KR102597729B1 - Liquid crystal orientation agent, liquid crystal oriented film, and liquid crystal display element - Google Patents

Abstract

A liquid crystal alignment agent and a liquid crystal display device that enable a liquid crystal display device with a fast response speed and excellent AC-derived afterimage characteristics are provided. A liquid crystal display element formed by containing the polymeric compound represented by Formula (1) in a liquid crystal aligning agent and/or a liquid crystal layer. ^{( X 1 and _ _ _ _} It is chosen to be this.)

Description

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

The present invention provides a liquid crystal aligning agent that can be suitably used in a liquid crystal display element manufactured by irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules, a liquid crystal aligning film formed from the liquid crystal aligning agent, and a liquid crystal display having the liquid crystal aligning film. It's about elements.

Among liquid crystal display elements in which liquid crystal molecules aligned perpendicularly to the substrate are responded to by an electric field (also called vertical alignment (VA) method), in the manufacturing process, ultraviolet rays are irradiated while applying a voltage to the liquid crystal molecules. There is something that involves a process.

In such a vertically aligned liquid crystal display device (PSA (Polymer Sustained Alignment) type liquid crystal display, etc.), a photopolymerizable compound is added in advance to the liquid crystal composition and used together with a vertical alignment film such as polyimide to apply a voltage to the liquid crystal cell. A technology is known to speed up the response speed of liquid crystal by irradiating ultraviolet rays while applying them (see Patent Document 1 and Non-Patent Document 1).

Typically, the tilting direction of liquid crystal molecules in response to an electric field is controlled by protrusions formed on the substrate or slits formed in the display electrode, but a photopolymerizable compound is added to the liquid crystal composition and a voltage is applied to the liquid crystal cell. By irradiating ultraviolet rays while irradiating ultraviolet rays, a polymer structure that remembers the direction in which the liquid crystal molecules are tilted is formed on the liquid crystal alignment film. Therefore, compared to a method of controlling the tilt direction of the liquid crystal molecules with only protrusions or slits, the response speed of the liquid crystal display device is increased. They say it gets faster.

Moreover, it has been reported that the response speed of a liquid crystal display element becomes faster even when a photopolymerizable compound is added not in the liquid crystal composition but in the liquid crystal alignment film (SC-PVA type liquid crystal display) (see Non-Patent Document 2).

Japanese Patent Publication No. 2003-307720.

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

In recent years, it has been desired to further speed up the response speed of liquid crystal display elements, and it is thought to increase the addition amount of the photopolymerizable compound to speed up the response speed of the liquid crystal display element. However, conventional photopolymerizable compounds are: It has the property of being difficult to dissolve in solvents used in liquid crystal aligning agents. Therefore, when storing a liquid crystal aligning agent, the problem of storage stability that the photopolymerizable compound precipitates arises. Moreover, when a liquid crystal display element is exposed to a temperature change during the manufacturing process, a part of a polymeric compound may elute into a liquid crystal from a liquid crystal alignment film, or may crystallize in a liquid crystal. In particular, when the solubility of the polymerizable compound in the liquid crystal is low, it is thought that crystallization in the liquid crystal is likely to occur. Such crystallization of the polymerizable compound in the liquid crystal becomes a bright point source in the display device, leading to a decrease in the display quality of the device.

Additionally, another problem with liquid crystal display elements is exposure (afterimage), which may occur when the same pattern is displayed for a long period of time. One of the causes of this exposure is the accumulation of electric charges. Exposure resulting from charge accumulation is also called DC exposure, but can be suppressed to some extent by driving by applying a voltage with the polarity reversed, that is, polarity inversion driving. On the other hand, exposure occurs even if the pretilt angle changes slightly. Since the V-T characteristics are affected when the pretilt angle changes, the transmittance changes even when the same voltage is applied. Since the applied voltage during white display is different from the applied voltage during black display, the amount of change in the tilt angle varies depending on the applied voltage, and then, when the entire thing is converted to the same gradation, the change in tilt angle results in There are cases where exposure is recognized. Such exposure cannot be suppressed even if polarity inversion driving is performed, and is therefore also called AC exposure.

The purpose of the present invention is to solve the problems of the prior art described above.

As a result of repeated research to achieve the above object, the present inventor has arrived at the present invention, the summary of which is as follows.

1. A liquid crystal aligning agent containing a polymerizable compound represented by the following formula (1) and at least one polymer selected from the group consisting of a polyimide precursor and polyimide.

[Formula 1]

⁽ In the formula, ^{X 1 and} In addition, S ¹ , X ¹ , X ² and S ² are selected so that the molecule is left-right asymmetric.)

2. In the polymerizable compound (1), the liquid crystal aligning agent according to 1 above, wherein S ¹ and S ² are alkylene groups having mutually different carbon numbers.

3. In the polymerizable compound (1), either one of X ¹ and X ² is an ether bond and the ^other is an ester bond, or X ¹ is an ester bond bonded to S ¹ on the carbonyl side, and The liquid crystal aligning agent according to item 1 or 2 above, which is an ester group bonded to S ² on the oxygen atom side.

4. The liquid crystal aligning agent according to any one of 1 to 3 above, wherein at least one polymer selected from the group consisting of a polyimide precursor and a polyimide has a side chain that vertically aligns the liquid crystal.

5. The liquid crystal aligning agent according to any one of said items 1 to 4, wherein at least one polymer selected from the group consisting of a polyimide precursor and a polyimide further has a photoreactive side chain.

6. A liquid crystal aligning film formed using the liquid crystal aligning agent according to any one of 1 to 5 above.

7. A liquid crystal display element having the liquid crystal alignment film according to item 6 above.

8. A liquid crystal alignment agent containing at least one polymer selected from the group consisting of a polyimide precursor and polyimide is applied on two substrates to form a liquid crystal alignment layer, and the two liquid crystal alignment layers are opposed to each other. A method of manufacturing a vertically aligned liquid crystal display element in which a substrate is disposed, a liquid crystal layer is sandwiched between the two substrates, and ultraviolet rays are irradiated while applying an electric field to the liquid crystal layer,

A method for producing a liquid crystal display element, characterized in that at least one of the liquid crystal aligning agent and the liquid crystal layer contains a polymerizable compound represented by Formula (1).

[Formula 2]

⁽ In the formula, ^{X 1 and} Additionally, S ¹ , X ¹ , X ² and S ² are selected so that the molecule is left-right asymmetric.)

9. The production method according to 8 above, wherein in the polymerizable compound (1), S ¹ and S ² are alkylene groups having different carbon numbers.

10. In the polymerizable compound (1), either one of X ^{1 and} X ² is an ether bond and the other is an ester bond, or X ¹ is an ester bond bonded to S ¹ on the carbonyl side, and The production method according to 8 or 9 above, wherein the ester group is bonded to S ² on the oxygen atom side.

11. The manufacturing method according to any one of the above 8 to 10, wherein at least one polymer selected from the group consisting of a polyimide precursor and a polyimide has a side chain that vertically aligns the liquid crystal.

12. The manufacturing method according to any one of the above 8 to 11, wherein at least one polymer selected from the group consisting of a polyimide precursor and a polyimide further has a photoreactive side chain.

13. A polymerizable compound represented by the following formula (1).

[Formula 3]

⁽ In the formula, ^{X 1 and} Additionally, S ¹ , X ¹ , X ² and S ² are selected so that the molecule is left-right asymmetric.)

14. The polymerizable compound according to item 13 above, wherein in formula (1), S ¹ and S ² are alkylene groups having different carbon numbers.

15. In formula (1), one of X ¹ and X ² is an ether bond and the other is an ester bond, or X ¹ is ^an ester bond bonded to S ¹ on the carbonyl side and The polymerizable compound according to item 13 or 14 above, which is an ester group bonded to S ² .

According to the present invention, a liquid crystal aligning agent containing a novel polymerizable compound that makes it possible to provide a liquid crystal display element with a fast response speed and excellent afterimage characteristics derived from AC by including it in the liquid crystal aligning agent and/or the liquid crystal layer, A liquid crystal aligning film formed using the liquid crystal aligning agent and a device with a fast response speed, especially a vertical alignment type device, are obtained.

＜Polymerizable compound＞

The polymeric compound contained in the liquid crystal aligning agent of this invention is represented by following formula (1).

[Formula 4]

In formula (1), the definitions of X ¹ , X ² , S ¹ , and S ² are each as described above. Among them, S ¹ and S ² are each independently preferably a linear alkylene group having 2 to 6 carbon atoms.

Preferred methods ^for making the molecules ^of S ^{1 ,} X ^{1 ,} There is a method (method ² ) to select a coupler in which ¹ and Here, it is also possible to use method 1 and method 2 together.

Method ² is, specifically ^, a method ⁱⁿ which one of X ¹ and and a method in which X ² is an ester group that bonds to S ² on the oxygen atom side (Method 2-2).

Among such compounds, compounds having alkylene groups having different carbon numbers can be obtained by the production method described in International Patent Application Publication No. WO2012/002513. In addition, in the case where one side is intended to be an ether bond and the other side is an ester bond, in the production method described in International Patent Application Publication No. WO2012/002513, 4-(4-hydroxyphenyl)benzoic acid is used as a raw material instead of bisphenol. You can use it to manufacture it.

In addition, methods for making the molecule left-right asymmetric include, in addition to Methods 1 and 2 above, a method in which the left and right polymerizable groups are different (Method 3), a method in which a substituent is introduced into the benzene ring to make it left-right asymmetric (Method 4), etc. There is.

It was found that by selecting at least one method selected from Method 1 and Method 2 above, the solubility of the polymerizable compound was improved and the afterimage characteristics derived from AC were superior to those in the case of selecting Method 3 or Method 4. . Although the reason for this is not clear, it is thought that the stacking of the ring structure of the polymerizable compound is the cause of the afterimage characteristics derived from AC. However, when Method 1 or Method 2 is selected, compared to when Method 3 or Method 4 is selected, , I think this is because stacking is not impaired.

