by ultraviolet irradiation, and the polymerizable compound in the liquid crystal and/or the liquid crystal aligning film is reacted through the use of this liquid crystal aligning agent. A liquid crystal aligning agent that can improve the response speed of a liquid crystal display element by increasing the reactivity of the polymerizable compound in the liquid crystal display element obtained using is proposed (see patent document 2).

Meanwhile, a first alignment layer is formed on a first substrate using a first alignment liquid containing a first alignment agent, and a second alignment layer is formed on a second substrate using a second alignment liquid containing a second alignment agent. Then, light is irradiated while applying an electric field with a liquid crystal layer between these substrates to cause the liquid crystal molecules adjacent to the first alignment layer to develop a first pretilt angle, while the liquid crystal molecules adjacent to the second alignment layer are exposed to a first pretilt angle. A method of manufacturing a liquid crystal display element that allows a pretilt angle to be expressed has been proposed (see Patent Document 3).

Japanese Patent Publication No. 2003-307720 WO2015/033921 Republic of Korea Publication No. 10-2016-0002599

K. Hanaoka, SID 04 DIGEST, P.1200 - 1202

However, in the method of patent document 3, it is necessary to use two types of liquid crystal aligning agents, and there is a problem that a large investment in equipment is required due to an increase in the number of steps and an increase in the number of production lines.

The object of the present invention is to provide a manufacturing method of a liquid crystal display device that can more simply manufacture a liquid crystal display device having liquid crystal layers with different orientation states on both sides without accompanying the above-mentioned problems, and using this manufacturing method. The object is to provide a substrate for a liquid crystal display device and a liquid crystal display device assembly.

As a result of intensive study, the present inventors used a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation, and before forming a liquid crystal layer, it was previously applied to at least one side of the liquid crystal aligning film. By irradiating light to nullify at least a part of the radical generating structure of the radical generating structure of the liquid crystal alignment film on one side, or by irradiating light so that the amount of light irradiation is different for both sides to make the radical generating ability of both sides different, the liquid crystal The present invention was completed by discovering that liquid crystal layers with different orientation states can be formed on both sides of the layer.

That is, the present invention has the following gist.

A liquid crystal aligning film forming step of forming a liquid crystal aligning film on each surface of a pair of substrates with a liquid crystal aligning agent of the same composition containing a polymer having a radical generating structure that generates radicals by light irradiation, and the pair of substrates A liquid crystal alignment film light irradiation step in which at least one side is irradiated with light to set the light irradiation amounts to both liquid crystal alignment films in different states, and thereafter, a liquid crystal layer is formed between the pair of substrates and a liquid crystal compound. A method of manufacturing a liquid crystal display device comprising a layer forming process.

Moreover, it is a substrate for forming a liquid crystal display element provided with a liquid crystal alignment film, wherein the liquid crystal alignment film is formed of a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation, and the radicals are generated by light irradiation. A substrate for forming a liquid crystal display device, characterized in that radicals are generated from at least part of the generating structure.

Also, a liquid crystal display assembly comprising a substrate for forming a liquid crystal display device having a pair of liquid crystal alignment films, and a liquid crystal layer formed between the pair of substrates for the liquid crystal display device, wherein the pair of liquid crystal display device forming devices includes: The liquid crystal alignment film of the substrate is formed of a liquid crystal aligning agent of the same composition containing a polymer having a radical generating structure that generates radicals upon light irradiation, and light irradiation is applied to at least one side, so that the light irradiation amounts of both are different. A liquid crystal display device assembly characterized in that.

According to the present invention, before forming the liquid crystal layer, using a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation, at least one liquid crystal alignment film is previously irradiated with light. Alignment is achieved on both sides of the liquid crystal layer by nullifying at least part of the radical generating ability of the radical generating structure of the liquid crystal alignment film on one side, or by irradiating both sides with different amounts of light to make the radical generating ability of both sides different. A manufacturing method of a liquid crystal display element that can form liquid crystal layers in different states and more easily manufacture a liquid crystal display element having liquid crystal layers in different orientation states on both sides, and a liquid crystal display element used in this manufacturing method A substrate and a liquid crystal display device assembly can be provided.

Moreover, according to the present invention, it is possible to provide a liquid crystal aligning agent suitable for a vertically aligned liquid crystal display element with a fast response speed, especially a PSA type liquid crystal display element.

Hereinafter, the present invention will be described in detail.

＜Manufacturing method of liquid crystal display device＞

The manufacturing method of a liquid crystal display element of this invention is a liquid crystal alignment film formation process of forming a liquid crystal alignment film on each of the surfaces of a pair of substrates with a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation. and a liquid crystal alignment film light irradiation step in which light is irradiated to at least one of the pair of substrates to vary the amount of light irradiation to both liquid crystal alignment films, and thereafter, a liquid crystal compound is placed between the pair of substrates. It is characterized by comprising a liquid crystal layer forming process to form a liquid crystal layer containing the liquid crystal layer.

In the liquid crystal aligning film formation process of this invention, the board|substrate with which the liquid crystal aligning film formed with the liquid crystal aligning agent of the same composition was formed is prepared. Although the liquid crystal aligning agent used here is a liquid crystal aligning agent containing a polymer which has a radical generation structure which generates radicals by light irradiation, the details of this liquid crystal aligning agent are mentioned later.

In the present invention, a liquid crystal alignment film light irradiation step is then provided, in which light is irradiated to at least one side of a pair of substrates and the light irradiation amounts to both liquid crystal alignment films are made different. This liquid crystal alignment film light irradiation step irradiates light to the liquid crystal alignment film of the substrate used on one side to nullify at least part of the radical generation ability of the radical generation structure of the liquid crystal alignment film on one side, or the amount of light irradiation is different between the two. Light irradiation is performed so that the radical generation abilities of both sides are different.

Here, light irradiation nullifies at least a part of the radical generation structure of the formed liquid crystal alignment film, that is, generates radicals at this point, and prevents radicals from being generated thereafter. Light irradiation may be specifically performed with light of a wavelength necessary to deactivate the radical generating structure.

Specifically, the liquid crystal alignment film light irradiation step irradiates light to the liquid crystal alignment film of the substrate used on one side, nullifies at least a part of the radical generating structure, and nullifies the radical generating ability. As a result, one side is a liquid crystal alignment film that does not have a radical generation ability and the other side is a liquid crystal alignment film that has a radical generation ability, or one side is a liquid crystal alignment film that has a low radical generation ability and the other side is a liquid crystal alignment film that has a high radical generation ability, so that both sides Ensure that the radical generation ability is different.

Moreover, for example, light is irradiated to the liquid crystal alignment film of the substrate on both sides, but the amount of light irradiation is made to be different on both sides, and the amount of the radical generating structure to be nullified is made to be different on both sides. As a result, one side is a liquid crystal alignment film with a low radical generation ability, and the other side is a liquid crystal alignment film with a high radical generation ability, so that the radical generation abilities of both sides are different.

The present invention includes a liquid crystal layer forming step of forming a liquid crystal layer containing a polymerizable compound between the pair of substrates. As a result, a liquid crystal layer is formed sandwiched between a pair of liquid crystal alignment films with different radical generation capabilities, so that an asymmetric liquid crystal layer with different pretilt angles on both sides can be obtained.

＜Polymer with radical generating structure＞

Although the polymer which has a radical generating structure contained in the liquid crystal aligning agent used in this invention is demonstrated by giving a specific example, it is not limited to the following specific examples.

The polymer having a radical generating structure (hereinafter also referred to as a specific polymer) used in the present invention has as a side chain a site where radicals are generated by light irradiation, for example, ultraviolet irradiation. As a specific polymer, a radical generating structure in which radicals are generated by ultraviolet irradiation, for example, a polymer containing a side chain structure represented by the following formula (I) can be mentioned.

[Formula 1]

Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, which may be substituted with an organic group, and the hydrogen atom may be substituted with a halogen atom. R ₁ and R ₂ are each independently an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and T1 and T2 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 fluorine An alkylene group having 1 to 20 carbon atoms substituted by an atom. 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 listed below in cases 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 group below.

[Formula 2]

(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-.)

In the above formula (I), Ar to which the carbonyl is bonded is involved in the absorption wavelength of ultraviolet rays, so when the wavelength is increased, 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.

