KR102529347B1 - Liquid crystal orientation agent, liquid crystal oriented film, and liquid crystal display element - Google Patents

Abstract

A liquid crystal aligning agent and a liquid crystal display element enabling a liquid crystal display element having a fast response speed and excellent in AC-derived afterimage characteristics are provided. The liquid crystal display element formed by making a liquid crystal aligning agent and/or a liquid crystal layer contain the polymeric compound represented by Formula (1). (X ¹ , X ² represents a bonding group such as an ether bond, S ¹ , S ² represents a straight-chain alkylene group having 2 to 9 carbon atoms, and S ¹ , X ¹ , X ² , S ² represents a left-right asymmetric molecule is chosen to be.)

Description

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

The present invention is a liquid crystal display having a liquid crystal aligning agent that can be preferably used in a liquid crystal display element produced by irradiating ultraviolet rays in a state in which a voltage is applied to liquid crystal molecules, a liquid crystal aligning film formed with the liquid crystal aligning agent, and the liquid crystal aligning film. It's about the little ones.

Among liquid crystal display elements of a system in which liquid crystal molecules aligned vertically with respect to the substrate are responded to by an electric field (also referred to as a vertical alignment (VA) system), ultraviolet rays are irradiated while applying a voltage to the liquid crystal molecules in the manufacturing process. There are some that include a process to do.

In such a vertical alignment type liquid crystal display device (PSA (Polymer Sustained Alignment) type liquid crystal display or the like), a photopolymerizable compound is previously added to a liquid crystal composition and used together with a vertical alignment film such as polyimide to increase voltage to a liquid crystal cell. A technique for speeding up the response speed of a liquid crystal by irradiating ultraviolet rays while applying is known (see Patent Document 1 and Non-Patent Document 1).

Usually, the inclination direction of liquid crystal molecules in response to an electric field is controlled by protrusions formed on a substrate or slits formed in electrodes for display, but a photopolymerizable compound is added to the liquid crystal composition and a voltage is applied to the liquid crystal cell. Since a polymer structure in which the direction in which the liquid crystal molecules were tilted is stored is formed on the liquid crystal alignment film by irradiating ultraviolet rays while doing so, the response speed of the liquid crystal display element is improved compared to the method of controlling the tilt direction of the liquid crystal molecules only with protrusions or slits. It is said to speed up

In addition, it has been reported that the response speed of the liquid crystal display element is increased by adding the photopolymerizable compound 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 Unexamined 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, the response speed of the liquid crystal display element has been desired to be made even faster, and it is considered that the response speed of the liquid crystal display element is increased by increasing the amount of addition of the photopolymerizable compound, but the conventional photopolymerizable compound, It has a property that it is difficult to dissolve in the solvent used for the liquid crystal aligning agent. Therefore, when preserving 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 in the manufacturing process, some polymeric compounds may elute into a liquid crystal from a liquid crystal aligning 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 considered that crystallization in the liquid crystal occurs easily. Crystallization of the polymerizable compound in such a liquid crystal serves as a bright spot source in a display element, leading to a decrease in display quality of the element.

Moreover, as another subject of a liquid crystal display element, there exists exposure (afterimage), and it may arise when the same pattern is displayed for a long time. One of the causes of this exposure is due to the accumulation of electric charges. Exposure resulting from charge accumulation is also referred to as DC exposure, but can be suppressed to some extent by driving for applying a voltage in which the polarity is reversed, that is, polarity inversion driving. On the other hand, even if the pretilt angle changes minutely, exposure occurs. Since the V-T characteristics are affected when the pretilt angle is changed, the transmittance is changed even when the same voltage is applied. Since the voltage applied during white display is different from the voltage applied during black display, the amount of change in the tilt angle varies depending on the applied voltage. Exposure may be recognized. Such exposure cannot be suppressed even if polarity inversion driving is performed, and is also called AC exposure.

An object of the present invention is to solve the problems of the prior art described above.

As a result of repeated researches in order to achieve the above object, the present inventors have reached the present invention having the following as a summary.

1. The liquid crystal aligning agent containing the polymeric compound represented by following formula (1), and the at least 1 polymer chosen from the group which consists of a polyimide precursor and a polyimide.

[Formula 1]

(Wherein, X ¹ and X ² each independently represent a bonding group selected from an ether bond and an ester bond, and S ¹ and S ² each independently represent a linear alkylene group having 2 to 9 carbon atoms; In addition, the S ¹ , X ¹ , X ² and S ² are selected so that the molecule is left-right asymmetric.)