<Polyimide precursor and/or polymer from polyimide>

In a liquid crystal display element formed by containing a liquid crystal aligning agent and/or a liquid crystal layer, at least one polymer (hereinafter also referred to as a specific polymer) selected from the group consisting of a polyimide precursor and polyimide that is preferably used is: Known polyimide precursors or polyimides used as liquid crystal aligning agents can be used. In addition, the polyimide precursor specifically includes polyamic acid and polyamic acid ester.

The polyimide precursor or polyimide, which is a specific polymer, preferably has a side chain (I) that orients the liquid crystals vertically for PSA type liquid crystal displays, and has a side chain (I) that orients the liquid crystals vertically for SC-PVA type liquid crystal displays. In addition to the side chain (I), it is preferable to have a photoreactive side chain (II).

<Side chain (I) that vertically orients the liquid crystal>

The side chain (I) (hereinafter also referred to as side chain A) that orients the liquid crystal vertically is a side chain that has the ability to orient the liquid crystal molecules vertically with respect to the substrate, and if it has this ability, its structure is limited. It doesn't work. As such side chains, for example, long-chain alkyl groups, fluoroalkyl groups, cyclic groups having an alkyl group or fluoroalkyl group at the terminal, steroid groups, etc. are known, and are preferably used in the present invention. As long as these groups have the above-mentioned capabilities, they may be directly bonded to the main chain of a specific polymer or may be bonded through an appropriate linking group.

Examples of side chain A include those represented by the following formula (a).

In addition, in formula (a), l, m and n each independently represent an integer of 0 or 1, and R ¹ is an alkylene group having 1 to 6 carbon atoms, -O-, -COO-, -OCO-, -NH-, -NHCO-, -CONH-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ COO-, -OCOCH ₂ - or an alkylene-ether group having 1 to 3 carbon atoms. R ² , R ³ and R ⁴ each independently represent a phenylene group or a cycloalkylene group, and R ⁵ is a hydrogen atom, an alkyl group with 1 to 24 carbon atoms, an alkoxy group with 1 to 24 carbon atoms, or fluorine with 1 to 24 carbon atoms. Containing alkyl group, fluorine-containing alkoxy group having 1 to 24 carbon atoms, fluorine group, cyano group, nitro group, azo group, formyl group, acetyl group, acetoxy group, hydroxyl group, aromatic ring, aliphatic ring, heterocyclic ring, or a group consisting of them. Represents a hetero-type substituent.

[Formula 5]

From the viewpoint of ease of synthesis, R ¹ is preferably -O-, -COO-, -CONH-, or an alkylene-ether group having 1 to 3 carbon atoms.

R ² , R ³ and R ⁴ are preferably a combination of l, m, n, R ² , R ³ and R ⁴ shown in Table 1 below from the viewpoint of ease of synthesis and ability to vertically align the liquid crystal. do.

When at least one of l, m, and n is 1, R ⁵ is preferably a hydrogen atom, an alkyl group with 2 to 14 carbon atoms, or a fluorine-containing alkyl group with 2 to 14 carbon atoms, and more preferably a hydrogen atom, with 2 to 14 carbon atoms. It is an alkyl group of 12 or a fluorine-containing alkyl group of 2 to 12 carbon atoms. Moreover, when l, m and n are all 0, R ⁵ is preferably an alkyl group having 12 to 22 carbon atoms, a fluorine-containing alkyl group having 12 to 22 carbon atoms, an aromatic ring, an aliphatic ring, a heterocycle, or a group consisting of them. It is a ring-type substituent, and more preferably, it is an alkyl group with 12 to 20 carbon atoms or a fluorine-containing alkyl group with 12 to 20 carbon atoms.

The ability to vertically align liquid crystals varies depending on the structure of the side chain A described above, but generally, as the amount of side chain A contained in the polymer increases, the ability to vertically align liquid crystals increases, and as it decreases, it decreases. . Moreover, the side chain A containing a cyclic structure tends to vertically align the liquid crystal even at a small content compared to the side chain A of the long-chain alkyl group.

The amount of side chain A in the specific polymer will not be particularly limited as long as the liquid crystal aligning film is within a range that can vertically align the liquid crystal. However, in a liquid crystal display element provided with a liquid crystal alignment film, when it is intended to make the response speed of the liquid crystal faster, it is preferable that the content of the side chain A is as small as possible within the range where vertical alignment can be maintained.

＜Photoreactive side chain (II)＞

Photoreactive side chain (II) (hereinafter also referred to as side chain B) is a crosslinkable side chain that has a functional group (hereinafter also referred to as photocrosslinking group) that can form a covalent bond by reacting with irradiation of ultraviolet rays. , or a photo-radical generating side chain having a functional group that generates radicals upon ultraviolet irradiation, and its structure is not limited as long as it has this ability.

Such side chains include, for example, those containing a vinyl group, an acrylic group, a methacryl group, an anthracenyl group, a cinnamoyl group, a carconyl group, a coumarin group, a maleimide group, a stilbene group, etc. as a photocrosslinking group. Chains and the like are known and are preferably used in the present invention. In addition, structures that generate radicals by ultraviolet irradiation include acylphosphine oxide structure, acetophenone structure, alkylphenone structure, anthraquinone structure, carbazole structure, xanthone structure, thioxanthone structure, triphenylamine structure, and fluorine structure. Lennon structure, benzaldehyde structure, benzoin structure, benzophenone structure, fluorene structure, etc. are mentioned, and photo radical generating side chains having these structures are also preferably used. Among them, a side chain having an acetophenone structure, a benzophenone structure, or a benzoin structure is preferable.

As long as these groups have the above-mentioned capabilities, they may be directly bonded to the main chain of a specific polymer or may be bonded through an appropriate linking group.

As side chain B, the following formulas (b-1) to (b-3) can be exemplified, for example. In addition, the side chain represented by formula (b-2) has a structure having a cinnamoyl group and a methacryl group, and the side chain represented by formula (b-3) has a structure that generates a radical by ultraviolet irradiation.

[Formula 6]

In formula (b-1), R ⁶ is -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-. From the viewpoint of ease of synthesis, R ⁶ is preferably -CH ₂ -, -O-, -COO-, -NHCO-, -NH-, or -CH ₂ O-.

R ⁷ represents an alkylene group having 1 to 20 carbon atoms that is cyclic, unsubstituted, or substituted with a fluorine atom, and any -CH ₂ - of the alkylene group is substituted with -CF ₂ - or -CH=CH-. In the case where any of the groups exemplified below are not adjacent to each other, they may be substituted with these groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, carbon Ring, or complex ring.

Specific examples of the carbon ring and heterocycle include, but are not limited to, the following structures.

[Formula 7]

[Formula 8]

R ⁸ is -CH ₂ -, -O-, -CH ₂ O-, -COO-, -OCO-, -NH-, -CONH-, -NHCO-, -N(CH ₃ )-, -CON( CH ₃ )-, -N(CH ₃ )CO-, a carbon ring, or a heterocycle. From the viewpoint of ease of synthesis, -CH ₂ -, -O-, -COO-, -OCO-, NHCO-, -NH-, a carbon ring, or a heterocycle are preferable. Specific examples of carbon rings and heterocycles are as described above.

R ⁹ is a styryl group, -CR ¹⁸ =CH ₂ group, carbon ring, heterocycle, or one of the following formulas (R9-1) to (R9-34), and R ¹⁸ may be substituted with a hydrogen atom or a fluorine atom. represents a methyl group.

[Formula 9]

[Formula 10]

[Formula 11]

Among them, from the viewpoint of photoreactivity, R ⁹ may be a styryl group, -CH=CH ₂ , -C(CH ₃ )=CH ₂ , or (R9-2), (R9-12) or (R9-15) above. ) is more preferable.

[Formula 12]

In the above formula (b-2), R ¹⁰ is -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, or -CO-.

R ¹¹ is an alkylene group, a divalent carbon ring, or a divalent heterocycle having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group, the divalent carbon ring, and the divalent heterocycle may be substituted with a fluorine atom or an organic group. do. In addition, any -CH ₂ - in R ¹¹ may be substituted with any of the groups illustrated below in the case where they are not adjacent to each other; -O-, -NHCO-, -CONH-, -COO- , -OCO-, -NH-, -NHCONH-, or -CO-.

R ¹² is -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, or a single bond.

R ¹³ is a cinnamoyl group, a chalcone group, or a coumarin group, and represents a photo-crosslinking group.

R ¹⁴ is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbon ring, or a divalent heterocycle, and one or more hydrogen atoms of the alkylene group, the divalent carbon ring, and the divalent heterocycle are a fluorine atom or an organic group. It may be substituted. In addition, any -CH ₂ - in R ¹⁴ may be substituted with any of the groups illustrated below in the case where they are not adjacent to each other; -O-, -NHCO-, -CONH-, -COO- , -OCO-, -NH-, -NHCONH-, or -CO-.

R ¹⁵ is an acrylic group or a methacryl group and represents a photopolymerizable group.

Among the side chains represented by the formula (b-2), specific examples of the group represented by -R ¹³ -R ¹⁴ -R ¹⁵ include the following structures, but are not limited to these. In addition, in the structures below, R represents a hydrogen atom or a methyl group.

[Formula 13]

[Formula 14]

In formula (b-3), Ar ₄ represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, these groups may be substituted with an organic group, and the hydrogen atoms of these groups are halogen atoms. It may be substituted.

R ₁₆ and R ₁₇ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a benzyl group, or a phenethyl group. In the case of an alkyl group or an alkoxy group, a ring is formed with R ₁₆ and R ₁₇ You can do it.

T ₁ and T ₂ are each independently a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ ) It represents a linking group of -, -CON(CH ₃ )- or -N(CH ₃ )CO-.