In formula (I), when Ar has a structure like naphthylene or biphenylene, solubility worsens and the difficulty of synthesis also increases. If the wavelength of ultraviolet rays is in the range of 250 nm to 380 nm, sufficient characteristics can be obtained even with a phenyl group, so a phenyl group is most preferable.

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. In the case of an alkyl group or an alkoxy group, R ₁ and R ₂ may form a ring. do.

In formula (I), Q is preferably an electron-donating organic group, and this group is 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.

When attempting to introduce the structure of the formula (I) into the side chain using a polyimide precursor and or polyimide as a specific polymer, the side chain structure of the formula (I) is used to improve the handling properties of the raw materials and the polymer. It is preferable in view of ease of synthesis.

The site that generates radicals by ultraviolet irradiation in the formula (I) is specifically preferably as follows. In particular, (b) or (c) is preferable from the viewpoint of reliability of the resulting liquid crystal display element.

[Formula 3]

In addition, in formula (I), -T ₁ -ST ₂ - serves as a linking group that connects diaminobenzene and the site that generates a radical 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- , may be substituted with any of the following groups if they are not adjacent to each other; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, is a divalent carbon ring or heterocyclic ring .) 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.

Moreover, as a specific polymer used in this invention, a polymer containing the side chain structure represented by the following formula (II) is mentioned, for example.

[Formula 4]

In formula (II), the dot means a bond to the main chain of the polymer, n is an integer selected from 1 to 12, and X is a single bond, -O-, -COO-, -OCO-, -NHCO- , -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-. Cy represents a cyclic hydrocarbon group having 5 to 14 carbon atoms, which has at least one unsaturated bond necessarily bonded to the carbonyl carbon of the imide group, and some of the carbon atoms constituting the cyclic hydrocarbon may be substituted with heteroatoms. .

This specific polymer has an organic group represented by the above formula (II) in the side chain. This organic group is thought to have the function of being excited by ultraviolet irradiation to generate radicals or chain-transferring radicals generated by other organic groups, and functioning as a radical generating structure. A structure having the function of chain-transferring this radical is also included in the radical generating structure of the present invention.

In the above formula (I), it is important that Cy, that is, a cyclic hydrocarbon group having at least one unsaturated bond is bonded to two carbonyl carbons in the imide ring, and in particular, the unsaturated bond is directly bonded to two carbonyl carbons. The structure being used is desirable. In particular, as the number of unsaturated bonds increases, the absorbance in the ultraviolet region increases and the absorption wavelength becomes longer, so it is preferable when performing long-wavelength exposure. Moreover, aromatic hydrocarbon groups and heterocyclic compounds having 6 to 14 carbon atoms are more preferable. Considering the availability of reagents and the difficulty of synthesis, a cyclic hydrocarbon group that does not contain a hetero atom is preferable. Examples of preferred Cy are shown below, but are not limited to these. Additionally, the two dots of Cy each represent a bond to the imide carbonyl carbon.

[Formula 5]

On the other hand, as the number of carbon atoms forming the ring structure increases, the more rigid the structure becomes, the less solubility in solvents becomes. Therefore, from the viewpoint of monomer synthesis and ease of handling of the monomer, cyclic hydrocarbons with relatively few carbon atoms are preferred. Preferred, particularly preferably cyclohexene, benzene, naphthalene, biphenylene, etc. More preferably, it has the following structure.

[Formula 6]

The hydrogen atom of the cyclic hydrocarbon group directly connected to the imide ring may be substituted with a fluorine atom or the like, or may be substituted with an organic group. There is no particular limitation on the organic group to be substituted, but introduction of an organic group with strong electron donating or electron accepting properties is desirable because the effect of increasing the absorption wavelength is expected to be longer. On the other hand, since nitro groups, amino groups, etc. have the possibility of trapping generated radicals, monovalent organic groups with a molecular weight of 14 to 100 are preferred. Examples include organic groups such as hydroxyl groups and hydroxyl groups, and relatively Examples include alkoxyl groups and alkyl groups with small molecular weights, but care must be taken in selecting the substituent because the introduced substituent may trap the generated radical. For the above reasons, it is most preferably unsubstituted.

In the above formula (II), -XC _n (H ₂ ) _n - represents the linking site with the polymer chain. Since the structure that binds to the imide carbonyl group of the side chain represented by the formula (II) above is important in the present invention, there is no need to specifically limit the linking site. However, given the preferred structure of -X-, X is a single bond, - O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ ) CO-, etc. can be mentioned. Moreover, the alkylene connected to It can be done. From the viewpoint of availability of reagents and synthesis, the structure that is easiest to synthesize is -O-, where X is -O-, and alkylene is a straight chain alkylene having 1 to 6 carbon atoms.

In the present invention, for a polymer having an organic group represented by the above formula (II) as a side chain, the means for introducing the side chain into the polymer is not particularly limited. Examples include a method of obtaining a polymer by polymerization using a monomer having a side chain structure represented by the above formula (II), a method of introducing the polymer through polymer modification, etc. Preferably, it is a method of introducing into the polymer using a monomer having an organic group represented by the above formula (I).

The radical generating structure of the present invention is not limited to that described above, and any side chain structure other than the described side chain structure can be preferably used as long as it has a radical generating structure. For example, a polymer containing a radical generating structure including a reactive mesogenic structure (see patent document 3 claim 1, etc.) in the side chain can also be used.

＜Side chains that orient the liquid crystal vertically＞

The specific polymer contained in the liquid crystal aligning agent used in the present invention orients the liquid crystal vertically other than the side chain (hereinafter also referred to as specific side chain) having a radical generating structure represented by the above formula (I) or (II). It is desirable to have side chains. The side chain that vertically aligns the liquid crystal is represented by the following formula [III-1] or formula [III-2]. Additionally, apart from the specific polymer mentioned above, a polymer having a side chain that vertically aligns the liquid crystal may be blended with the liquid crystal aligning agent.

[Formula 7]

(X ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, or ^-OCO- . Represents a single _bond or (CH ₂ ) _b - ( _b ^is an integer from 1 to 15). , -CH ₂ O- ^, -COO- or -OCO-. It may be substituted with an alkyl group of 1 to 3 carbon atoms, an alkoxyl group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine atom, and X ⁴ has a steroid skeleton. It may be a divalent organic group selected from organic groups having 17 to ⁵¹ carbon atoms. It may be substituted with an alkyl group with 1 to 3 carbon atoms, an alkoxyl group with 1 to 3 carbon atoms, a fluorine-containing alkyl group with 1 to 3 carbon atoms, a fluorine-containing alkoxyl group with 1 to 3 carbon atoms, or a fluorine atom. n represents an integer from 0 to 4. ⁶ represents an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, an alkoxyl group with 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group with 1 to 18 carbon atoms.)

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. And 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, among others, 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 ^them , 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.

Preferred combinations 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 page 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 and a steroid skeleton is read as an organic group having 17 to 51 carbon atoms and 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 8]

X ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO- indicates. X ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. _Among ^them _, , -CONH- or -COO-. Among these, X ⁸ is preferably an alkyl group having 8 to 18 carbon atoms.

As the side chain for vertically aligning the liquid crystal, it is preferable to use the structure represented by the formula [III-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 orient the liquid crystal varies depending on the structure of the side chain to vertically orient the liquid crystal, but generally, the ability of the side chain to vertically orient the liquid crystal As the amount 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＞

For example, the specific polymer contained in the liquid crystal aligning agent of this invention may have a photoreactive side chain other than the side chain which has a radical generating structure represented by said formula (I) or (II). 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. Moreover, separately from the specific polymer mentioned above, you may mix|blend a polymer which has a photoreactive side chain with a liquid crystal aligning agent.

The photoreactive side chain may be directly bonded to the main chain of the polymer, or may be bonded to it through a linking group. The photoreactive side chain is represented by the following formula [IV], for example.

[Formula 9]

R ⁸ is a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-. R ⁹ represents a single bond and an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and -CH ₂ - of the alkylene group may be optionally substituted with -CF ₂ - or -CH=CH-, and If any 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. R ¹⁰ represents a photoreactive group selected from the following formula. 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.

[Formula 10]

[Formula 11]

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 methacryl.

In addition, in the formula [IV], the divalent carbon ring or heterocycle substituting any -CH ₂ - of R ⁹ is specifically exemplified by the following.

[Formula 12]

R ¹⁰ is preferably a methacrylic group, an acrylic group, or a vinyl 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.