2. The said liquid crystal aligning agent of 1 which is an alkylene group which has mutually different carbon number in ^S1 and ^S2 in the said polymeric compound (1).

3. In the above 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 X ² is The liquid crystal aligning agent as described in said 1 or 2 which is an ester group couple|bonded with ^S2 on the oxygen atom side.

4. The liquid crystal aligning agent in any one of said 1-3 which has a side chain in which the at least 1 polymer chosen from the group which consists of a polyimide precursor and a polyimide vertically orientates a liquid crystal.

5. The liquid crystal aligning agent in any one of said 1-4 in which the at least 1 polymer chosen from the group which consists of a polyimide precursor and polyimide has a photoreactive side chain further.

6. Liquid crystal aligning film formed using the liquid crystal aligning agent in any one of said 1-5.

7. Liquid crystal display element which has liquid crystal aligning film of said 6.

8. A liquid crystal aligning agent containing at least one polymer selected from the group consisting of a polyimide precursor and polyimide is coated on two substrates to form a liquid crystal alignment layer, and the liquid crystal alignment layer is opposed to the two sheets A method of manufacturing a liquid crystal display device of a vertical alignment system 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,

The manufacturing method of the liquid crystal display element characterized by making at least one of a liquid crystal aligning agent and a liquid crystal layer contain the polymeric compound represented by Formula (1).

[Formula 2]

(Wherein, X ¹ and X ² each independently represent a bonding group selected from an ether bond and an ester bond, and S ¹ and S ² each independently represent a linear alkylene group having 2 to 9 carbon atoms; In addition, the S ¹ , X ¹ , X ² and S ² are selected such that the molecule is left-right asymmetric.)

9. In the above polymerizable compound (1), S ¹ and S ² are alkylene groups having mutually different carbon atoms, the production method described in the above 8.

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 X ² is The production method described in the above 8 or 9, which is an ester group bonded to S ² on the oxygen atom side.

11. The manufacturing method in any one of said 8-10 which has a side chain in which the at least 1 polymer chosen from the group which consists of a polyimide precursor and polyimide vertically orientates a liquid crystal.

12. The manufacturing method as described in any one of said 8-11 in which at least 1 polymer selected from the group which consists of a polyimide precursor and polyimide has a photoreactive side chain further.

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

[Formula 3]

(Wherein, X ¹ and X ² each independently represent a bonding group selected from an ether bond and an ester bond, and S ¹ and S ² each independently represent a linear alkylene group having 2 to 9 carbon atoms; Further, S ¹ , X ¹ , X ² and S ² are selected such that the molecule is left-right asymmetric.)

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

15. In formula (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 X ² is an oxygen atom side. The polymerizable compound according to 13 or 14, which is an ester group bonded to S ² .

ADVANTAGE OF THE INVENTION According to this invention, by containing in a liquid crystal aligning agent and/or a liquid crystal layer, a liquid crystal aligning agent containing a novel polymerizable compound capable of providing a liquid crystal display element having a fast response speed and excellent afterimage characteristics derived from AC, The liquid crystal aligning film formed using this liquid crystal aligning agent and the response speed are fast, and the element of a vertical alignment system is obtained especially.

<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 as described above, respectively. Especially, S ¹ and S ² are each independently preferably a linear alkylene group having 2 to 6 carbon atoms.

Preferred methods for making S ¹ , X ¹ , X ² and S ² so that the molecules are left-right asymmetric include a method in which S ¹ and S ² select an alkylene group having different carbon atoms from each other (Method 1), and X There is a method (method 2) for selecting a coupling group in which ¹ and X ² are left-right asymmetric with each other. 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 X ² is an ether bond and the other is an ester bond (Method 2-1), and an ester bond in which X ¹ is bonded to S ¹ on the carbonyl side. and a method in which X ² is an ester group bonded to S ² on the oxygen atom side (Method 2-2).

Among such compounds, a compound having an alkylene group having mutually different carbon atoms can be obtained by the production method described in International Patent Application Publication No. WO2012/002513. In addition, when 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 make it.

Further, as a method for making the molecule asymmetrical, in addition to the methods 1 to 2 described 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 so as to be asymmetrical (method 4), etc. there is

By selecting at least one method selected from the above method 1 and method 2, while the solubility of the polymerizable compound is improved, it has been found that the afterimage characteristic derived from AC is superior to the case where method 3 or method 4 is selected. . 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 characteristic derived from AC. , it is thought that this is because stacking is not inhibited.