S ⁴ represents a single bond, unsubstituted or an alkylene group having 1 to 20 carbon atoms substituted with a fluorine atom (however, -CH ₂ - or -CF ₂ - of the alkylene group is optionally represented by -CH=CH- It may be substituted, and in cases where any of the groups exemplified below are not adjacent to each other, it may be substituted with these groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH- , divalent carbon ring, or divalent heterocycle.).

n2 represents 0 or 1. Q represents the structure represented by the formula below.

[Formula 15]

(Wherein, 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-)

Among the side chains represented by formula (b-3), specific examples of the group represented by -Ar ₄ -CO-CQR ¹⁶ R ¹⁷ include the structures of the following formulas (b-3-1) to (b-3-6): It may be mentioned, but it is not limited to these.

[Formula 16]

The amount of side chain B in the specific polymer is not particularly limited as long as it is within a range that can speed up the response speed of the liquid crystal in the liquid crystal display element. When it is intended to make the response speed of the liquid crystal in a liquid crystal display element faster, it is preferable to have as much as possible within the range that does not affect other characteristics.

＜Polyimide precursor＞

Polyimide precursor means polyamic acid and polyamic acid ester. Hereinafter, the preparation method for polyamic acid will be described. However, polyamic acid ester can be prepared by a conventionally known method or a method that is the same or similar to the polyamic acid described below.

＜Polyamic acid＞

The polyamic acid having side chain A can be obtained by reacting the raw materials, such as diamine and tetracarboxylic acid anhydride, when either one has side chain A or both have side chain A. Among these, the method of using a diamine having a side chain A is preferable from the viewpoint of ease of synthesizing raw materials, etc.

In addition, the polyamic acid having side chains A and B has only one side chain A and side chain B among the diamine and tetracarboxylic acid anhydride as raw materials, or one side has only side chain A, In addition, either the other party has only side chain B, or one party has side chain A and side chain B, and the other party has side chain A, or either party has side chain A and side chain B, and the other party has side chain A and side chain B. It can be obtained by reacting the raw materials by having chain B, or by both having side chain A and side chain B. Among these, for ease of raw material synthesis, etc., it is preferable to contain side chain A and side chain B only in diamine.

＜Diamine with side chain A＞

Examples of the diamine having a side chain A (hereinafter referred to as diamine A) include diamines having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocycle, or a macrocyclic substituent thereof in the diamine side chain. You can. Specifically, diamine having a side chain represented by the above formula (a) can be mentioned. More specifically, diamines represented by the following formulas (1), (3), (4), and (5) can be mentioned, but are not limited to these. In addition, the definitions of l, m, n, and R ¹ to R ⁵ in formula (1) are the same as those in formula (a).

[Formula 17]

In formulas (3) and (4), A ₁₀ is each independently -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or - represents NH-, A ₁₁ represents a single bond or a phenylene group, a represents the side chain A, and a' represents an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocycle, or any structure selected from these. It represents a macrocyclic substituent consisting of a combination of .

[Formula 18]

In formula (5), A ₁₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₁₅ is a 1,4-cyclohexylene group or a 1,4-phenylene group, and A ₁₆ is , an oxygen atom, or -COO-* (however, the bond to which “*” is assigned combines with A ₃ ), and A ₁₇ is an oxygen atom, or -COO-* (however, the bond to which “*” is assigned is (CH ₂ )a ₂ combines with). 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.)

The bonding position of two amino groups (-NH ₂ ) in formula (1) is not limited. Specifically, with respect to the linking group in the side chain, the positions 2 and 3, positions 2 and 4, positions 2 and 5, positions 2 and 6, positions 3 and 4, and positions 3 and 5 on the benzene ring. I can hear it. Among them, from the viewpoint of reactivity when synthesizing polyamic acid, the positions 2 and 4, the positions 2 and 5, or the positions 3 and 5 are preferable. Considering the ease of synthesizing diamine, positions 2 and 4, or positions 3 and 5 are more preferable.

As a specific structure of formula (1), diamines represented by the following formulas [A-1] to formulas [A-24] can be exemplified, but are not limited to this.

[Formula 19]

[Formula 20]

[Formula 21]

In formulas [A-1] to formulas [A-5], A ₁ is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group having 2 to 24 carbon atoms.

In formulas [A-6] and formulas [A-7], A ₂ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -, or -CH ₂ OCO-, and A ₃ is an alkyl group with 1 to 22 carbon atoms, an alkoxy group with 1 to 22 carbon atoms, a fluorine-containing alkyl group with 1 to 22 carbon atoms, or a fluorine-containing alkoxy group with 1 to 22 carbon atoms.

In formula [A-8] to formula [A-10], A ₄ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, or -CH ₂ -, and A ₅ is an alkyl group with 1 to 22 carbon atoms, an alkoxy group with 1 to 22 carbon atoms, a fluorine-containing alkyl group with 1 to 22 carbon atoms, or a fluorine-containing alkyl group with 1 to 22 carbon atoms. It is an alkoxy group.

[Formula 22]

[Formula 23]

[Formula 24]

In formula [A-11] and formula [A-12], A ₆ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, -CH ₂ -, -O-, or -NH-, and A ₇ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, It is an acetoxy group or a hydroxyl group.

In formulas [A-13] and [A-14], A ₈ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is each trans isomer.

In formulas [A-15] and formulas [A-16], A ₉ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is each trans isomer.

[Formula 25]

[Formula 26]

[Formula 27]

Specific examples of diamine represented by formula (3) include diamines represented by the following formula [A-25] to formula [A-30], but are not limited to these.

[Formula 28]

(A ₁₂ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or -NH-, and A ₁₃ represents a group having 1 to 22 carbon atoms. Represents an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms.)

Specific examples of diamine represented by formula (4) include diamines represented by the following formulas [A-31] to formulas [A-32], but are not limited to these.

[Formula 29]

Among these, in terms of the ability to vertically align the liquid crystal and the response speed of the liquid crystal, [A-1], [A-2], [A-3], [A-7], [A-14], [ Diamines of [A-16], [A-21], or [A-22] are preferable.

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

Among 100 mol% of diamine components used in the synthesis of the polyamic acid having side chain A, diamine A is preferably 5 to 70 mol%, preferably 10 to 50 mol%, more preferably 20 to 50 mol%. .

<Diamine with side chain B>

As an example of a diamine having a side chain B (hereinafter also referred to as diamine B), the diamine side chain includes a vinyl group, an acrylic group, a methacryl group, an anthracenyl group, a cinnamoyl group, a carconyl group, a coumarin group, and a maleimide group. , diamines having photo-crosslinking groups such as stilbene groups, and diamines having functional groups that generate radicals when irradiated with ultraviolet rays. Specifically, diamines having side chains represented by the above formulas (b-1) to (b-3) can be mentioned. Specific examples include diamines represented by the following general formula (2) (the definitions of R ⁶ , R ⁷ , R ⁸ and R ⁹ in formula (2) are the same as those in the above formula (b-1)). , but is not limited to this.

[Formula 30]

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

Specifically, the following compounds can be mentioned, but are not limited to these. In addition ^, in the following compounds, Represents an alkylene group of 1 to 20. In addition, l, m, and n each independently represent an integer of 0 to 20.

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

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

Among 100 mol% of diamine components used for the synthesis of polyamic acid, diamine B is 0 to 95 mol%, preferably 20 to 80 mol%, more preferably 40 to 70 mol%.

＜Other diamines＞

The polyamic acid used in the present invention contains, as a diamine component, other diamines other than diamines having side chains that vertically orient the liquid crystal and diamines having photoreactive groups, as long as the effects of the present invention are not impaired. Can be used together. Specifically, 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'-diaminobi Phenyl, 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'-dia Minobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'- Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfo Nyldianiline, 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'-diaminodi Phenylamine, 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'-diamino) Diphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diamino Benzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene Minonaphthalene, 2,6diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl) Ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl) )Butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4 -bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]dianiline, 4,4'-[1,3-phenylenebis(methylene)]dianiline, 3,4'-[1,4- Phenylenebis(methylene)]dianiline, 3,4'-[1,3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis(methylene)]dianiline, 3,3'-[1,3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-amino) phenyl)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, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenok Si) ethane, 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-bis(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-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3) -Aromatic diamines such as aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, and bis(4-aminocyclohexyl) Alicyclic diamines such as methane and bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-dia minohexane, 1,7-diaminoheptane, 1,8-diaminoctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-dia Aliphatic diamines such as minododecane 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 characteristics, and accumulated charge.

＜Tetracarboxylic dianhydride＞

In the synthesis of the polyamic acid used in the present invention, the tetracarboxylic dianhydride reacted with the above diamine component is not particularly limited. Specific examples are given below.

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-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic 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, 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-tetrahydrinaphthalene-1,2-dicarboxylic acid, B Cyclo[2,2,2]oct-7-en-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexane- 1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxylic acid Norbornane-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc. are mentioned.

Tetracarboxylic dianhydride can 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.

＜Synthesis of polyamic acid＞

In obtaining a polyamic acid by reaction of a diamine component and tetracarboxylic dianhydride, a known synthetic method can be used. Generally, this is a method of reacting a diamine component and tetracarboxylic dianhydride 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 that does not dissolve the polyamic acid, 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.

Examples of organic solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N -Ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N-methylcaprolactam, dimethyl sulfoxide , tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl. Ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate. , ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene. Glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3- Methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 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 monoethyl ether acetate, methyl pyruvate. , ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxypropionic acid. Butyl, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, etc. are mentioned. These organic solvents may be used individually or may be used in combination.

When reacting the diamine component and the tetracarboxylic dianhydride component in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is left as is or dispersed or dissolved in the organic solvent. A method of adding the tetracarboxylic dianhydride component in an organic solvent, or 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. and any of these methods may be used. In addition, when the diamine component or tetracarboxylic dianhydride component consists of multiple types of compounds, they may be reacted in a premixed state, may be reacted individually sequentially, or may be mixed and reacted with individually reacted low molecular weight substances to form a polymer. It may be used as a monomer.