<Polymer forming liquid crystal aligning agent>

The polymer having a radical generating structure used in the present invention is not particularly limited, but polyimide-based, poly(meth)acrylate-based, polysiloxane-based polymers, etc. can be preferably used. Hereinafter, in this specification, only the polyimide structure will be described in detail, but other polymers can also be synthesized using known techniques (radical polymerization, sol/gel method, etc.).

The method for producing a polyimide precursor having a specific side chain and a polyimide obtained by imidizing the polyimide precursor is not particularly limited. For example, a method of polymerizing a diamine and tetracarboxylic acid dianhydride having a specific side chain, a method of polymerizing a diamine and a tetracarboxylic acid diester having a specific side chain, and a method of polymerizing tetracarboxylic acid dianhydride having a specific side chain. Examples include a method of polymerizing water and a diamine compound, a method of polymerizing tetracarboxylic dianhydride and diamine, and then modifying the polymer with a compound containing a specific side chain through any reaction. Among these, from the viewpoint of ease of production, a method of polymerizing a diamine compound containing a specific side chain and tetracarboxylic dianhydride or tetracarboxylic acid diester is preferable.

In addition to the specific side chain, the same method as described above can be used for producing a polyimide precursor having a side chain that vertically aligns the liquid crystal, and a polyimide obtained by imidizing the polyimide precursor. Likewise, the preferred method is a method of polymerizing a diamine compound containing a side chain that vertically aligns the liquid crystal and tetracarboxylic dianhydride or tetracarboxylic acid diester.

A polyimide having a radical generating structure in the side chain can be prepared, for example, by using one or more types of diamines such as the following specific diamines 1 to 3.

＜Specific diamine 1＞

The diamine (hereinafter also referred to as specific diamine) used in the production of the polymer forming the liquid crystal aligning agent of the present invention has as a side chain a site having a radical generating structure that is decomposed by ultraviolet irradiation and generates radicals, It is expressed by the following formula (1).

[Formula 13]

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

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

As for specific diamine 1, 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 14]

＜Synthesis of specific diamine 1＞

In the present invention, the specific diamine 1 is synthesized through each step to form a dinitro form, a mononitro form having an amino group with a removable protecting group in the reduction step, or a diamine, and then remove the nitro group by a commonly used reduction reaction. It can be obtained by converting to an amino group or deprotecting a protecting group.

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 15]

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.

The method of reducing the dinitro compound, which is a diamine precursor, is not particularly limited, and usually palladium carbon, platinum oxide, Raney nickel, platinum carbon, rhodium-alumina, platinum sulfide carbon, etc. are used as catalysts, and ethyl acetate, toluene, There is a method of performing reduction using hydrogen gas, hydrazine, hydrogen chloride, etc. in solvents such as tetrahydrofuran, dioxane, and alcohol. 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.

In addition, the diamine of the present invention can be obtained from diaminobenzene derivatives protected with a benzyl group or the like by similarly deprotecting them through the above reduction process.

Specific diamine 1 is preferably used in an amount of 10 to 80 mol%, more preferably 20 to 60 mol%, and particularly preferably 30 to 50 mol% of the diamine component used in the synthesis of polyamic acid. .

＜Specific diamine 2＞

The specific diamine 2 of the present invention is a diamine having an organic group represented by the above formula (II) as a side chain, that is, it can be represented by the following formula (VI).

[Formula 16]

In formula (VI), Sp is an alkylene group having 1 to 12 carbon atoms, and the alkylene group may have an unsaturated bond, a branched chain, or a cyclic structure. X represents a single bond or linking group. Cy represents a cyclic hydrocarbon group having 5 to 14 carbon atoms, which has at least one unsaturated bond necessarily bonded to the carbonyl carbon of the imide group, and some of the carbon atoms constituting the cyclic hydrocarbon may be substituted with heteroatoms. .

Diaminobenzene in formula (VI) may have any structure among o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine, but in terms of reactivity with acid dianhydride, m-phenylene Diamine, or p-phenylenediamine, is preferred. A preferable structure of formula (VI) is a diamine represented by the following formula (X),

[Formula 17]

(n in the formula is an integer from 1 to 6)

More preferably, from the viewpoint of ease of synthesis, high versatility, properties, etc., the structure represented by the following formula (XI) is most preferable.

[Formula 18]

(In the formula, m is an integer between 1 and 3)

＜Synthesis of specific diamine 2＞

In the present invention, the specific diamine 2 is synthesized through each step to form a dinitro form, a mononitro form having an amino group with a removable protecting group in a reduction step, or a diamine, and then remove the nitro group by a commonly used reduction reaction. It can be obtained by converting to an amino group or deprotecting a protecting group.

There are several possible methods for synthesizing diamine precursors. For example, a diamine precursor can be obtained by reacting an alcohol, alkylamine, or alkyl halide having the desired imide structure with dinitrobenzene, or by reacting an alkylamine into which dinitrobenzene has already been introduced with an acid anhydride. Methods include a photoreaction reaction between an alcohol into which dinitrobenzene has already been introduced and an N-unsubstituted imide, and a method of condensing an alkyl halide into which dinitrobenzene has already been introduced and an N-unsubstituted imide in the presence of a base or metal catalyst. there is.

[Formula 19]

The above is a synthesis example of a product in which the linkage with the dinitrobody is an ether bond, but other products in which the linkage group is an ester bond or an amide bond can also be synthesized according to the above method.

The method of reducing the dinitro compound, which is a diamine precursor, is not particularly limited, and usually palladium carbon, platinum oxide, Raney nickel, platinum carbon, rhodium-alumina, platinum sulfide carbon, etc. are used as catalysts, and ethyl acetate, toluene, There is a method of performing reduction using hydrogen gas, hydrazine, hydrogen chloride, etc. in solvents such as tetrahydrofuran, dioxane, and alcohol. 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.

In addition, the diamine of the present invention can be obtained from diaminobenzene derivatives protected with a benzyl group or the like by similarly deprotecting them through the above reduction process.

＜Specific diamine 3＞

Specific diamine 3 of the present invention is represented by the following formula (11).

[Formula 20]

Specific diamine 3 has, in its single molecule structure, a photoreactive structure that generates radicals by ultraviolet irradiation and a structure that vertically aligns the liquid crystal. That ^is , the ^{photoreactive} structure is a 4-chromanone structure bonded to the phenylenediamine skeleton through It has a structure of ¹³ -X ¹⁴ .

In the above formula (11), the definitions of X ¹¹ , X ¹² , X ¹³ , and X ¹⁴ are as described above. Among them, X ¹¹ is preferably -O- or -CH ₂ O- from the viewpoint of ease of synthesis. Moreover, X ¹² and X ¹³ are preferably cyclohexane rings from the viewpoint of high vertical alignment. Moreover, X ¹⁴ is preferably an alkyl group having 3 to 7 carbon atoms from the viewpoint of availability of raw materials.

Preferred specific examples of the specific diamine 3 include the following.

[Formula 21]

＜Production of specific diamine 3＞

The method for synthesizing specific diamine 3 in the present invention is not particularly limited, but it can be synthesized, for example, by the method shown below.

That is, by synthesizing a dinitro compound ^represented by the following general formula (12) corresponding to the specific diamine 3 (wherein X ¹¹ to obtained.

[Formula 22]

There is no particular limitation on the method of reducing the dinitro compound, and usually palladium-carbon, platinum-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, rhodium-alumina, platinum carbon sulfide, etc. are used as catalysts. There is a method of carrying out the reaction using solvents such as ethyl acetate, toluene, tetrahydrofuran, dioxane, alcohol, hydrogen gas, hydrazine, hydrogen chloride, ammonium chloride, etc.

The method for synthesizing the dinitro compound represented by the general formula (12) is not particularly limited and can be synthesized by any method. Specific examples thereof include, for example, the method shown in Scheme (13) below. It can be synthesized with

[Formula 23]

In scheme (13), dinitro compound A and compound B having a hydroxyl group are mixed in an organic solvent (e.g., ethyl acetate, toluene, tetrahydrofuran, dioxane, chloroform, dichloromethane, DMF, DMSO, etc.), It can be synthesized by reacting in the presence of alkali. As the alkali, for example, organic amines such as triethylamine, and inorganic salts such as potassium carbonate and sodium hydroxide can be used.