<Polyimide precursor and/or polymer from polyimide>

In the liquid crystal display element formed by being contained in the liquid crystal aligning agent and/or the liquid crystal layer, as at least one polymer (hereinafter also referred to as a specific polymer) selected from the group consisting of a polyimide precursor and polyimide preferably used, A well-known polyimide precursor or polyimide used as a liquid crystal aligning agent can be used. In addition, with a polyimide precursor, a polyamic acid and polyamic acid ester are contained specifically,.

The polyimide precursor or polyimide, which is a specific polymer, preferably has a side chain (I) that vertically aligns liquid crystals for use in PSA type liquid crystal displays, and vertically aligns liquid crystals for use in 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 orients the liquid crystal vertically>

The side chain (I) (hereinafter also referred to as side chain A) that vertically aligns liquid crystals is a side chain that has the ability to align 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 a side chain, for example, a long-chain alkyl group, a fluoroalkyl group, a cyclic group having an alkyl group or a fluoroalkyl group at the terminal, a steroid group, etc. are known, and are preferably used also in the present invention. These groups may be directly bonded to the main chain of a specific polymer as long as they have the above ability, or may be bonded through an appropriate bonding group.

As for side chain A, what is represented by following formula (a) is mentioned, for example.

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, R ⁵ is a hydrogen atom, an alkyl group of 1 to 24 carbon atoms, an alkoxy group of 1 to 24 carbon atoms, and fluorine of 1 to 24 carbon atoms containing an alkyl group, a fluorine-containing alkoxy group of 1 to 24 carbon atoms, a fluorine group, a cyano group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, a hydroxyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a compound thereof Represents a heterologous substituent.

[Formula 5]

As R ¹ , from the viewpoint of ease of synthesis, -O-, -COO-, -CONH-, or a C1-C3 alkylene-ether group is preferable.

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

When at least one of l, m, and n is 1, R ⁵ is preferably a hydrogen atom, an alkyl group of 2 to 14 carbon atoms, or a fluorine-containing alkyl group of 2 to 14 carbon atoms, more preferably a hydrogen atom or a carbon atom of 2 to 14 carbon atoms. It is an alkyl group of 12 or a fluorine-containing alkyl group of 2 to 12 carbon atoms. Further, when l, m and n are all 0, R ⁵ is preferably an alkyl group of 12 to 22 carbon atoms, a fluorine-containing alkyl group of 12 to 22 carbon atoms, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a group consisting of them. It is a release type substituent, More preferably, it is a C12-C20 alkyl group or a C12-C20 fluorine-containing alkyl group.

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

As quantity of side chain A in a specific polymer, it will not specifically limit, if a liquid crystal aligning film can orientate a liquid crystal vertically. However, in the liquid crystal display element provided with a liquid crystal aligning film, when trying to make the response speed of a liquid crystal faster, it is preferable that content of the side chain A is as small as possible within the range which can maintain vertical alignment.

<Photoreactive side chain (II)>

The photoreactive side chain (II) (hereinafter also referred to as side chain B) is a crosslinkable side chain having a functional group (hereinafter also referred to as a photocrosslinking group) capable of forming a covalent bond by reacting with ultraviolet irradiation. Or, it is an optical radical generating side chain having a functional group that generates a radical by ultraviolet irradiation, and the structure is not limited as long as it has this ability.

As such a side chain, for example, the side containing a vinyl group, an acryl 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, as structures that generate radicals by ultraviolet irradiation, acylphosphine oxide structure, acetophenone structure, alkylphenone structure, anthraquinone structure, carbazole structure, xanthone structure, thioxanthone structure, triphenylamine structure, fluorine 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. Especially, the side chain which has an acetophenone structure, a benzophenone structure, or a benzoin structure is preferable.

These groups may be bonded directly to the main chain of a specific polymer, or bonded through an appropriate bonding group, as long as they have the above ability.

As side chain B, following formula (b-1) - (b-3) can be illustrated, for example. Moreover, the side chain represented by formula (b-2) has a structure which has a cinnamoyl group and a methacryl group, and the side chain represented by formula (b-3) has a structure which 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, as R ⁶ , -CH ₂ -, -O-, -COO-, -NHCO-, -NH- or -CH ₂ O- is preferable.

R ⁷ represents a cyclic, unsubstituted or fluorine-substituted alkylene group having 1 to 20 carbon atoms, and any -CH ₂ - in the alkylene group is substituted with -CF ₂ - or -CH=CH- or, 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.