The temperature when reacting the diamine component and the tetracarboxylic dianhydride component can be any temperature, for example, -20 to 150°C, preferably in the range of -5 to 100°C. Moreover, the reaction can be performed at an arbitrary concentration, for example, 1 to 50 mass%, preferably 5 to 30 mass%.

In the above polymerization reaction, the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be any value depending on the molecular weight of the polyamic acid to be obtained. As with a typical polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced. As a preferable range, it 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 is similar to the method for synthesizing general polyamic acids, using tetracarboxylic acid or tetracarboxylic acid of the corresponding structure instead of the tetracarboxylic dianhydride. The corresponding polyamic acid can also be obtained by reacting by a known method using a tetracarboxylic acid derivative such as tetracarboxylic 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 the polyimide used in the present invention, the imidization rate from polyamic acid to polyimide does not necessarily need to be 100%.

The temperature in the case of heat imidizing a polyamic acid in a solution is 100-400 degreeC, Preferably it is 120-250 degreeC, and it is preferable to carry out while removing the water produced|generated by the imidation reaction to the outside of the system.

Catalyst imidization of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor 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. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction. Examples of the acid anhydride 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, reaction time, etc.

When recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be added to a poor solvent to cause precipitation. Examples of 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 precipitation-recovered polymer is re-dissolved in an organic solvent and the reprecipitation-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 these because the efficiency of purification increases further.

＜Liquid crystal alignment agent＞

The liquid crystal aligning agent of this invention contains the polymeric compound represented by said Formula (1), and at least 1 polymer chosen from the group which consists of the said polyimide precursor and polyimide. In addition to these components, other polymer components for forming a resin film may be contained. Content of all resin components is 1-20 mass % in 100 mass % of liquid crystal aligning agents, Preferably it is 3-15 mass %, More preferably, it is 3-10 mass %.

The resin component in the liquid crystal aligning agent of this invention may be at least 1 polymer chosen from the group which all consist of a polyimide precursor and polyimide which have side chain A and/or side chain B, and a mixture thereof may be sufficient as them. , and furthermore, other polymers may be mixed. At that time, the content of the other polymer in the resin component is preferably 0.5 to 15 mass%, more preferably 1 to 10 mass%.

Other polymers include, but are not limited to, polyimide precursors or polyimides that do not have side chain B, polyimide precursors or polyimides that do not have both side chains A and B, etc., for example. .

The molecular weight of the polymer of the above resin component is the weight average molecular weight (Mw) measured by GPC (Gel Permeation Chromatography) method when considering the strength of the resulting coating film, workability during coating film formation, and uniformity of the coating film, etc. It is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

Content of the polymeric compound represented by Formula (1) in the liquid crystal aligning agent of this invention is 3-30 mass parts with respect to 100 mass parts of resin components, Preferably it is 5-20 mass parts, More preferably, it is 5-5 mass parts. It is 15 parts by mass. In the case of this content, the effect of the present invention is obtained.

＜Solvent＞

The organic solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if it is an organic solvent which dissolves the resin component mentioned above. This organic solvent may be one type of solvent, or may be a mixed solvent of two or more types. Specific examples of the organic solvent include the organic solvents exemplified in the polyamic acid synthesis above. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, or 3-methoxy-N, N-dimethylpropanamide is preferable from the viewpoint of solubility of the resin component.

In addition, the solvents shown below have the effect of improving the uniformity and smoothness of the coating film, and are preferably used by mixing them with a solvent in which the resin component has high solubility.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol. , ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether. , propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene Glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3- Methoxybutylacetate, 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. 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 -Butyl methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol di. Acetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate ester, ethyl lactate Ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, 2-ethyl-1-hexanol, etc. You may mix multiple types of these solvents. When using these solvents, it is preferable that it is 5-80 mass % of the whole solvent contained in a liquid crystal aligning agent, More preferably, it is 20-60 mass %.

The liquid crystal aligning agent may contain components other than those mentioned above. For example, a compound which improves film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, a compound which improves the adhesiveness of a liquid crystal aligning film, and a board|substrate, etc. are mentioned.

Compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F Top EF301, EF303, EF352 (manufactured by Tochem Products), Megapack F171, F173, R-30 (manufactured by Dainippon Ink), Florad FC430, FC431 (manufactured by Sumitomo 3M) (manufactured by Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass), etc. When using these surfactants, the usage ratio is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the resin component 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, epoxy group-containing compounds, and the like. 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)cyclo Hexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3 -(N,N-diglycidyl)aminopropyltrimethoxysilane, etc. are mentioned.

In addition, in order to further improve the rubbing resistance of the coating film obtained from the liquid crystal aligning agent, 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, tetra(methoxymethyl)bisphenol, etc. A phenol compound may be added. When using these compounds, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of the resin component contained in a liquid crystal aligning agent, More preferably, it is 1-20 mass parts.

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

＜Liquid crystal alignment film＞

After apply|coating the liquid crystal aligning agent of this invention to a board|substrate, the cured film obtained by drying and baking can also be used as it is as a liquid crystal aligning film as needed. In addition, this cured film is rubbed, irradiated with polarized light or light of a specific wavelength, treated with an ion beam, etc., or irradiated with UV while applying voltage to the liquid crystal display element after liquid crystal charging as an alignment film for SC-PVA. It is also possible to do so.

The substrate is not particularly limited as long as it is a highly transparent substrate, and includes glass plates, polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyether ketone, trimethylpentene, and polyolefin. , polyethylene terephthalate, (meth)acrylonitrile, triacetylcellulose, diacetylcellulose, acetate butylate cellulose, etc. can be used. In addition, it is preferable to use a substrate on which ITO (Indium Tin Oxide) electrodes for liquid crystal driving are formed, from the viewpoint of process simplification. In addition, in a reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as only one side of the substrate is used, 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 examples include 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. . In terms of productivity, transfer printing 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 carried out 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 to 150°C, preferably 60 to 100°C, for 0.5 to 30 minutes, preferably 1 to 5 minutes, is included.

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

Moreover, the thickness of the liquid crystal aligning film obtained by baking is not specifically limited, but is preferably 5 to 300 nm, and more preferably 10 to 120 nm.

＜Liquid crystal display device＞

The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above-described method and then producing a liquid crystal cell by a known method.

As a specific example of the liquid crystal display element, a liquid crystal cell having two substrates arranged to face each other, a liquid crystal layer formed between the substrates, and a liquid crystal aligning 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. Specifically, the liquid crystal aligning agent of the present invention is applied to two substrates and baked to form a liquid crystal aligning film, the two substrates are placed so that the liquid crystal aligning films face each other, and a liquid crystal is formed between the two substrates. It is a vertically aligned liquid crystal display element including a liquid crystal cell produced by sandwiching the formed liquid crystal layer, contacting it with a liquid crystal alignment film to form a liquid crystal layer, and irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer.

Using the liquid crystal aligning film formed with the liquid crystal aligning agent of the present invention, ultraviolet rays are irradiated while applying 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 a polymerizable compound, the orientation of the liquid crystal is fixed more efficiently, resulting in a liquid crystal display device with a remarkably 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.

The liquid crystal display element of the present invention may use a substrate on which a conventional electrode pattern or a protrusion pattern is formed, but by having a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention, the liquid crystal display element of the present invention has, for example, 1 to 1 on one side of the substrate. The operation is possible even when a 10 ㎛ line/slit electrode pattern is formed and a substrate with a structure that does not form a slit pattern or a protrusion pattern is used on the opposing substrate. The process when manufacturing a liquid crystal display element can be simplified, and the high Transmittance can be obtained.

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

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

After apply|coating the liquid crystal aligning agent of this invention on this board|substrate, a liquid crystal aligning film is formed by baking, and is as mentioned above in detail.

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display device of the present invention is not particularly limited, and includes liquid crystal materials used in the conventional vertical alignment method, for example, negative type such as MLC-6608 and MLC-6609 manufactured by Merck & Co., Ltd. Liquid crystals can be used.

In addition, in order to manufacture the liquid crystal display element of this invention, the polymeric compound of this invention may be contained in at least one of a liquid crystal aligning agent and the said liquid crystal layer.

As a method of sandwiching this liquid crystal layer between two substrates, a known method can be used. 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, the surface on the side on which the liquid crystal alignment film is formed is inside, and the other substrate is A method of bonding and sealing by injecting liquid crystal under reduced pressure is included.

In addition, a pair of substrates on which a liquid crystal aligning film was formed were prepared, and after dispersing spacers such as beads on the liquid crystal aligning film of one of the substrates, the liquid crystal was dropped, and then the surface on the side on which the liquid crystal aligning film was formed became the inside. Therefore, a liquid crystal cell can be produced also by a method of bonding and sealing different substrates. The thickness of the spacer at this time 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, One method is to irradiate ultraviolet rays while maintaining this electric field. 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, and more preferably 20 J/cm2 or less. A smaller amount of ultraviolet irradiation is preferable because it can suppress the decrease in reliability caused by destruction of the liquid crystal or members constituting the liquid crystal display element, and also increases manufacturing efficiency by reducing the irradiation time of ultraviolet rays.

The wavelength of ultraviolet rays to be used is preferably 300 to 400 nm, and more preferably 310 to 370 nm.

When ultraviolet rays are irradiated while applying voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is remembered by this polymer, thereby speeding up the response speed of the resulting liquid crystal display device. You can.

Moreover, when ultraviolet rays are irradiated while applying voltage to the liquid crystal alignment film and the liquid crystal layer, at least one polymer selected from the group consisting of a polyimide precursor having a reactive side chain and a polyimide obtained by imidizing this polyimide precursor is Since the photoreactive side chains that the polymer has or the photoreactive side chains that the polymer has reacts with the polymerizable compound, the response speed of the resulting liquid crystal display device can be increased.

In addition, the liquid crystal aligning agent of the present invention is not only useful as a liquid crystal aligning agent for producing vertically aligned liquid crystal display elements such as PSA-type liquid crystal displays and SC-PVA-type liquid crystal displays, but is also useful in rubbing processing and photo-alignment processing. It can also be preferably used for production of a liquid crystal alignment film formed by .