In _{the dinitrobenzene} compound ^A , and X ¹² to X ¹⁴ in the phenol compound B are the same as in Formula 1. In addition, the compound shown here is an example and is not particularly limited.

The specific diamine is preferably used in an amount of 10 mol% to 80 mol%, more preferably 20 mol% to 60 mol%, and particularly preferably 30 mol% of the diamine component used in the synthesis of polyamic acid. It is ~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.

[Formula 24]

X represents the structure of the formula [III-1] or [III-2], and n represents an integer of 1 to 4.

[Formula 25]

R ⁸ , R ⁹ , and R ¹⁰ are as defined above.

[Formula 26]

Y ₁ to Y ₆ are as indicated above.

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

[Formula 27]

(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 28]

(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 29]

(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 30]

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

[Formula 31]

(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 32]

(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). Additionally, 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 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

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

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

[Formula 38]

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

[Formula 39]

[Formula 40]

[Formula 41]

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 holding 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 70 mol% of the diamine component used in the synthesis of polyamic acid, more preferably in an amount of 20 mol% to 60 mol% of the diamine component. , especially preferably 20 mol% to 50 mol%.

<Diamine containing photoreactive side chains>

In the method of introducing a photoreactive side chain into a polyimide polymer, it is preferable to use a diamine with a specific side chain structure as part of the diamine component. As diamine which has a photoreactive side chain, it is diamine which has a side chain represented by formula [VIII] or formula [IX].

[Formula 42]

(The definitions of R ⁸ , R ⁹ and R ¹⁰ in [VIII] are the same as those in the above formula [IV].)

[Formula 43]

(The definitions of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , and Y ₆ in formula [IX] are the same as those of formula [V] above.)

The bonding positions of two amino groups (-NH ₂ ) in formulas [VIII] and formula [IX] are 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, but are not limited to, the following.

[Formula 44]

(X ^{9 and} indicates.)

Moreover, the diamine which has a photoreactive side chain also includes the diamine which has in the side chain the group which causes a photo dimerization reaction shown by the following formula, and the group which causes a photopolymerization reaction.

[Formula 45]

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 the photoreactive side chain is one type depending on the 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. Alternatively, two or more types can be mixed and used.

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%.

＜(B) Ingredient＞

The liquid crystal aligning agent of this invention is (A) a polyimide precursor which has a side chain which vertically aligns a liquid crystal, a side chain which has a radical generating structure represented by said formula (I), and this polyimide precursor as component (A) A diamine component containing at least one type of polymer selected from polyimides obtained by imidizing and, as component (B), at least one type of diamine selected from the following formulas (B-1) to (B-5) A polymer selected from a polyimide precursor obtained as a raw material, and a polyimide obtained by imidizing this polyimide precursor, or at least one tetracarboxylic dianhydride selected from the following formulas (3) and (4) It can contain a polymer selected from a polyimide precursor obtained by reaction of a tetracarboxylic dianhydride component containing a diamine, and a polyimide obtained by imidizing this polyimide precursor.

[Formula 46]

(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. .)

[Formula 47]

(In the formula, n, m are 0 or 1, and X, y are a single bond, carbonyl, ester, phenylene, or sulfonyl group.)
If at least one tetracarboxylic dianhydride selected from the above formulas (3) and (4) is used as a raw material, the accumulated charge characteristics can be improved, possibly due to interaction between [liquid crystal-alignment film] by light irradiation. You can. 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 48]

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 diamine included as the 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 A polymer selected from polyimides obtained by imidizing a precursor may be used.

[Formula 49]

(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 diamine having a highly polar specific structure selected from the above formulas (B-1) to (B-5) is used, or a diamine having a carboxyl group and a diamine having a nitrogen-containing aromatic heterocycle are used, respectively. By using at least 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 50]

＜Other diamines＞

In addition, when producing a polyimide precursor and/or polyimide, diamines other than the above-described 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'-diamino Diphenyl 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- Aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]dianiline, 4,4'-[1,3-phenylenebis(methylene)]dianiline, 3,4' -[1,4-phenylenebis(methylene)]dianiline, 3,4'-[1,3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis( methylene)]dianiline, 3,3'-[1,3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylene Bis[(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) Hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl) ) Propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 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- Aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1, 7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy) ) Octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-(4-aminophenoxy)decane, 1,10-(3 -Aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-aminophenoxy)dodecane, 1 , Aromatic diamines such as 12-(3-aminophenoxy)dodecane, alicyclic diamines such as bis(4-aminocyclohexyl)methane and bis(4-amino-3-methylcyclohexyl)methane, 1,3- Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminoctane, 1,9-diamine Aliphatic diamines such as nononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminodecane can be mentioned.

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]octo-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- Tricarboxynorbornane-2:3, 5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc. are mentioned. 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.

＜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 causes polymerization by irradiating light. In addition, the compound having a photocrosslinking group is a compound that reacts with at least one type of polymer selected from a polymer of a polymerizable compound, a polyimide precursor, and a polyimide obtained by imidizing this polyimide precursor by irradiating light. 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.

Examples of the group to be photopolymerized or photocrosslinked include a monovalent group represented by the following formula (X).

[Formula 51]

(R ¹² represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. Z ¹ represents a divalent aromatic ring or heterocyclic ring that may be substituted with an alkyl group with 1 to 12 carbon atoms or an alkoxyl group with 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 (XI), a terminal having a photopolymerizable group represented by the following formula (XII), and a terminal having a photocrosslinking group. and compounds having a photocrosslinking group at each of the two terminals represented by the following formula (XIII).

In addition, in the following formulas (XI) to (XIII), R ¹² , Z ¹ and Z ² are the same as R ¹² , Z ¹ and Z ² in the formula (X), 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 52]

[Formula 53]

[Formula 54]

Specific examples of the polymerizable compound represented by formula [XI] 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 55]

Furthermore, even if the group to be photopolymerized or photocrosslinked is a polymerizable compound that has an acrylate group or a methacrylate group rather than an α-methylene-γ-butyrolactone group, the acrylate group or methacrylate group may be used as a spacer such as an oxyalkylene group. A polymerizable compound having a structure in which a phenylene group is bonded 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 a 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 sintering temperature of 200°C or higher. can sufficiently withstand.

＜Synthesis of polyamic acid＞

When obtaining a polyamic acid by reaction between 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, and N-methyl-2. -Pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N-methyl Caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, 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. , dioxane, 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 acetate. 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, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, etc. 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 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 tetracarboxylic dianhydride component is composed 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 example, the total concentration of the diamine component and the tetracarboxylic dianhydride component in the reaction liquid is preferably 1 to 50 mass%, and more preferably 5 to 30 mass%.

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 reacting by a known method using a tetracarboxylic acid derivative such as acid dihalide.

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. In other words, 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＞

The agent of the present invention contains at least one specific polymer having a radical generating structure in the side chain. The content of this specific polymer is preferably 0.5 to 20% by mass, more preferably 0.5 to 15% by mass, particularly preferably is 1 to 10 mass%.

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 possessed by the liquid crystal aligning agent is the weight average molecular weight 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. It 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 each has a polymer having a structure represented by the above formula (I) in the side chain and a group that is photopolymerized or photocrosslinked at two or more terminals contained as needed. Any material that can dissolve or disperse components such as polymerizable compounds may be sufficient. For example, the organic solvents exemplified in the synthesis of the polyamic acid above 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 mono Methyl 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 butylate, butyl ether , diisobutyl 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 glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-meth Propyl toxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol mono Acetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, lactic acid Examples include methyl ester, ethyl lactic acid, n-propyl lactic acid, n-butyl lactic acid, isoamyl lactic acid, and 2-ethyl-1-hexanol. 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, SC106 (manufactured by Asahi Glass), etc. The usage ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to the total amount of 100 parts by mass 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-ureide propyltrimethoxysilane, 3-ureide propyltriethoxysilane, 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, in addition to the above, you may add a dielectric or a conductive substance for the purpose of changing the electrical properties, such as the 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.

By applying this liquid crystal aligning agent onto 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 each 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 made to contain in a liquid crystal aligning agent, or is contained in a liquid crystal together with a liquid crystal aligning agent. By doing so, the light reaction becomes highly sensitive even in the so-called PSA mode, and a tilt angle can be provided even with a small amount of ultraviolet rays.