Although the following structures are specifically mentioned as a carbon ring and a heterocyclic ring, It is not limited to this.

[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 carbocyclic ring, or a heterocyclic ring. From the viewpoint of ease of synthesis, -CH ₂ -, -O-, -COO-, -OCO-, NHCO-, -NH-, a carbon ring, or a heterocyclic ring is preferable. Specific examples of the carbon ring and the heterocyclic ring are as described above.

R ⁹ is a styryl group, -CR ¹⁸ =CH ₂ group, a carbocyclic ring, a heterocyclic ring, or the following formulas (R9-1) to (R9-34), and even if R ¹⁸ is 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, as R ⁹ , a styryl group, -CH=CH ₂ , -C(CH ₃ )=CH ₂ , or the above (R9-2), (R9-12) or (R9-15 ) is more preferred.

[Formula 12]

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

R ¹¹ is an alkylene group having 1 to 30 carbon atoms, a divalent carbon ring, or a divalent heterocyclic ring, and one or more hydrogen atoms of the alkylene group, the divalent carbocyclic ring, and the divalent heterocyclic ring may be substituted with a fluorine atom or an organic group. do. Optional -CH ₂ - in R ¹¹ may be substituted with any of the groups listed below, if they are not adjacent to each other; -O-, -NHCO-, -CONH-, or -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 photocrosslinking group.

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

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

Although the following structures are mentioned as a specific example of the group represented by ^-R13 - ^R14 - ^R15 among the side chains represented by Formula (b-2), it is not limited to these. In addition, in the following structure, 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, and these groups may be substituted with organic groups, and the hydrogen atoms of these groups are halogen atoms. 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, and in the case of an alkyl group or an alkoxy group, R ₁₆ and R ₁₇ form a ring 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 ) -, -CON(CH ₃ )- or -N(CH ₃ )CO- group.

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 - in the alkylene group is optionally -CH=CH- It may be substituted, and in the case where any group illustrated below is not adjacent to each other, it may be substituted with any of these groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH- , a divalent carbon ring, or a divalent heterocyclic ring.).

n2 represents 0 or 1; Q represents a structure represented by the following formula.

[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-)

As a specific example of the group represented by -Ar ₄ -CO-CQR ¹⁶ R ¹⁷ in the side chain represented by the formula (b-3), the structures of the following formulas (b-3-1) to (b-3-6) Although exemplified, it is not limited to these.

[Formula 16]

The quantity of side chain B in a specific polymer will not be specifically limited if it is the range which can speed up the response speed of the liquid crystal in a liquid crystal display element. When intending to speed up the response speed of the liquid crystal in a liquid crystal display element, it is preferable to have as many as possible within the range which does not affect other characteristics.

<Polyimide precursor>

A polyimide precursor means a polyamic acid and polyamic acid ester. Hereinafter, although the preparation method concerning a polyamic acid is described, polyamic acid ester can be prepared by the conventionally well-known method, or the method same as or similar to the polyamic acid described below.

<Polyamic acid>

The polyamic acid having side chain A can be obtained by reacting the raw material when either diamine and tetracarboxylic acid anhydride as raw materials have side chain A or both have side chain A. Among these, a method using a diamine having side chain A is preferable from the viewpoint of easiness of raw material synthesis and the like.

Further, in the polyamic acid having side chains A and B, only one of diamine and tetracarboxylic anhydride as a raw material has side chain A and side chain B, or either one has only side chain A, Further, the other side has only side chain B, one side has side chain A and side chain B, and the other side has side chain A, either side chain A and side chain B are present, and the other side chain It can obtain by having chain B or making the raw material react because both sides have side chain A and side chain B. Among these, it is preferable that the side chain A and the side chain B are contained only in diamine from the viewpoint of ease of synthesis of raw materials and the like.

<Diamine having side chain A>

Examples of the diamine having side chain A (hereinafter, referred to as diamine A) include diamine having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a macrocyclic substituent composed of them in the diamine side chain. can Diamine which has a side chain specifically, represented by the said formula (a) is mentioned. More specifically, although diamine represented by following formula (1), (3), (4), (5) is mentioned, it is not limited to this. In addition, the definition of l, m, n, and R1- ^R5 in formula ( ¹ ) is the same as that of the said 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 a side chain A, and a' represents an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or any structure selected from these. 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-* (provided that the bond attached with "*" bonds to A ₃ ), and A ₁₇ is an oxygen atom, or -COO-* (provided, the bond attached with "*" is bonded to A 3 ) It combines with (CH ₂ )a ₂ ). Further, a ₁ is 0 or an integer of 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.)