Example

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these. The abbreviations of the compounds below are as follows.

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

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

PMDA: Pyromellitic anhydride.

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

DBA: 3,5-diaminobenzoic acid

[Formula 35]

NMP: N-methyl-2-pyrrolidone.

BCS: Butylcellosolve.

3AMP: 3-picorylamine.

[Formula 36]

<Synthesis Example 1>

[Formula 37]

＜Synthesis of RM1-A＞

At room temperature, in a 500 mL (milliliter) four-necked flask equipped with a magnetic stirrer, 20 g (93.4 mmol) of 4-(4-hydroxyphenyl)benzoic acid, 70.0 g (3.5 wt) of NMP, and 38.7 g (3.0 g) of potassium carbonate. eq), and 0.776 g (5.0 mol%) of potassium iodide were added, and 10.0 g (0.5 wt) of NMP was added to the reaction solution while washing the wall of the flask, followed by stirring. Thereafter, the temperature was raised to 100°C, and 35.7 g (2.5 eq) of 4-chlorobutyraldehyde dimethylacetal and 10.0 g (0.5 wt) of NMP were flowed into the reaction system while washing the powder adhering to the wall of the flask, and The reaction was stirred for some time.

After the reaction, 120 g (6.0 wt) of toluene was added and filtered, and the filtrate was washed twice with 20.0 g (1 wt) of toluene. Next, the collected toluene filtrate was washed three times with 80.0 g (4 wt) of water. After that, it was vacuum dried at 50°C and the solvent was distilled off. 30.0 g (1.5 wt) of ethyl acetate was added to the residue, and the temperature was raised to 50°C to dissolve. After that, 140 g (7 wt) of heptane was added dropwise, and the mixture was cooled to 0°C. A small amount of seed crystal was added to precipitate crystals. The crystals were filtered, washed twice with 20.0 g (1 wt) of heptane, and then dried under vacuum at 30°C to obtain 38.0 g of RM1-A (yield: 91%, appearance: white solid).

＜Synthesis of RM1＞

At room temperature, 35.0 g (78.4 mmol) of RM1-A and 105 g (3.0 wt) of THF were charged into a 1 L four-necked flask equipped with a magnetic stirrer, stirred to confirm dissolution, and then tin chloride dihydrate. 38.9 g (2.2 eq) and 33.4 g (2.2 eq) of ethyl 2-(bromomethyl)acrylate were sequentially added, and the temperature was raised to 60°C. Next, 125 g (3.6 wt) of 0.1 M hydrochloric acid was added dropwise, and then 245 g (7 wt) of THF was poured into the reaction system while washing the powder adhering to the wall of the flask, and stirred for 14.5 hours to cause reaction.

The reaction liquid was cooled to 50°C, 350 g (10 wt) of toluene was added, the mixture was separated, and the hydrochloric acid layer was removed. After that, the organic layer was added dropwise to 263 g (7.5 wt) of a 12.9 mass% potassium hydroxide aqueous solution at 50°C over 30 minutes and stirred, and then the organic layer was separated. 262 g (7.5 wt) of a 5.2% by mass potassium hydroxide aqueous solution was added to the obtained organic layer and stirred, followed by liquid separation at 50°C. 3.49 g (10 wt%) of activated carbon was added to the separated organic layer, stirred at 50°C for 30 minutes, and then filtered at 50°C. The filtrate was washed twice with 17.5 g (0.5 wt) of toluene, and the collected toluene filtrate was cooled to 5°C with stirring and aged for 1 hour. The precipitated solid was filtered, and the filtrate was washed twice with 17.5 g (0.5 wt) of heptane. The filtrate was vacuum dried at 40°C to obtain 19.7 g of RM1 (yield: 51%, appearance: white crystals).

<Synthesis Example 2>

[Formula 38]

＜Synthesis of RM2-A＞

At room temperature, 80.0 g (430 mmol) of 4,4'-biphenol and 160.0 g (2.0 wt) of DMF were charged into a 500 mL four-necked flask equipped with a magnetic stirrer and stirred to dissolve. After that, 77.2 g (1.3 eq) of potassium carbonate and 3.57 g (5.0 mol%) of potassium iodide were sequentially added. After that, the temperature was raised to 80°C, 65.6 g (1.0 eq) of 4-chlorobutyraldehyde dimethylacetal was added dropwise over 1 hour, and the mixture was stirred for 19.5 hours to cause reaction.

The reaction solution was added dropwise into 1600 g (20 wt) of water, stirred for 0.5 hours, and the precipitated solid was filtered. The filtrate was washed twice with 40.0 g (0.5 wt) of water. After that, the filtrate was dried under reduced pressure at 40°C for 1.5 hours. To the dried filtrate, 880 g (11 wt) of methanol was added and the crystals were washed by stirring in a suspended state (hereinafter referred to as slurry washing) and then filtered. The filtrate was washed twice with 8.00 g (0.1 wt) of methanol. The solvent of the collected filtrate, such as methanol, was distilled off under reduced pressure to obtain a residue. The obtained residue was slurry washed with 1040 g (13 wt) of chloroform and filtered. The filtrate was washed twice with 16.0 g (0.2 wt) of chloroform, and the solvent in the collected filtrate of chloroform was distilled off. To the obtained residue, 104 g (1.3 wt) of THF and 326 g (4.1 wt) of heptane were added, cooled to 0°C, and crystallized. 400 g (5 wt) of methanol was added to the precipitated solid, followed by slurry washing and filtration. The filtrate was dried under reduced pressure at 40°C to obtain 33.6 g of RM2-A (yield: 26%, appearance: white solid).

＜Synthesis of RM2-B＞

At room temperature, 33.6 g (111 mmol) of RM2-A and 169 g (5 wt) of DMF were charged into a 500 mL four-necked flask equipped with a magnetic stirrer, stirred to dissolve, and 20.0 g (1.3 eq.) of potassium carbonate. ) was added. After that, the temperature was raised to 80°C, 25.6 g (1.3 eq) of 2-(4-bromobutyl)-1,3-dioxolane was added dropwise, and the mixture was stirred for 24.5 hours to cause reaction.

The reaction solution was added dropwise to 672 g (20 wt) of water, stirred for 0.5 hours, and the precipitated solid was filtered. The filtrate was washed twice with 16.8 g (0.5 wt) of water. The filtrate was then vacuum dried at 40°C for 1.5 hours. 100 g (3.0 wt) of toluene was added to the dried filtrate, and the temperature was raised to 70°C to dissolve. After that, 198 g (6.0 wt) of heptane was added dropwise, the mixture was cooled to 0°C, and the precipitated solid was filtered. The obtained filtrate was washed twice with 10.0 g (0.3 wt) of heptane. The filtrate was vacuum dried at 40°C to obtain 35.6 g of RM2-B (yield: 75%, appearance: white solid).

＜Synthesis of RM2＞

At room temperature, 50.0 g (116 mmol) of RM2-B and 500 g (10 wt) of THF were charged into a 1 L four-necked flask equipped with a magnetic stirrer, stirred to confirm dissolution, and then tin chloride dihydrate. 57.7 g (2.2 eq) and 49.3 g (2.2 eq) of ethyl 2-(bromomethyl)acrylate were sequentially added, and the temperature was raised to 60°C. After that, 179 g (3.6 wt) of 0.1 M hydrochloric acid was added dropwise, and the mixture was stirred for 26 hours to cause reaction.

The reaction liquid was cooled to 50°C, 500 g (10 wt) of toluene was added, and the liquid was separated to remove the hydrochloric acid layer. The organic layer was added dropwise to 375 g (7.5 wt) of a 12.9% by mass potassium hydroxide aqueous solution at 50°C over 30 minutes, and the organic layer was then separated into liquid. 375 g (7.5 wt) of a 5.2 mass% potassium hydroxide aqueous solution was added to the organic layer, and the layers were separated at 50°C. The separated organic layer was washed with 375 g (7.5 wt) of water. 5.12 g (10 wt%) of activated carbon was added to the washed organic layer, stirred at 50°C for 30 minutes, and then filtered at 50°C. The filtrate was washed twice with 25.0 g (0.5 wt) of toluene, and the collected toluene filtrate was cooled to 5°C while stirring and aged for 1 hour. The precipitated solid was filtered, and the filtrate was washed twice with 25.0 g (0.5 wt) of heptane. The filtrate was vacuum dried at 40°C to obtain 35.6 g of RM2 (yield: 83%, appearance: white crystals).

<Synthesis Example 3>

[Formula 39]

＜Synthesis of RM3-A＞

At room temperature, 50.0 g (269 mmol) of 4,4'-biphenol and 175 g of DMF were charged into a 500 mL four-necked flask equipped with a magnetic stirrer and stirred to dissolve, and then 48.24 g (1.3 g) of potassium carbonate was added. eq) was added. After that, the temperature was raised to 80°C, 48.61 g (1.0 eq) of 2-(2-bromoethyl)-1,3-dioxolane was added dropwise over 1 hour, and the mixture was stirred for 7 hours to cause reaction. Next, the reaction solution was added dropwise into 1000 g of water and stirred at room temperature for 0.5 hours, and then the precipitated solid was filtered. 550 g of methanol was added to the filtrate, slurry-washed at room temperature, and then filtered at 0 to 5°C. 650 g of chloroform was added to the residue after distilling off the solvent of the filtrate, and the mixture was slurry washed at room temperature and then filtered. To the residue after distilling off the solvent of the filtrate, 15 g of THF was added and dissolved, then 37.5 g of toluene was added, and the mixture was stirred in an ice bath for 0.5 hours. The precipitated crystals were filtered, washed (12.5 g of toluene), and then dried under reduced pressure at 40°C to obtain 9.0 g of RM3-A (yield: 12%, appearance: gray crystals).