For example, after apply|coating the liquid crystal aligning agent of this invention to a board|substrate, the cured film obtained by drying and baking as needed 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. Plastic substrates such as trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetylcellulose, diacetylcellulose, and acetate butylate cellulose can be used. In addition, it is preferable to use a substrate on which ITO electrodes for driving liquid crystal are formed, from the viewpoint of process simplification. Additionally, in a reflective liquid crystal display device, an opaque material such as a silicon wafer can be used as long as it is used as a substrate on only one side, 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 firing is not constant for each substrate, or when firing 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 20 to 200 nm.

＜Manufacturing method of liquid crystal display device＞

The manufacturing method of the liquid crystal display element of this invention first implements the liquid crystal aligning film formation process of forming a liquid crystal aligning film on each of the surfaces of a pair of board|substrates as mentioned above.

Next, light is irradiated to at least one of the pair of substrates, and a liquid crystal alignment film light irradiation step is performed in which the light irradiation amounts to both liquid crystal alignment films are made different.

This liquid crystal alignment film light irradiation step irradiates light to the liquid crystal alignment film of the substrate used on one side to nullify at least part of the radical generation ability of the radical generation structure of the liquid crystal alignment film on one side, or the amount of light irradiation is different between the two. Light irradiation is performed so that the radical generation abilities of both sides are different.

Specifically, the liquid crystal alignment film light irradiation step irradiates light to the liquid crystal alignment film of the substrate used on one side, nullifies at least a part of the radical generating structure, and nullifies the radical generating ability. As a result, one side is a liquid crystal alignment film that does not have a radical generation ability and the other side is a liquid crystal alignment film that has a radical generation ability, or one side is a liquid crystal alignment film that has a low radical generation ability and the other side is a liquid crystal alignment film that has a high radical generation ability, so that both sides Ensure that the radical generation ability is different.

Moreover, for example, light is irradiated to the liquid crystal alignment film of the substrate on both sides, but the amount of light irradiation is made to be different on both sides, and the amount of the radical generating structure to be nullified is made to be different on both sides. As a result, one side is a liquid crystal alignment film with a low radical generation ability, and the other side is a liquid crystal alignment film with a high radical generation ability, so that the radical generation abilities of both sides are different.

In this way, the liquid crystal aligning film using the liquid crystal aligning agent of the same composition of the present invention has a predetermined liquid crystal aligning ability based on the functions of the various side chains of the polymer described above, but the radical generating ability is different as described above. By processing, the amount of radicals generated by ultraviolet rays during PSA treatment varies for each substrate.

For this reason, the reaction rate of the polymerizable compound is different at each substrate interface, and the liquid crystal alignment ability is also different.

As light irradiation for treatment to deactivate the radical generating structure, a wavelength of about 250 nm to 600 nm can be used, and the wavelength is preferably adjusted to suit the radical generating structure.

For example, since the structure represented by formula (I) often has absorption ranging from approximately 250 nm to 420 nm, it is desirable to irradiate ultraviolet rays of 250 nm to 420 nm according to the absorption wavelength. Regarding the desired amount of light irradiation, it is necessary to match the desired panel characteristics, but since long-time light irradiation leads to a shortened tact time in the device manufacturing process, it is desirable to change it appropriately. In general, it is believed that the radical generating structure can be deactivated more efficiently by irradiating light according to the maximum absorption wavelength of the radical generating structure. Considering the influence on the tact time of the production line and damage to other members, the preferable light irradiation amount is preferably 500 mJ/cm2 to 100 J/cm2, and more preferably 1 J/cm2 to 70 J. /cm2, more preferably 1 J/cm2 to 40 J/cm2.

Therefore, when a liquid crystal layer is formed between a pair of substrates having liquid crystal aligning films of the same composition but different liquid crystal aligning abilities, the portion close to the surface of the liquid crystal layer is aligned with the liquid crystal aligning film of the adjacent liquid crystal aligning film. Since the orientation state is formed based on the function, the orientation state on both sides is different. Specifically, in the case of having vertically aligned side chains, it is possible to realize an asymmetric liquid crystal layer with different pretilt angles on both sides.

The method for manufacturing a liquid crystal display device of the present invention includes a liquid crystal layer forming step of forming a liquid crystal layer containing a liquid crystal compound between the pair of substrates. As a result, a liquid crystal layer is formed sandwiched between a pair of liquid crystal alignment films with different radical generation capabilities, so that an asymmetric liquid crystal layer with different pretilt angles on both sides can be obtained.

＜Substrate for liquid crystal display device＞

When a liquid crystal alignment film is formed using a liquid crystal aligning agent containing a specific polymer having a radical generating structure, the radical generating structure is usually used to generate radicals by light irradiation when forming the liquid crystal layer.

However, in the present invention, before forming the liquid crystal alignment film of the substrate used on at least one side into a liquid crystal layer, light is irradiated to nullify at least a part of the radical generating structure, thereby nullifying the radical generating ability.

As a substrate for a liquid crystal display element before forming a liquid crystal layer, a liquid crystal alignment film is formed using a liquid crystal alignment agent containing a specific polymer having a radical generating structure, and light is irradiated to form at least part of the radical generating structure. The substrate for a liquid crystal display element of the present invention is one in which is invalidated.

＜Liquid crystal display element assembly＞

The liquid crystal display element assembly of the present invention uses a substrate on which a liquid crystal alignment film is formed using a liquid crystal aligning agent of the same composition as the substrate for a liquid crystal display element of the present invention described above, and a liquid crystal raw material to become a liquid crystal layer is placed between them. It was narrow-minded. In addition, as a substrate for a liquid crystal display device of the present invention, a pair of substrates having different pre-irradiated light irradiation amounts is used, and a liquid crystal raw material forming a liquid crystal layer is sandwiched between them.

＜Liquid crystal display device＞

The liquid crystal display device manufactured by the method for manufacturing a liquid crystal display device of the present invention can produce a liquid crystal cell by a known method using the substrate for a liquid crystal display device of the present invention described above, whereby the radical generation ability is different. Since the liquid crystal layer sandwiched between a pair of liquid crystal alignment films is formed, an asymmetric liquid crystal layer with different pretilt angles on both sides can be formed.

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, the liquid crystal aligning agent of the present invention is applied to two substrates and baked to form a liquid crystal aligning film, and at least one side is irradiated with light to nullify at least a part of the radical generating structure, and the radical generating ability of the radical generating structure is different. Two substrates are arranged so that the liquid crystal alignment films face each other, and a liquid crystal layer made of liquid crystal is sandwiched between the two substrates, that is, a liquid crystal layer is formed by contacting the liquid crystal alignment film, and a voltage is applied to the liquid crystal alignment film and the liquid crystal layer. It is produced by irradiating ultraviolet rays. This results in a vertically aligned liquid crystal display device having asymmetric liquid crystal cells with different pretilt angles on both sides.

Using a liquid crystal aligning film formed by 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 in 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 of this structure, the manufacturing process can be simplified and high transmittance can be obtained. there is.

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 is a liquid crystal material used in a conventional vertical alignment method, for example, a negative type such as MLC-6608 or MLC-6609 manufactured by Merck & Co. Liquid crystals can be used. In addition, in PSA mode, for example, a liquid crystal containing a polymerizable compound as represented by the following formula can be used.

[Formula 56]

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. (貼合) and a method of sealing the liquid crystal by injecting it under reduced pressure. 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 substrate together 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 applying this electric field to the liquid crystal alignment film and the liquid crystal layer. A method of irradiating ultraviolet rays while maintaining . Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of ultraviolet rays is, for example, 1 to 60 J/cm2, preferably 40 J/cm2 or less. A smaller irradiation amount of ultraviolet rays can suppress the decrease in reliability caused by destruction of the members constituting the liquid crystal display element. In addition, it is preferable because manufacturing efficiency increases by reducing the ultraviolet irradiation time.

As described above, when ultraviolet rays are irradiated while applying a 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 inclined 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 precursor obtained by imidizing this polyimide precursor are formed. Since the photoreactive side chains of at least one type of polymer selected from mead 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 dianhydride

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

PMDA: pyromellitic dianhydride

(diamine)

DBA: 3,5-diaminobenzoic acid

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

TCA: 2,3,5 tricarboxycyclopentylacetic dianhydride

DSDA: 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride

[Formula 57]

Diamine having a radical generating structure represented by the following formula DA-1 obtained in the synthesis examples

[Formula 58]

Vertically oriented diamine represented by the following formulas DA-2 to DA-3

[Formula 59]

Diamine compounds represented by the following formulas DA-4 to DA-7.