The bonding position of the two amino groups (-NH ₂ ) in Formula (1) is not limited. Specifically, with respect to the bonding group of 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 can be heard Especially, from a reactive viewpoint at the time of synthesize|combining a polyamic acid, the position of 2 and 4, the position of 2 and 5, or the position of 3 and 5 are preferable. If the ease at the time of synthesize|combining diamine is also taken into consideration, the position of 2 and 4 or the position of 3 and 5 is more preferable.

As a specific structure of formula (1), although diamine represented by following formula [A-1] - formula [A-24] can be illustrated, it is not limited to this.

[Formula 19]

[Formula 20]

[Formula 21]

In formula [A-1] - formula [A-5], _A1 is a C2-C24 alkyl group or a C2-C24 fluorine-containing alkyl group.

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

In the formulas [A-8] to [A-10], A ₄ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O Represents -, -OCH ₂ -, or -CH ₂ -, and A ₅ is an alkyl group of 1 to 22 carbon atoms, an alkoxy group of 1 to 22 carbon atoms, a fluorine-containing alkyl group of 1 to 22 carbon atoms, or a fluorine-containing group of 1 to 22 carbon atoms. 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 formula [A-13] and formula [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 a trans isomer.

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

[Formula 25]

[Formula 26]

[Formula 27]

Although diamine represented by the following formula [A-25] - a formula [A-30] is mentioned as a specific example of the diamine represented by Formula (3), It is not limited to these.

[Formula 28]

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

Although diamine represented by the following formula [A-31] - a formula [A-32] is mentioned as a specific example of the diamine represented by Formula (4), It is not limited to these.

[Formula 29]

Among these, [A-1], [A-2], [A-3], [A-7], [A-14], [A-14], [A-1], [A-2], [A-14], [ The diamine of [A-16], [A-21], or [A-22] is preferable.

Said diamine can also be used in mixture of 1 type or 2 or more types according to characteristics, such as liquid-crystal orientation at the time of setting it as a liquid crystal aligning film, a pretilt angle, a voltage retention characteristic, and a stored electric charge.

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

<Diamine having side chain B>

As an example of the diamine having side chain B (hereinafter also referred to as diamine B), a vinyl group, an acryl group, a methacrylic group, an anthracenyl group, a cinnamoyl group, a carconyl group, a coumarin group, a maleimide group in the diamine side chain. , diamines having photocrosslinking groups such as stilbene groups, and diamines having functional groups that generate radicals upon irradiation with ultraviolet rays. Specifically, the diamine which has a side chain represented by the said formula (b-1) - (b-3) is 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 formula (b-1) above); , but is not limited to this.

[Formula 30]

The bonding position of the two amino groups (-NH ₂ ) in formula (2) is not particularly limited. Specifically, with respect to the bonding group of 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 can be heard Especially, from a reactive viewpoint at the time of synthesize|combining a polyamic acid, the position of 2 and 4, the position of 2 and 5, or the position of 3 and 5 are preferable. If the ease at the time of synthesize|combining diamine is also taken into consideration, the position of 2 and 4 or the position of 3 and 5 is more preferable.

Specifically, although the following compounds are mentioned, it is not limited to these. In addition, in the following compounds, X represents a bonding group selected from the group consisting of ether, ester, amide and amino, R represents a hydrogen atom or a methyl group, S ³ represents a single bond, or a carbon number unsubstituted or substituted by a fluorine atom. An alkylene group of 1 to 20 is shown. Moreover, l, m, and n represent the integer of 0-20 each independently.

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

The diamines described above are one type or a mixture of two or more depending on properties such as liquid crystal orientation when used as a liquid crystal aligning film, a pretilt angle, voltage retention characteristics, stored charge, etc., and the response speed of a liquid crystal when used as a liquid crystal display element. can also be used.

Among 100 mol% of the diamine component used for synthesis|combination of a polyamic acid, diamine B is 0-95 mol%, Preferably it is 20-80 mol%, More preferably, it is 40-70 mol%.

<Other diamines>

The polyamic acid used in the present invention is a diamine having a side chain that vertically aligns the liquid crystal or a diamine other than a diamine having a photoreactive group as a diamine component, as long as the effect of the present invention is not impaired. can be combined Specifically, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, and 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-dia Minonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl) Ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4aminophenyl)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-aminophenoxy) cy)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, bis(4-aminocyclohexyl) Alicyclic diamines such as methane and bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-dialysis Minohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-dia Aliphatic diamines, such as minododecane, are mentioned.