＜Synthesis of RM3-B＞

At room temperature, 8.31 g (29 mmol) of RM3-A and 12.5 g of NMP were charged into a 500 mL four-neck flask equipped with a magnetic stirrer and stirred to dissolve, and then 6.01 g (1.5 eq.) of potassium carbonate was added. added. After that, the temperature was raised to 80°C, 5.79 g (1.1 eq) of 2-(4-bromobutyl)-1,3-dioxolane was added dropwise over 10 minutes, and the mixture was stirred for 19 hours to cause reaction. Next, 83 g of ethyl acetate was added to the reaction liquid, and the precipitated inorganic salt was filtered. After that, the filtrate was separated and washed three times with 24 g of water, and the solvent in the filtrate was distilled off. 24 g of toluene was added to the obtained residue, and after dissolving at 70°C, 48 g of heptane was added, and the mixture was briefly stirred in an ice bath. The precipitated crystals were filtered and dried under reduced pressure at 40°C to obtain 12.2 g of RM3-B (yield: 91%, appearance: white solid).

＜Synthesis of RM3＞

At room temperature, 11.0 g (26.5 mmol) of RM3-B and 110 g of THF were injected into a 500 mL four-neck flask equipped with a magnetic stirrer and stirred to dissolve, and then 14.4 g (2.4 eq) of tin chloride dihydrate was added. , and 49.3 g (2.2 eq) of 2-(bromomethyl)ethyl acrylate were sequentially added. After that, 38.5 g of 10% by mass hydrochloric acid was added dropwise, and reaction was performed for 120 hours. The reaction solution was concentrated under reduced pressure to about one-third, cooled to 15°C, and the precipitated crystals were filtered and washed (44 g of water x 3 times). Next, this crystal was dissolved in 165 g of THF and diluted by adding 110 g of toluene. The obtained solution was added dropwise into 82.5 g of a 12.9% by mass potassium hydroxide aqueous solution at room temperature, and the aqueous layer was separated and removed. To the obtained organic layer, 82.5 g of a 5.2% by mass potassium hydroxide aqueous solution was added at room temperature, and the aqueous layer was separated and removed. After that, the organic layer was washed 5 times with 82.5 g of water, 0.55 g (5% by mass) of specially made egret activated carbon was added, the mixture was stirred at room temperature for 1 hour, and this was filtered. After that, the filtrate was concentrated under reduced pressure to about 15 g and stirred for a while at 5°C. The precipitated crystals were filtered, washed (heptane 5.5 g x 2 times), and dried under reduced pressure at 40°C to obtain 7.1 g of RM3 (yield: 53%, appearance: white crystals).

<Synthesis Example 4>

RM4 was synthesized by the method disclosed in WO2012/002513.

<Synthesis Example 5>

RM5 was synthesized by the method disclosed in Japanese Patent Application No. 2014-015830.

<Synthesis Example 6>

[Formula 40]

＜Synthesis of RM6-A＞

At room temperature, 55.8 g (300 mmol) of 4,4'-biphenol and 62.7 g (62.7 g) of 2-(4-bromobutyl)-1,3-dioxolane were added to a 1 L 4-neck flask equipped with a magnetic stirrer. 1.0 eq), and 234 g (4.2 wt) of acetone were sequentially injected, and while stirring, 53.9 g (1.3 eq) of potassium carbonate was further added, and then 156 g (2.8 wt) of acetone was added to the flask attached to the wall. While washing the powder, it was poured into the reaction system. After that, the temperature was raised to 60°C and stirred for 41.5 hours to cause reaction.

After leaving to cool to room temperature, the reaction solution was added dropwise into 3013 g (54 wt) of water and stirred for 30 minutes. Next, the precipitated solid was filtered, and the filtrate was dried under reduced pressure at 30°C. 614 g (11 wt) of methanol was added to the dried solid, stirred, and slurry washing was performed. After that, it was filtered and the obtained filtrate was concentrated. To the obtained residue, 725 g (13 wt) of chloroform was added, stirred, and slurry washing was performed. Next, the obtained filtrate was concentrated under reduced pressure. To the obtained residue, 72.5 g (1.3 wt) of THF was added, and 273 g (4.9 wt) of heptane was added dropwise, followed by cooling to 0°C. The precipitated solid was filtered, washed with heptane, and then dried under reduced pressure to obtain 31.6 g of RM6-A (yield: 34%, appearance: white solid).

＜Synthesis of RM6-B＞

At room temperature, in a 500 mL four-necked flask equipped with a magnetic stirrer, 19.7 g (62.6 mmol) of RM6-A, 43.1 g (5.0 eq) of potassium carbonate, 1.04 g (10 mol%) of potassium iodide, and 148 g of DMF ( 7.5 wt) was sequentially added, stirred, and the temperature was raised to 100°C. Additionally, 4.80 g (1.8 eq) of 4-chloro-1-butanol was added dropwise and stirred for 27 hours to cause reaction. Since the reaction slowed down along the way, 2.40 g (0.3 eq) of 4-chloro-1-butanol was added twice.

After that, the reaction liquid was filtered, and potassium carbonate was separated by filtration. The filtrate was concentrated to 4.3 wt, and the residue was added dropwise to 400 g (20 wt) of water to precipitate crystals. 197 g (10 wt) of THF was added to the obtained crystal, dissolved at 40°C, and 197 g (10 wt) of heptane was added dropwise to precipitate the crystal. After that, the solution containing the crystals was cooled to 0°C, filtered, and the obtained crystals were dried under reduced pressure to obtain 19.4 g of RM6-B (yield: 80%, appearance: light brown solid).

＜Synthesis of RM6-C＞

At room temperature, 155 g (8.0 wt) of THF was added to 19.4 g (50.3 mmol) of RM6-B, and after confirming that it was dissolved while stirring, 55.4 mg (0.5 mol%) of BHT and 20.4 g (1.8 eq.) of tin chloride dihydrate were added. ), and 17.5 g (1.8 eq) of 2-(bromomethyl)ethyl acrylate were sequentially injected. After that, the temperature was raised to 60°C, 69.4 g (3.6 wt) of 0.1 M hydrochloric acid was added dropwise, and the mixture was stirred for 18 hours to cause reaction.

Next, after adjusting the temperature to 50°C, 194 g (10 wt) of toluene was added and the liquid was separated. The organic layer was added dropwise to 150 g (7.5 wt) of a 12.9% by mass potassium hydroxide aqueous solution at 50°C over 30 minutes, but insoluble matter precipitated. Therefore, 637 g (32.8 wt) of a 12.9 mass% potassium hydroxide aqueous solution was added to dissolve the insoluble matter, and then the liquid was separated at 50°C. Next, the separated organic layer was washed with 150 g (7.5 wt) of a 5.2 mass% potassium hydroxide aqueous solution and further with 150 g (7.5 wt) of water. To the washed organic layer, 2.00 g of activated carbon (specially made egret, 10 wt%) was added, stirred at 50°C for 30 minutes, and then filtered. The filtrate was washed twice with 10.5 g (0.5 wt) of toluene, and the collected filtrate was aged at 5°C for 30 minutes. After that, the precipitated solid was filtered and washed twice with 10.5 g (0.5 wt) of heptane. The obtained solid was dried under reduced pressure at 40°C, and 3.2 g of RM6-C was obtained (yield: 16%, appearance: white solid).

＜Synthesis of RM6＞

At room temperature, 3.1 g (7.5 mmol) of RM6-C was injected into a 500 mL four-necked flask equipped with a magnetic stirrer, and 308 g (100 wt) of THF was added, and it was confirmed that it was dissolved while stirring. After that, 10.3 g (13.6 eq.) of triethylamine and 10.2 g (13 eq.) of methacrylic acid chloride were added dropwise over 1 hour, and stirred for 19.5 hours to cause reaction.

Next, 217 g (70 wt) of water was added to dissolve triethylamine hydrochloride, and 208 g (67 wt) of toluene was further added to separate the layers. The separated organic layer was washed twice with 151 g (49 wt) of water. Thereafter, in order to avoid polymerization reaction occurring, the solvent was distilled off under reduced pressure at 25°C until the amount of solvent reached 10 g (3.3 wt). After adding 40.3 g (13 wt) of heptane dropwise to the obtained residue, it was cooled to 0°C and aged for 1 hour. The precipitated solid was filtered and washed twice with 9.3 g (3.0 wt) of heptane. The obtained solid was vacuum dried at 25°C, and 2.4 g of RM6 was obtained (yield: 67%, appearance: white crystal).

In addition, the hydrogen nuclear magnetic resonance ( ^1HNMR ) of the synthesis example was measured in a deuterated dimethyl sulfoxide (DMSO-d6) solvent using an NMR meter (JNW-ECA500, manufactured by Nippon Electronics Datum Co., Ltd.), and the chemical shift was: Expressed as δ value (ppm) using tetramethylsilane as an internal standard.

＜Measurement of polyimide molecular weight＞

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

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

Column temperature: 50℃,

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

Flow rate: 1.0 mL/min,

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

＜Measurement of imidization rate＞

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 mass% TMS mixture), and apply ultrasonic waves to completely dissolved. Proton NMR at 500 MHz was measured for this solution using an NMR measuring instrument (JNW-ECA500, manufactured by Nippon Electronics Datum Co., Ltd.). For the imidization rate, a proton derived from a structure that does not change before and after imidization is set as a reference proton, and the peak integrated value of this proton and the proton peak integrated value derived from the NH group of amic acid appearing around 9.5 to 10.0 ppm are used. It was obtained using the following equation. In the formula below, x is the integrated peak value of the proton derived from the NH group of the amic acid, y is the integrated peak value of the reference proton, and α is the NH value of the amic acid in the case of polyamic acid (imidation rate of 0%). It is the ratio of the number of standard protons to one basic proton.