[Formula 60]

Vertically oriented diamine represented by the following formula DA-8.

[Formula 61]

＜Solvent＞

NMP: N-methyl-2-pyrrolidone

BCS: Butylcellosolve

＜Additives＞

3AMP: 3-picolylamine

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, Column: Column (KD-803, KD-805) manufactured by Shodex, Column temperature: 50°C 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, and tetrahydrofuran (THF) is 10 ml/L) Flow rate: 1.0 ml/min Standard sample for creating a calibration curve: TSK standard polyethylene oxide manufactured by Tosoh (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 the peak integrated value of this proton and the integrated peak value of the proton derived from the NH group of amic acid appearing around 9.5 to 10.0 ppm. It was obtained 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 (3.75 g, 15.0 mmol), DA-1 (4.96 g, 15.0 mmol), and DA-2 (5.71 g, 15.0 mmol) were dissolved in NMP (51.9 g), reacted at 60°C for 5 hours, and CBDA (2.88 g, 14.7 mmol) and NMP (17.3 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 (50 g) and diluting it to 6.5 mass%, acetic anhydride (8.8 g) and pyridine (2.7 g) were added as imidization catalysts, and the reaction was allowed to proceed at 75°C for 2.5 hours. This reaction solution was added to methanol (700 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 (A) was obtained. The imidization rate of this polyimide was 71%, the number average molecular weight was 12000, and the weight average molecular weight was 49000.

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 wt% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added to this solution, and the liquid crystal aligning agent (A1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 2)

BODA (3.75, 15.0 mmol), DA-3 (3.91 g, 9.0 mmol), DBA (0.91 g, 6.0 mmol), DA-1 (4.96 g, 15.0 mmol) were dissolved in NMP (49.3 g) and incubated at 60°C. After reacting for 5 hours, CBDA (2.88 g, 14.7 mmol) and NMP (16.4 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 (50 g) and diluting it to 6.5 mass%, acetic anhydride (9.3 g) and pyridine (2.9 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 (700 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 71%, the number average molecular weight was 13000, and the weight average molecular weight was 51000.

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. 6.0 g of 3AMP (1 wt% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added to this solution, and the liquid crystal aligning agent (B1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 3)

BODA (1.50 g, 6.0 mmol), DBA (1.83 g, 12.0 mmol), 3AMPDA (2.18 g, 9.0 mmol), DA-2 (3.43 g, 9.0 mmol) were dissolved in NMP (41.1 g) and incubated at 60°C. After reacting for 3 hours, PMDA (1.31 g, 6.0 mmol), followed by CBDA (3.47 g, 17.7 mmol) and NMP (13.71 g) were added and reacted at 25°C for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (50 g) and diluting it to 6.5 mass%, acetic anhydride (11.1 g) and pyridine (3.4 g) were added as imidization catalysts, and the reaction was allowed to proceed at 60°C for 3 hours. This reaction solution was added to methanol (700 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 imidation rate of this polyimide was 79%, the number average molecular weight was 11000, and the weight average molecular weight was 24000.

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 mass % NMP solution), NMP (4.0 g), and BCS (40.0 g) were added to this solution, and the liquid crystal aligning agent (C1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 4)

Liquid crystal aligning agent (A2) is obtained by mixing 3.0 g of the liquid crystal aligning agent (A1) obtained in Synthesis Example 1 as a first component and 7.0 g of the liquid crystal aligning agent (C1) obtained in Synthesis Example 3 as a second component, and stirring for 1 hour. ) was prepared.

(Synthesis Example 5)

Liquid crystal aligning agent (B2) is prepared by mixing 3.0 g of the liquid crystal aligning agent (B1) obtained in Example 1 as a first component and 7.0 g of the liquid crystal aligning agent (C1) obtained in Synthesis Example 3 as a second component, and stirring for 1 hour. ) was prepared.

(Synthesis Example 6) TCA

TCA (11.1 g, 50.0 mmol), DA-1 (6.61 g, 20.0 mmol), DA-4 (3.97 g, 20.0 mmol), DA-8 (4.95 g, 10.0 mmol) were dissolved in NMP (106.5 g) , and reacted at 60°C for 6 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (50 g) and diluting it to 6.5 mass%, acetic anhydride (9.5 g) and pyridine (3.0 g) were added as imidization catalysts, and the reaction was allowed to proceed at 100°C for 3 hours. This reaction solution was added to methanol (700 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 (D) was obtained. The imidization rate of this polyimide was 67%, the number average molecular weight was 13000, and the weight average molecular weight was 31000.

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. NMP (10.0 g) and BCS (40.0 g) were added to this solution, and the liquid crystal aligning agent (D1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 7) BEMS

BODA (5.00 g, 20.0 mmol), DA-1 (3.96 g, 12.0 mmol), DA-5 (2.11 g, 8.0 mmol), DA-2 (7.61 g, 20.0 mmol) were dissolved in NMP (67.6 g) , After reacting at 60°C for 5 hours, CBDA (3.84 g, 20.0 mmol) and NMP (22.5 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 (50 g) and diluting it to 6.5 mass%, acetic anhydride (3.6 g) and pyridine (14.0 g) were added as an imidization catalyst, and the reaction was carried out at 50°C for 3 hours. This reaction solution was added to methanol (700 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 imidation rate of this polyimide was 51%, the number average molecular weight was 18,000, and the weight average molecular weight was 53,000.

NMP (44.0 g) was added to the obtained polyimide powder (E) (6.0 g), and stirred at 50°C for 10 hours to dissolve. 6.0 g of 3AMP (1 wt% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added to this solution, and the liquid crystal aligning agent (E1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 8) DSDA

BODA (5.00 g, 20.0 mmol), DBA (3.04 g, 20.0 mmol), DA-7 (4.93 g, 12.0 mmol), DA-2 (3.04 g, 8.0 mmol) were dissolved in NMP (65.2 g), 60 After reacting at ℃ for 3 hours, CBDA (1.41 g, 7.0 mmol) was added and reacted at 40℃ for 1 hour. After that, DSDA (4.30 g, 12.0 mmol) and NMP (21.7 g) were added and reacted at 25°C for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (50 g) and diluting it to 6.5 mass%, acetic anhydride (9.3 g) and pyridine (2.9 g) were added as imidization catalysts, and the reaction was allowed to proceed at 80°C for 2 hours. This reaction solution was added to methanol (700 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 (F) was obtained. The imidization rate of this polyimide was 76%, the number average molecular weight was 13000, and the weight average molecular weight was 34000.

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. 6.0 g of 3AMP (1 wt% NMP solution), NMP (4.0 g), and BCS (40.0 g) were added to this solution, and the liquid crystal aligning agent (F1) was obtained by stirring at room temperature for 5 hours.

(Synthesis Example 9) A199

BODA (2.50 g, 10.0 mmol), DA-6 (3.49 g, 14.0 mmol), and DA-2 (2.28 g, 6.00 mmol) were mixed in NMP (40.2 g), reacted at 50°C for 3 hours, and CBDA (1.76 g, 9.00 mmol) was added and reacted at 40°C for 3 hours to obtain a polyamic acid solution.

(Synthesis Example 10)

Liquid crystal aligning agent (D2) was prepared by mixing 5.0 g of the liquid crystal aligning agent (D1) obtained in Synthesis Example 6 as a first component and 5.0 g of the liquid crystal aligning agent (F1) obtained in Synthesis Example 8 as a second component, and stirring for 1 hour. ) was prepared.

(Synthesis Example 11)

Liquid crystal aligning agent (E2) was prepared by mixing 5.0 g of the liquid crystal aligning agent (E1) obtained in Synthesis Example 7 as a first component and 5.0 g of the liquid crystal aligning agent (G1) obtained in Synthesis Example 9 as a second component, and stirring for 1 hour. ) was prepared.

Table 1 shows the compositions of liquid crystal aligning agents A1, B1, and C1. Moreover, in Table 2, the composition of liquid crystal aligning agent D1, E1, F1, and G1 is shown.

＜Production of liquid crystal cell＞

(Example 1)

The liquid crystal cell was produced in the procedures as shown below using the liquid crystal aligning agent (A2) obtained in Synthesis Example 4. The liquid crystal aligning agent (A2) obtained in Synthesis Example 4 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 with a hot plate for 90 seconds, baking was performed for 30 minutes in a hot air circulation oven at 230°C to form a liquid crystal alignment film (A2-1) with a film thickness of 100 nm.