According to characteristics, such as liquid-crystal orientation at the time of setting it as a liquid crystal aligning film, a pretilt angle, a voltage retention characteristic, and a stored electric charge, said other diamine can also mix and use 1 type or 2 or more types.

<Tetracarboxylic dianhydride>

Synthesis of the polyamic acid used in the present invention WHEREIN: The said diamine component and the tetracarboxylic dianhydride made to react are not specifically limited. The specific example is 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-Anthracentetracarboxylic acid, 1,2,5,6-Anthracentetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4' -Biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)sulfone, bis (3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3 ,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylsilane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3,4,5-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, oxydiphthaltetracarboxylic 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-ene-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-tricarboxy Norbornane-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc. are mentioned.

One type or two or more types of tetracarboxylic dianhydride can be used together according to characteristics, such as liquid-crystal orientation at the time of setting it as a liquid crystal aligning film, a voltage retention characteristic, and a stored electric charge.

<Synthesis of polyamic acid>

When obtaining a polyamic acid by reaction of a diamine component and tetracarboxylic dianhydride, a well-known synthesis method can be used. Generally, it is the method of making a diamine component and tetracarboxylic dianhydride react 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 produce by-products.

As an organic solvent used for the said reaction, it will not specifically limit, if the produced|generated polyamic acid melt|dissolves. In addition, even if it is an organic solvent that does not dissolve the polyamic acid, you may mix it with the said solvent and use it within the range in which the produced|generated polyamic acid does not precipitate. In addition, since moisture in the organic solvent inhibits the polymerization reaction and consequently causes the produced polyamic acid to be hydrolyzed, it is preferable to use a dehydrated organic solvent.

As an organic solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N -Ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide , tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl Ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate , ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene Glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3- Methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butylate, 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 acetate, methyl pyruvate , Ethyl pyruvate, 3-methoxymethylpropionate, 3-ethoxymethylethylpropionate, 3-methoxyethylpropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropylpropionate, 3-methoxypropionic acid butyl, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol and the like. These organic solvents may be used alone or in combination.

When the diamine component and the tetracarboxylic dianhydride component are reacted 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 dispersed or dissolved in the organic solvent as it is or dissolved. Conversely, a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent, a method of adding tetracarboxylic dianhydride component and a diamine component alternately, and the like. Yes, and any of these methods may be used. In addition, when the diamine component or tetracarboxylic dianhydride component consists of plural types of compounds, they may be reacted in a premixed state, or may be reacted sequentially individually, or a mixture reaction of low molecular weight substances reacted separately to form a polymer. It can be done in bulk.

The temperature at the time of making the diamine component and tetracarboxylic dianhydride component react can select arbitrary temperature, For example, it is -20-150 degreeC, Preferably it is the range of -5-100 degreeC. In addition, the reaction can be carried out at an arbitrary concentration, for example, 1 to 50% by mass, preferably 5 to 30% by 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 selected according to the molecular weight of the polyamic acid to be obtained. Similar to a typical polycondensation reaction, the closer this molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced. As a preferable range, it is 0.8-1.2.

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

Examples of the method of imidizing the polyamic acid to obtain a polyimide include thermal imidation in which a solution of polyamic acid is heated as it is, and catalyst imidation in which a catalyst is added to a solution of polyamic acid.

In the polyimide used in the present invention, the imidation rate from the polyamic acid to the polyimide is not necessarily 100%.

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

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

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

<liquid crystal aligning agent>

The liquid crystal aligning agent of this invention contains the polymeric compound represented by said Formula (1), and the at least 1 polymer chosen from the group which consists of the said polyimide precursor and polyimide. Other than these components, you may contain other polymer components for forming a resin film. 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 the present invention may be at least one polymer selected from the group consisting of polyimide precursors and polyimides, all of which have side chains A and/or side chains B, or may be a mixture thereof. Furthermore, other polymers other than that may be mixed. In that case, the content of the other polymer in the resin component is preferably from 0.5 to 15% by mass, more preferably from 1 to 10% by mass.

As another polymer, although the polyimide precursor or polyimide which does not have side chain B, the polyimide precursor which does not have both side chain A and side chain B, or polyimide etc. are mentioned, for example, it is not limited to these .