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

<Synthesis Example 7>

BODA (10.0 g, 40.0 mmol), DA-1 (15.2 g, 40.0 mmol), DA-2 (4.85 g, 20.0 mmol), and DA-3 (13.2 g, 40.0 mmol) in NMP (164.4 g) It was dissolved and reacted at 60°C for 3 hours. Next, CBDA (11.5 g, 58.6 mmol) and NMP (54.8 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 (250 g) and diluting it to 6.5% by mass, acetic anhydride (46.4 g) and pyridine (14.4 g) were added as imidization catalysts, and reaction was performed at 70°C for 3 hours. This reaction solution was added to methanol (2900 g), 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 imidation rate of this polyimide was 73%, Mn was 13000, and Mw was 39000.

NMP (48.8 g) was added to the obtained polyimide powder A (10.0 g), and stirred at 70°C for 12 hours to dissolve. 10.0 g of 3AMP (1 wt% NMP solution), NMP (31.2 g), and BCS (66.7 g) were added to this solution, and it stirred at room temperature for 5 hours, and liquid crystal aligning agent A1 was obtained.

<Synthesis Example 8>

BODA (18.0 g, 72.0 mmol), DA-1 (13.7 g, 36.0 mmol), DA-2 (8.72 g, 36.0 mmol), and DBA (7.30 g, 48.0 mmol) were dissolved in NMP (173.5 g), The reaction was performed at 60°C for 3 hours. After that, PMDA (10.1 g, 46.3 mmol) and NMP (57.8 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (250 g) and diluting it to 10% by mass, acetic anhydride (52.6 g) and pyridine (40.8 g) were added as imidization catalysts, and reaction was performed at 80°C for 4 hours. This reaction solution was added to methanol (2900 g), and the obtained precipitate was separated by filtration. This deposit was washed with methanol, dried under reduced pressure at 100°C, and polyimide powder B was obtained. The imidation rate of this polyimide was 77%, Mn was 12000, and Mw was 35000. Liquid crystal aligning agent B1 was obtained in the same manner as in Synthesis Example 7 except that polyimide powder B (10.0 g) was used instead of polyimide powder A.

<Synthesis Example 9>

Liquid crystal aligning agent C1 was obtained by adding 30.0 g of liquid crystal aligning agent B1 obtained in Synthesis Example 8 to 70.0 g of liquid crystal aligning agent A1 obtained in Synthesis Example 7, and stirring at room temperature for 5 hours.

<Synthesis Example 10>

BODA (6.51 g, 26.0 mmol), DA-1 (14.8 g, 38.9 mmol), and DBA (13.9 g, 91.0 mmol) were dissolved in NMP (165.3 g) and reacted at 60°C for 3 hours. After that, CBDA (19.9 g, 101.5 mmol) and NMP (55.1 g) were added and reacted at 40°C for 12 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (250 g) and diluting it to 6.5% by mass, acetic anhydride (59.7 g) and pyridine (18.5 g) were added as imidization catalysts, and reaction was performed at 50°C for 3 hours. This reaction solution was added to methanol (2900 g), and the obtained precipitate was separated by filtration. This deposit was washed with methanol, dried under reduced pressure at 100°C, and polyimide powder D was obtained. The imidation rate of this polyimide was 75%, Mn was 12000, and Mw was 32000. Liquid crystal aligning agent D1 was obtained in the same manner as in Synthesis Example 7 except that polyimide powder D (10.0 g) was used instead of polyimide powder A.

<Synthesis Example 11>

Liquid crystal aligning agent E1 was obtained by adding 30.0 g of liquid crystal aligning agent D1 obtained in Synthesis Example 10 to 70.0 g of liquid crystal aligning agent A1 obtained in Synthesis Example 7, and stirring at room temperature for 5 hours.

<Synthesis Example 12>

BODA (10.0 g, 40.0 mmol), DA-1 (19.0 g, 50.0 mmol), and DA-3 (16.5 g, 50.0 mmol) were dissolved in NMP (171.1 g) and reacted at 60°C for 3 hours. After that, CBDA (11.5 g, 58.6 mmol) and NMP (57.0 g) were added and reacted at 40°C for 12 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (250 g) and diluting it to 6.5% by mass, acetic anhydride (44.5 g) and pyridine (13.8 g) were added as imidization catalysts, and reaction was performed at 70°C for 3 hours. This reaction solution was added to methanol (2900 g), and the obtained precipitate was separated by filtration. This deposit was washed with methanol, dried under reduced pressure at 100°C, and polyimide powder F was obtained. The imidation rate of this polyimide was 73%, Mn was 14000, and Mw was 38000. Liquid crystal aligning agent F1 was obtained in the same manner as in Synthesis Example 7 except that polyimide powder F (10.0 g) was used instead of polyimide powder A.

<Synthesis Example 13>

With respect to 70.0 g of liquid crystal aligning agent F1 obtained in Synthesis Example 12, 30.0 g of liquid crystal aligning agent B1 obtained in Synthesis Example 8 was added, and the mixture was stirred at room temperature for 5 hours to obtain liquid crystal aligning agent G1.

<Synthesis Example 14>

BODA (10.0 g, 40.0 mmol), DA-1 (15.2 g, 40.0 mmol), DA-3 (9.91 g, 30.0 mmol), and DA-5 (7.93 g, 30.0 mmol) were dissolved in NMP (163.7 g) and reacted at 60°C for 3 hours. After that, CBDA (11.5 g, 58.6 mmol) and NMP (54.6 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 (250 g) and diluting it to 6.5 mass%, acetic anhydride (46.5 g) and pyridine (14.4 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 (2900 g), and the obtained precipitate was separated by filtration. This deposit was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder H. The imidation rate of this polyimide was 74%, Mn was 16,000, and Mw was 45,000. Liquid crystal aligning agent H1 was obtained in the same manner as in Synthesis Example 7 except that polyimide powder H (10.0 g) was used instead of polyimide powder A.

<Synthesis Example 15>

TCA (1.35 g, 6.0 mmol), DA-1 (2.28 g, 6.0 mmol), and DA-3 (2.97 g, 9.0 mmol) were dissolved in NMP (24.9 g) and reacted at 80°C for 3 hours. After that, CBDA (1.74 g, 8.9 mmol) and NMP (8.3 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (36 g) and diluting it to 6% by mass, acetic anhydride (4.0 g) and pyridine (2.1 g) were added as imidization catalysts, and reaction was performed 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 and dried under reduced pressure at 100°C to obtain polyimide powder I. The imidation rate of this polyimide was 60%, Mn was 20000, and Mw was 43000.

NMP (44.0 g) was added to the obtained polyimide powder I (6.0 g), and stirred at 50°C for 5 hours to dissolve. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g), and BCS (30.0 g) were added to this solution, and it was stirred at room temperature for 5 hours to obtain liquid crystal aligning agent I1.

<Synthesis Example 16>

BODA (2.00 g, 8.0 mmol), DA-3 (4.63 g, 14.0 mmol), and DA-4 (2.61 g, 6.0 mmol) were dissolved in NMP (34.5 g) and reacted at 60°C for 3 hours. After that, CBDA (2.27 g, 11.6 mmol) and NMP (11.5 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (50 g) and diluting it to 6% by mass, acetic anhydride (5.3 g) and pyridine (2.7 g) were added as imidization catalysts, and reaction was performed at 50°C for 3 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 J was obtained. The imidation rate of this polyimide was 60%, Mn was 17,000, and Mw was 35,000. Liquid crystal aligning agent J1 was obtained in the same manner as in Synthesis Example 15 except that polyimide powder J (10.0 g) was used instead of polyimide powder I.

<Synthesis Example 17>

BODA (1.30 g, 5.2 mmol), DA-6 (2.03 g, 3.9 mmol), and DA-3 (3.00 g, 9.1 mmol) were dissolved in NMP (23.5 g) and reacted at 60°C for 3 hours. After that, CBDA (1.43 g, 7.3 mmol) and NMP (7.8 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic acid solution (36 g) and diluting it to 6% by mass, acetic anhydride (3.6 g) and pyridine (1.9 g) were added as imidization catalysts, and reaction was performed 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 and dried under reduced pressure at 100°C to obtain polyimide powder K. The imidation rate of this polyimide was 60%, Mn was 16000, and Mw was 36000. Liquid crystal aligning agent K1 was obtained in the same manner as in Synthesis Example 15 except that polyimide powder K (10.0 g) was used instead of polyimide powder I.

(Example 1)

To 10.0 g of liquid crystal aligning agent C1 obtained in Synthesis Example 9, 0.042 g (7% by mass relative to solid content) of polymerizable compound RM1 obtained in Synthesis Example 1 was added, stirred at room temperature for 3 hours to dissolve, and liquid crystal aligning agent L1 was added. was prepared.

(Example 2)

Liquid crystal aligning agent L2 was prepared by the same method as Example 1 except that the quantity of polymeric compound RM1 was 0.06 g (10 mass % with respect to solid content).

(Example 3)

Liquid crystal aligning agent L3 was prepared by the same method as Example 1 except that RM2 obtained in Synthesis Example 2 was used instead of polymeric compound RM1.

(Example 4)

Liquid crystal aligning agent L4 was prepared by the same method as Example 1 except that RM3 obtained in Synthesis Example 3 was used instead of polymeric compound RM1.

(Example 5)

Instead of liquid crystal aligning agent C1, liquid crystal aligning agent M1 was prepared by the same method as Example 1 except that liquid crystal aligning agent A1 obtained in Synthesis Example 7 was used.

(Example 6)

Liquid crystal aligning agent N1 was prepared by the same method as Example 1 except that liquid crystal aligning agent E1 obtained in Synthesis Example 11 was used instead of liquid crystal aligning agent C1.

(Example 7)

Instead of liquid crystal aligning agent C1, liquid crystal aligning agent O1 was prepared by the same method as Example 1 except that liquid crystal aligning agent G1 obtained in Synthesis Example 13 was used.

(Example 8)

Instead of liquid crystal aligning agent C1, liquid crystal aligning agent P1 was prepared by the same method as Example 1 except that liquid crystal aligning agent H1 obtained in Synthesis Example 14 was used.