In addition, the liquid crystal aligning agent (A2) is spin-coated on the ITO surface on which the electrode pattern is not formed, dried for 90 seconds on an 80°C hot plate, and then baked in a 230°C hot air circulation oven for 30 minutes. A liquid crystal alignment film (A2-2) with a film thickness of 100 nm was formed.

Subsequently, each of the liquid crystal alignment films (A2-1, A2-2) was irradiated with 10 J/cm 2 UV of a high-pressure mercury lamp with a wavelength of 325 nm or less cut to deactivate the radical generating structure present in the alignment film (Pre- UV). To measure the irradiation amount, a UV-35 photoreceptor was connected to UV-M03A manufactured by ORC.

After dispersing a 4 µm bead spacer on the liquid crystal alignment film of one of the two substrates, a sealant (thermosetting sealant XN-1500T, manufactured by Mitsui Chemicals) was printed 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. Negative 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.

With a DC voltage of 15 V applied to this liquid crystal cell, 10 J/cm2 UV of a high-pressure mercury lamp that passed through a 365 nm band-pass filter was irradiated from the outside of this liquid crystal cell (1st-UV). Thereafter, the liquid crystal cell was irradiated for 30 minutes (2nd-UV) using a fluorescent UV lamp (FLR40SUV32/A-1) without applying voltage to deactivate the unreacted polymerizable compound present in the liquid crystal cell. .

Afterwards, the pretilt angle and response speed of the pixel portion of the liquid crystal cell were measured (liquid crystal cell with pretilt angle symmetry). The results are shown in Table 2.

“Measurement of pre-tilt angle”

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

“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 taken with an oscilloscope, and the luminance when no voltage is applied is obtained. A voltage of 0%, ±7 V was applied, the saturated luminance value was set to 100%, and the time it took for the luminance to change from 10% to 90% was taken as the response speed.

In addition, except that Pre-UV was not irradiated to the liquid crystal alignment film (A2-1), a liquid crystal cell having an asymmetric pretilt angle was produced in the same procedure as above, and the response speed was measured. The results are shown in Table 3.

(Examples 2 to 3)

Except that 20 to 40 J/cm2 was irradiated as Pre-UV instead of 10 J/cm2 in Example 1, the same operation as in Example 1 was performed to produce a liquid crystal cell, and the pretilt angle of the liquid crystal cell was measured. It was carried out.

(Example 4)

The same operation as in Example 1 was performed except that 1 J/cm2 of UV from a high-pressure mercury lamp that passed through a band-pass filter with a wavelength of 313 nm was irradiated instead of 10 J/cm2 irradiated as Pre-UV in Example 1, and liquid crystal A cell was produced, and the pretilt angle of the liquid crystal cell was measured.

(Examples 5 to 8)

Except that the used aligning agent was changed from liquid crystal aligning agent (A2) to liquid crystal aligning agent (B2), the same operation as Examples 1 to 4 was performed, a liquid crystal cell was produced, and the pretilt angle of the liquid crystal cell was measured. It was carried out.

In addition, an alignment film (B2-1) applied to the ITO side of an ITO electrode substrate on which an ITO electrode pattern with a pixel size of 100 ㎛ × 300 ㎛ and a line/space of 5 ㎛ is formed was used, and The alignment film applied to the ITO surface was designated as (B2-2).

(Comparative Example 1)

Except that Pre-UV was not irradiated in Example 1, the same operation as in Example 1 was performed to produce a liquid crystal cell, and the pretilt angle of the liquid crystal cell was measured.

(Comparative Example 2)

Except that Pre-UV was not irradiated in Example 5, the same operation as Example 5 was performed to produce a liquid crystal cell, and the pretilt angle of the liquid crystal cell was measured.

(Examples 9 to 12)

Except changing from the liquid crystal aligning agent (A2) to the liquid crystal aligning agent (D2), the same operation as Examples 1 to 4 was performed, a liquid crystal cell was produced, and the pretilt angle of the liquid crystal cell was measured.

In addition, an alignment film (D2-1) applied to the ITO side of an ITO electrode substrate with a pixel size of 100 ㎛ × 300 ㎛ and an ITO electrode pattern of 5 ㎛ each line/space was formed, The alignment film applied to the ITO surface was designated as (D2-2).

(Examples 13 to 16)

Except changing from the liquid crystal aligning agent (A2) to the liquid crystal aligning agent (E2), the same operation as Examples 1 to 4 was performed, a liquid crystal cell was produced, and the pretilt angle of the liquid crystal cell was measured.

In addition, an alignment film (E2-1) applied to the ITO side of an ITO electrode substrate on which an ITO electrode pattern with a pixel size of 100 ㎛ × 300 ㎛ and a line/space of 5 ㎛ is formed was used, and The alignment film applied to the ITO surface was designated as (E2-2).

(Comparative Example 3)

Except that Pre-UV was not irradiated in Example 9, the same operation as Example 9 was performed to produce a liquid crystal cell, and the pretilt angle of the liquid crystal cell was measured.

(Comparative Example 4)

Except that Pre-UV was not irradiated in Example 13, the same operation as Example 13 was performed to produce a liquid crystal cell, and the pretilt angle of the liquid crystal cell was measured.

First, from the results in Tables 3 and 5, by irradiating the substrate with Pre-UV, the radical generating structure in the alignment film is deactivated, making it difficult to develop a pretilt angle during PSA treatment (1st-UV), and the response speed is also slow. It has been confirmed. On the other hand, in the comparative example, since Pre-UV irradiation was not performed, the radical generating structure remained in the alignment layer, so even when using a relatively weak wavelength of 365 nm during PSA treatment (1st-UV), sufficient pretilt angle and response were achieved. It can be seen that speed is obtained.

Next, from the results in Tables 4 and 6, it was found that sufficient response speed was obtained when only one side of the substrate was irradiated with Pre-UV. The pre-tilt angle on the pre-UV irradiated side (in this example, the side on which the ITO electrode pattern is not formed) is the pre-tilt angle described in the examples in Tables 3 and 5, but on the side that was not pre-UV irradiated (In this example, the ITO electrode pattern side) is considered to be the pretilt angle described in the comparative examples in Table 3 and Table 5.

In this way, by applying Pre-UV irradiation to only one side of the substrate, it is possible to produce a liquid crystal display device with an asymmetric pretilt angle using one type of liquid crystal alignment agent without impairing the response speed required for the liquid crystal display device. It becomes possible.

Claims (16)

A liquid crystal aligning film forming step of forming a liquid crystal aligning film on each surface of a pair of substrates with a liquid crystal aligning agent of the same composition containing a specific polymer having a radical generating structure that generates radicals by light irradiation, and the pair of substrates A liquid crystal alignment film light irradiation step of irradiating light to at least one side of the liquid crystal alignment film to set the amount of light irradiation to both liquid crystal alignment films in different states, and thereafter forming a liquid crystal layer containing a liquid crystal compound between the pair of substrates. Including a liquid crystal layer formation process,
The specific polymer includes a polymer having a side chain structure represented by the following formula (I), and is selected from the group consisting of a polyimide precursor having a side chain structure represented by the following formula (I) and a polyimide obtained by imidating the same. A method of manufacturing a liquid crystal display device, characterized in that it is made of at least one polymer.

(Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, which may be substituted with an organic group, and the hydrogen atom may be substituted with a halogen atom. R ₁ and R ₂ are each independently carbon It is an alkyl group or alkoxy group having 1 to 10 atoms, and T ₁ and T ₂ are each independently a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, - It is a bonding group of CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, and -N(CH ₃ )CO-, and S is a single bond or a carbon atom that is unsubstituted or substituted by a fluorine atom. An alkylene group having a number of 1 to 20. However, -CH ₂ - or -CF ₂ - of the alkylene group may be optionally substituted with -CH=CH-, and in cases where any of the groups listed below are not adjacent to each other, these groups may be used. It may be substituted; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbon ring, a divalent heterocycle, and Q represents a structure selected from the group below.