The molecular weight of the polymer of the above resin component is the weight average molecular weight (Mw) measured by the GPC (Gel Permeation Chromatography) method when considering the strength of the obtained coating film, workability at the time of forming the coating film, and uniformity of the coating film 5,000 to 1,000,000 are preferred, and 10,000 to 150,000 are more preferred.

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 5-20 mass parts. 15 parts by mass. In the case of such content, the effect of this invention is acquired.

<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 a mixed solvent of two or more types. Specific examples of the organic solvent include the organic solvents exemplified in the above polyamic acid synthesis. 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 solvent as shown below has an effect of improving the uniformity and smoothness of the coating film, and is preferably used by mixing with a solvent having high solubility of the resin component.

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- Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butylate, butyl ether, diisobutyl ketone , methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate Ether, methyl pyruvate, ethyl pyruvate, 3-methoxymethylpropionate, 3-ethoxymethylethylpropionate, 3-methoxyethylpropionate, 3-ethoxypropionate, 3-methoxypropionate, 3-methoxypropylpropionate, 3 -Methoxybutyl propionate, 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, ethyl lactate ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, 2-ethyl-1-hexanol, and the like. These solvents may mix multiple types. 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 the above. For example, the compound which improves the film thickness uniformity or surface smoothness at the time of apply|coating a liquid crystal aligning agent, the compound which improves the adhesiveness of a liquid crystal aligning film, and a board|substrate, etc. are mentioned.

As a compound which improves the uniformity of film thickness and surface smoothness, a fluorochemical surfactant, silicone type surfactant, a nonionic surfactant, etc. are mentioned. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), Megapack F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Florad FC430, FC431 (manufactured by Sumitomo 3M) manufacture), Asahi Guard AG710, Suffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and the like. When using these surfactants, the usage ratio is preferably from 0.01 to 2 parts by mass, more preferably from 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, a functional silane containing compound, an epoxy group containing compound, etc. are mentioned. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidpropyltrimethoxysilane, 3-ureidpropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltri Ethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol di Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglyceride Cydyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclo Hexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3 -(N,N-diglycidyl) aminopropyltrimethoxysilane etc. are mentioned.

Moreover, 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 phenolic 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, as long as the effect of the present invention is not impaired, a dielectric or conductive material intended to change electrical properties such as dielectric constant or conductivity of the liquid crystal aligning film may be added.

<Liquid crystal alignment film>

After apply|coating the liquid crystal aligning agent of this invention to a board|substrate, you can also use the cured film obtained by making it dry and baking as needed as a liquid crystal aligning film as it is. In addition, this cured film is rubbed, irradiated with polarized light or light of a specific wavelength, treated with an ion beam or the like, or irradiated with UV as an alignment film for SC-PVA in a state in which a voltage is applied to a liquid crystal display element after liquid crystal charging. It is also possible to do

The substrate is not particularly limited as long as it is a substrate having high transparency, and is not particularly limited, but is a glass plate, polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, and polyolefin. , polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose, acetate butylate cellulose and the like can be used. In addition, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving the liquid crystal is formed, from the viewpoint of simplifying the process. In addition, in the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is only a substrate on one side, and a material that reflects light such as aluminum can also be used for the electrode in this case.

The coating method of the liquid crystal aligning agent is not particularly limited, and printing methods such as screen printing, offset printing, and flexographic printing, inkjet method, spray method, roll coating method, dip, roll coater, slit coater, spinner, etc. are exemplified. . In terms of productivity, the transfer printing method is widely used industrially, and is preferably used in the present invention as well.

The coating film formed by apply|coating a liquid crystal aligning agent by said method can be baked and used as a cured film. The drying step after applying the liquid crystal aligning agent is not necessarily necessary, but when the time from application to firing is not constant for each substrate, or when firing is not immediately after application, it is preferable to perform the drying step. . This drying is performed as long as the solvent is removed to such an extent that the coating film shape is not deformed by transport of the substrate or the like, 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 exemplified.

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, for example, 100 to 350 ° C., but is preferably 120 to 300 ° C., more preferably 150 to 250 ° C. is ℃. The firing time can be fired at an arbitrary time of 5 to 240 minutes. Preferably it is 10 to 90 minutes, More preferably, it is 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, or the like.

Moreover, although the thickness of the liquid crystal aligning film obtained by baking is not specifically limited, Preferably it is 5-300 nm, More preferably, it is 10-120 nm.

<Liquid crystal display element>

The liquid crystal display element of this invention can produce and obtain a liquid crystal cell by a well-known method, after forming a liquid crystal aligning film in a board|substrate by said method.