(Example 9)

Instead of liquid crystal aligning agent C1, liquid crystal aligning agent Q1 was prepared by the same method as Example 1 except that liquid crystal aligning agent I1 obtained in Synthesis Example 15 was used.

(Example 10)

Instead of liquid crystal aligning agent C1, liquid crystal aligning agent R1 was prepared by the same method as Example 1 except that liquid crystal aligning agent J1 obtained in Synthesis Example 16 was used.

(Example 11)

Instead of liquid crystal aligning agent C1, liquid crystal aligning agent S1 was prepared by the same method as Example 1 except that liquid crystal aligning agent K1 obtained in Synthesis Example 17 was used.

(Comparative Example 1)

Liquid crystal aligning agent L5 was prepared by the same method as Example 1 except that RM4 obtained in Synthesis Example 4 was used instead of polymeric compound RM1.

(Comparative Example 2)

Liquid crystal aligning agent L6 was prepared by the same method as Example 1 except that RM5 obtained in Synthesis Example 5 was used instead of polymeric compound RM1.

(Comparative Example 3)

Liquid crystal aligning agent L7 was prepared by the same method as Example 2 except that RM5 obtained in Synthesis Example 5 was used instead of polymeric compound RM1.

(Comparative Example 4)

Liquid crystal aligning agent L8 was prepared by the same method as Example 1 except that RM6 obtained in Synthesis Example 6 was used instead of polymeric compound RM1.

(Comparative Example 5)

Liquid crystal aligning agent L9 was prepared by the same method as Example 2 except that RM6 obtained in Synthesis Example 6 was used instead of polymeric compound RM1.

＜Production of liquid crystal cell＞

(Example 12)

Using the liquid crystal aligning agent L1 obtained in Example 1, the liquid crystal cell was produced in the following procedure.

Liquid crystal aligning agent L1 was spin-coated on the IZO surface of a 4-pixel IZO electrode substrate on which an IZO electrode pattern (fishbone) with a pixel size of 87 μm × 89 μm and a line/space of 3 μm each was formed, and 80 It was dried on a hot plate at ℃ for 90 seconds. Then, baking was performed for 20 minutes in a 200 degreeC hot air circulation type oven, and the liquid crystal aligning film with a film thickness of 100 nm was formed.

Additionally, liquid crystal aligning agent L1 was spin-coated on the ITO surface of the ITO electrode substrate on which no electrode pattern was formed, and dried with an 80°C hot plate for 90 seconds. After that, baking was performed for 20 minutes in a hot air circulation oven at 200°C, and a liquid crystal alignment film with a film thickness of 100 nm was formed.

About the above-mentioned two board|substrates, after dispersing the 3.3-micrometer bead spacer on the liquid crystal alignment film of one board|substrate, the sealing agent (solvent-type thermosetting type epoxy resin) was printed from thereon. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was turned inside and bonded to the previous substrate, and then the sealant was cured to produce an empty cell. Liquid crystal MLC-6608 (manufactured by Merck & Co., Ltd.) was injected into this empty cell by a reduced-pressure injection method. After that, the reorientation process of the liquid crystal was performed by putting it into a hot air circulation oven at 120°C for 1 hour, and liquid crystal cell 1 was produced.

“Observation of bright spots in liquid crystal cells”

The bright point in the obtained liquid crystal cell 1 was observed by the following method. The liquid crystal cell 1 immediately after the above reorientation treatment was left at room temperature for 2 days, and the liquid crystal cell was then observed with a polarizing microscope. It is thought that when the solubility of a polymeric compound in liquid crystal is low, it becomes easy to precipitate in a liquid crystal cell and a bright spot occurs. If a bright spot does not occur, it is considered good, and if a bright spot does occur, it is considered bad.

“Evaluation of AC-derived afterimages”

The afterimage derived from AC of the obtained liquid crystal cell 1 was measured by the following method.

With a DC voltage of 15 V applied to the liquid crystal cell 1, 6 J/cm2 of UV that had passed through a 365 nm band-pass filter was irradiated from the outside of the liquid crystal cell 1. In addition, the UV illuminance was measured using UV-MO3A manufactured by ORC. Thereafter, without applying voltage, UV (UV lamp: FLR40SUV32/A-1) was irradiated for 30 minutes using a UV-FL irradiation device manufactured by Toshiba Litec. A polarizing film was affixed to both sides of liquid crystal cell 1 in a cross nicol state so that the polarization axis of the polarizing film and the director of the liquid crystal formed an angle of 45°. Among the four pixels, a rectangular wave of 30 Hz and 20 Vpp was applied to only one random pixel and one pixel diagonal from the pixel for 70 hours. After turning off the voltage, the electrodes of the liquid crystal cell were connected and short-circuited. Thereafter, this liquid crystal cell was placed on a backlight, and the luminance of the voltage-applied pixel and the non-voltage-applied pixel were compared with the naked eye. When the afterimage characteristics are good, the luminance difference between the voltage-applied pixel and the non-voltage-applied pixel is thought to be small. When the cell was observed from the front, a cell in which the luminance difference could not be recognized was considered good, and a cell that could be recognized was considered bad.

“Measurement of pretilt angle”

In the production of liquid crystal cell 1, instead of an IZO electrode substrate with 4 pixels, 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 each is formed is used, 3.3 Liquid crystal cell 2 was produced in the same manner as the production of liquid crystal cell 1, except that a 4 μm bead spacer was used instead of the μm bead spacer.

With a DC voltage of 15 V applied to the obtained liquid crystal cell 2, 6 J/cm 2 of UV that had passed through a 365 nm band-pass filter was irradiated from the outside of this liquid crystal cell 2. In addition, the UV illuminance was measured using UV-MO3A manufactured by ORC. After that, without applying voltage, UV (UV lamp: FLR40SUV32/A-1) was irradiated for 30 minutes using a UV-FL irradiation device (manufactured by Toshiba Litec).

Using the LCD analyzer LCA-LUV42A (manufactured by Mayyo Technica), the pretilt angle of the pixel portion after UV irradiation was measured.

(Examples 13 to 22, Comparative Examples 6 to 10)

Except having used each liquid crystal aligning agent shown in Table 2 instead of liquid crystal aligning agent L1, the same operation as Example 12 was performed to produce a liquid crystal cell, and the said evaluation was performed about each liquid crystal cell. The results are summarized and shown in Table 2.

From the bright point observation results of Examples 12 to 15 and Comparative Example 6, it can be seen that the solubility in the liquid crystal is improved by making the molecular structure of the polymerizable compound used asymmetrical.

Moreover, from the comparison between Examples 12, 14, and 15 and Comparative Examples 7 and 8, the method of asymmetry of the molecular structure of the polymerizable compound of the present invention (methods 1 and 2 above) is such that the benzene ring is left and right asymmetric. Compared with the method of introducing a substituent (Method 4), it can be seen that the residual image characteristics derived from AC are excellent.

Likewise, from the results of Examples 12, 14, and 15 and Comparative Examples 9 and 10, the method of asymmetry of the molecular structure of the polymerizable compound of the present invention is superior even when compared with the method (Method 3) in which the left and right polymerizable groups are different. , it can be seen that AC-derived afterimage characteristics are excellent.

This is believed to be because the stacking of the ring structure is stronger compared to compounds of a methacrylic group where one side of the polymerizable group is not a ring structure, and thus the resulting polymer network is more rigid.

A liquid crystal display element having a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention has a fast liquid crystal response speed, and can be widely used as a vertically aligned liquid crystal display element such as a PSA type liquid crystal display, for example.

In addition, the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2015-22123 filed on February 6, 2015 are hereby cited and accepted as disclosure of the specification of the present invention.

Claims (12)

A polyimide precursor obtained from a polymerizable compound (1) represented by the following formula (1), a diamine containing a diamine having a side chain that vertically orients the liquid crystal, and a diamine having a photoreactive side chain, and the polyimide precursor. A liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyimides obtained by imidizing.
[Formula 1]

⁽ In the formula, ^{X 1 and} Additionally, S ¹ , X ¹ , X ² and S ² are selected so that the molecule is left-right asymmetric.) According to claim 1,
In the polymerizable compound (1), S ¹ and S ² are alkylene groups having different carbon numbers. According to claim 1,
In the polymerizable compound (1), one of X ¹ and X ² is an ether bond and the other ^is an ester bond, or X ¹ is an ester bond bonded to S ¹ on the carbonyl side, and A liquid crystal aligning agent that is an ester bond bonded to S ² on the side. A liquid crystal aligning film formed using the liquid crystal aligning agent according to any one of claims 1 to 3. A liquid crystal display element having the liquid crystal alignment film according to claim 4. At least one selected from the group consisting of a polyimide precursor obtained from a diamine containing a diamine having a side chain that vertically aligns the liquid crystal and a diamine having a photoreactive side chain, and a polyimide obtained by imidizing the polyimide precursor. A liquid crystal aligning agent containing a polymer is applied onto two substrates to form a liquid crystal alignment layer, the two substrates are arranged so that the liquid crystal alignment layers face each other, and a liquid crystal layer is placed between the two substrates. A method of manufacturing a vertically aligned liquid crystal display device in which an electric field is applied to the liquid crystal layer and irradiated with ultraviolet rays, comprising:
A method for producing a liquid crystal display element, characterized in that at least one of the liquid crystal aligning agent and the liquid crystal layer contains a polymerizable compound represented by Formula (1).
[Formula 2]

⁽ In the formula, ^{X 1 and} Additionally, S ¹ , X ¹ , X ² and S ² are selected so that the molecule is left-right asymmetric.) According to claim 6,
In the polymerizable compound (1), S ¹ and S ² are alkylene groups having different carbon numbers. According to claim 6 or 7,
In the polymerizable compound (1), one of X ¹ and X ² is an ether bond and the other ^is an ester bond, or X ¹ is an ester bond bonded to S ¹ on the carbonyl side, and A production method in which the ester bond is bonded to S ² on the side. delete delete delete delete