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-.) According to claim 1,
The liquid crystal layer is a PSA type liquid crystal layer, and in the liquid crystal layer forming step, radicals are generated from the radical generating structure by light irradiation while applying a voltage. According to claim 1,
In the liquid crystal alignment film light irradiation step, light is irradiated only to the liquid crystal alignment film of one substrate, and light is not irradiated to the liquid crystal alignment film of the other substrate. A method of manufacturing a liquid crystal display element, characterized in that. A liquid crystal aligning film forming step of forming a liquid crystal aligning film on each surface of a pair of substrates with a liquid crystal aligning agent of the same composition containing a specific polymer having a radical generating structure that generates radicals by light irradiation, and the pair of substrates A liquid crystal alignment film light irradiation step of irradiating light to at least one side of the liquid crystal alignment film to set the amount of light irradiation to both liquid crystal alignment films in different states, and thereafter forming a liquid crystal layer containing a liquid crystal compound between the pair of substrates. Including a liquid crystal layer formation process,
A method for producing a liquid crystal display element, characterized in that the specific polymer contains a polymer having a side chain structure represented by the following formula (II).

(In Formula (II), the dot means a bond to the main chain of the polymer, n is an integer selected from 1 to 12, and X is a single bond, -O-, -COO-, -OCO-, -NHCO -, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-. Cy is the carboxylic acid of the imide group. (Represents a cyclic hydrocarbon group having 5 to 14 carbon atoms, which has at least one unsaturated bond necessarily bonded to the bornyl carbon, and some of the carbon atoms constituting the cyclic hydrocarbon may be substituted with heteroatoms.) According to claim 4,
The liquid crystal layer is a PSA type liquid crystal layer, and in the liquid crystal layer forming step, radicals are generated from the radical generating structure by light irradiation while applying a voltage. According to claim 4,
In the liquid crystal alignment film light irradiation step, light is irradiated only to the liquid crystal alignment film of one substrate, and light is not irradiated to the liquid crystal alignment film of the other substrate. A method of manufacturing a liquid crystal display element, characterized in that. According to claim 4,
A method of manufacturing a liquid crystal display element in which n in the formula (II) is an integer of 1 to 6, Cy is a cyclic hydrocarbon group shown below, and the two dots each represent a bond to an imidecarbonyl carbon.

According to claim 4,
A method for producing a liquid crystal display element in which n in the formula (II) is an integer of 1 to 6, X represents -O-, and Cy is cyclohexene, benzene, naphthalene, or biphenylene. The method according to any one of claims 1 to 8,
A method for producing a liquid crystal display element, wherein the specific polymer further has a side chain that vertically aligns the liquid crystal. According to clause 9,
A method for producing a liquid crystal display element, wherein the side chain that vertically orients the liquid crystal is at least one selected from the following formulas (III-1) and (III-2).

(X ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, or ^-OCO- . Represents a single _bond or (CH ₂ ) _b - ( _b ^is an integer from 1 to 15). , -CH ₂ O- ^, -COO- or -OCO-. It may be substituted with an alkyl group of 1 to 3 carbon atoms, an alkoxyl group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine atom, and X ⁴ has a steroid skeleton. It may be a divalent organic group selected from organic groups having 17 to ⁵¹ carbon atoms. It may be substituted with an alkyl group with 1 to 3 carbon atoms, an alkoxyl group with 1 to 3 carbon atoms, a fluorine-containing alkyl group with 1 to 3 carbon atoms, a fluorine-containing alkoxyl group with 1 to 3 carbon atoms, or a fluorine atom. n represents an integer from 0 to 4. ⁶ represents an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, an alkoxyl group with 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group with 1 to 18 carbon atoms.)

(X ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO- X ⁸ represents an alkyl group with 8 to 22 carbon atoms or a fluorine-containing alkyl group with 6 to 18 carbon atoms.) According to claim 1 or 4,
The manufacturing method of a liquid crystal display element in which the said specific polymer contains at least 1 polymer among the polyimide precursor which has a diamine component represented by following formula (1) as a structural unit, and the polyimide obtained by imidating it.

(Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, which may be substituted with an organic group, and the hydrogen atom may be substituted with a halogen atom. R ₁ and R ₂ are each independently carbon It is an alkyl group or alkoxy group having 1 to 10 atoms, and T ₁ and T ₂ are each independently a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, - It is a bonding group of CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, and -N(CH ₃ )CO-, and S is a single bond or a carbon atom that is unsubstituted or substituted by a fluorine atom. An alkylene group having a number of 1 to 20. However, -CH ₂ - or -CF ₂ - of the alkylene group may be optionally substituted with -CH=CH-, and in cases where any of the groups listed below are not adjacent to each other, these groups may be used. It may be substituted; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbon ring, a divalent heterocycle, and Q represents a structure selected from the group below.

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-.) According to claim 11,
Production of a liquid crystal display element in which the specific polymer further contains at least one polymer among a polyimide precursor having as a structural unit a diamine component containing a diamine represented by the following formula (VII) and a polyimide obtained by imidating the same. method.

(X represents the structure of the following formula [III-1] or formula [III-2], and n represents an integer of 1 to 4.

X ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, or -OCO-. X ² represents a single bond or (CH ₂ ) _b - (b is an integer of 1 to 15). X ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, or -OCO-. X ⁴ is represented by a benzene ring, cyclohexane ring, and a two -fierce ring, and any hydrogen atom of these rings, alkuls of 1 to 3 carbon atoms, alkoxyl groups of 1 to 3 carbon atoms, carbon water 1 It may be substituted with a fluorine-containing alkyl group of -3, a fluorine-containing alkoxyl group of 1-3 carbon atoms, or a fluorine atom, and X ⁴ may be a divalent organic group selected from organic groups of 17-51 carbon atoms having a steroid skeleton. X ⁵ shows a two -family ring type selected from benzene ring, cyclohexane ring and complex ring, and any hydrogen atom of these rings, alkyl groups of 1 to 3 carbon atoms, alkoxyl groups of 1 to 3 carbon atoms, carbon water 1 ~ It may be substituted with a fluorine-containing alkyl group of 3, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine atom. n represents an integer from 0 to 4. X ⁶ represents an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, an alkoxyl group with 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group with 1 to 18 carbon atoms.

X ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- or -OCO- indicates. X ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.) According to claim 11,
A liquid crystal in which the above-mentioned specific polymer further contains at least one polymer of a polyimide precursor having as a structural unit a diamine component containing a diamine represented by the following formula (VIII) or (IX) and a polyimide obtained by imidating the same. Method for manufacturing display elements.

(R ⁸ is a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )- , -CON(CH ₃ )-, or -N(CH ₃ )CO-. R ⁹ represents a single bond, an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and -CH ₂ of the alkylene group. - may be optionally substituted with -CF ₂ - or -CH=CH-, and may be substituted with any of the following groups if they are not adjacent to each other: -O-, -COO-, -OCO-, -NHCO -, -CONH-, -NH-, divalent carbon ring or heterocycle. R ¹⁰ represents a photoreactive group selected from the formula below.)

(Y ₁ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, or -CO-. Y ₂ represents alkyl having 1 to 30 carbon atoms. It is a lene group, a divalent carbon ring, or _a heterocyclic ring, and one or more hydrogen atoms of the alkylene group, a divalent carbon ring, or a heterocyclic ring may be substituted with a fluorine atom or an organic group. When not adjacent, -CH ₂ - may be substituted with these groups: -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-.Y ₃ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO- or a single bond, and Y ₄ represents a cinnamoyl group. 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. 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 method according to any one of claims 1 to 6,
A method for producing a liquid crystal display element, characterized in that the polymer contains the following component (A) and the following component (B).
(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 irradiation with ultraviolet rays represented by the formula (I) below, and this polyimide precursor is imidized. At least one polymer selected from polyimides obtained by

(Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, which may be substituted with an organic group, and the hydrogen atom may be substituted with a halogen atom. R ₁ and R ₂ are each independently carbon It is an alkyl group or alkoxy group having 1 to 10 atoms, and T ₁ and T ₂ are each independently a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, - It is a bonding group of CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, and -N(CH ₃ )CO-, and S is a single bond or a carbon atom that is unsubstituted or substituted by a fluorine atom. An alkylene group having a number of 1 to 20. However, -CH ₂ - or -CF ₂ - of the alkylene group may be optionally substituted with -CH=CH-, and in cases where any of the groups listed below are not adjacent to each other, these groups may be used. It may be substituted; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbon ring, a divalent heterocycle, and Q represents a structure selected from the group below. )

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

(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.)

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