As a specific example of the liquid crystal display element, a liquid crystal cell having two substrates arranged so as to face each other, a liquid crystal layer formed between the substrates, and a liquid crystal alignment film formed between the substrate and the liquid crystal layer and formed of the liquid crystal aligning agent of the present invention. It is a liquid crystal display element of a vertical alignment system provided. Specifically, a liquid crystal aligning film is formed by applying the liquid crystal aligning agent of the present invention onto two substrates and firing them, arranging the two substrates so that the liquid crystal aligning films face each other, and forming a liquid crystal between the two substrates. It is a liquid crystal display element of a vertical alignment system provided with a liquid crystal cell produced by pinching the structured liquid crystal layer, bringing it into contact 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 of the liquid crystal aligning agent of the present invention, applying a voltage to the liquid crystal aligning film and the liquid crystal layer, irradiating ultraviolet rays to polymerize the polymerizable compound, and photoreactive side chains of the polymer, By making the photoreactive side chain of a polymer and a polymeric compound react, the orientation of a liquid crystal is fixed more efficiently and it becomes a liquid crystal display element remarkably excellent in response speed.

The substrate used for the liquid crystal display element of the present invention is not particularly limited as long as it is a substrate having high transparency, but is usually a substrate on which a transparent electrode for driving a liquid crystal is formed on the substrate. As a specific example, the thing similar to the board|substrate described with the said liquid crystal aligning film is mentioned.

Although the liquid crystal display element of this invention may use the board|substrate on which the conventional electrode pattern or projection pattern was formed, by having the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention, on one side board|substrate, for example, 1- Even if a substrate having a structure in which a 10 μm line/slit electrode pattern is formed and no slit pattern or projection pattern is formed on the counter substrate is used, the operation is possible, the process in manufacturing the liquid crystal display device can be simplified, and the high transmittance can be obtained.

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

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

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

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

Moreover, what is necessary is just to contain the polymeric compound of this invention in at least one of a liquid crystal aligning agent and the said liquid crystal layer, in order to manufacture the liquid crystal display element of this invention.

A well-known method is mentioned as a method of clamping this liquid crystal layer between two board|substrates. For example, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers such as beads on the liquid crystal alignment film of one substrate, and make the surface on the side on which the liquid crystal alignment film is formed turn inside, and the other one substrate The method of bonding together, injecting a liquid crystal under reduced pressure, and sealing is mentioned.

Moreover, after preparing a pair of board|substrate in which the liquid crystal aligning film was formed, and scattering spacers, such as a bead, on the liquid crystal aligning film of one board|substrate, liquid crystal was dripped and then the surface on the side in which the liquid crystal aligning film was formed turned inside. Then, a liquid crystal cell can be produced also by a method of bonding the other substrate together and sealing it. The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.

The process of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer is, for example, by applying a voltage between electrodes provided on the substrate, applying an electric field to the liquid crystal alignment film and the liquid crystal layer, A method of irradiating ultraviolet rays while maintaining this electric field is exemplified. 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/cm 2 , preferably 40 J/cm 2 or less, and more preferably 20 J/cm 2 or less. A smaller amount of ultraviolet irradiation is preferable because the decrease in reliability caused by destruction of the liquid crystal or members constituting the liquid crystal display element can be suppressed, and the irradiation time of ultraviolet rays can be reduced, thereby increasing the manufacturing efficiency.

300-400 nm is preferable and, as for the wavelength of the ultraviolet-ray to be used, 310-370 nm is more preferable.

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

Moreover, when an ultraviolet-ray is irradiated, applying a 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 Since the photoreactive side chains which it has, and the photoreactivity side chain which a polymer has, and a polymeric compound react, the response speed of the liquid crystal display element obtained can be sped up.

In addition, the liquid crystal aligning agent of the present invention is not only useful as a liquid crystal aligning agent for producing a liquid crystal display element of a vertical alignment system such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but also a rubbing treatment or an optical alignment treatment. It can be used suitably also for preparation of the liquid crystal aligning film formed by.

Example

Examples are given below to explain the present invention more specifically, but the present invention is not limited thereto. The symbol of the compound in the following is as follows.

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

CBDA: 1,2,3,4-cyclobutane tetracarboxylic 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: butyl cellosolve.

3AMP: 3-picorylamine.

[Formula 36]

<Synthesis Example 1>

[Formula 37]

<Synthesis of RM1-A>

At room temperature, in a 500 ml (milliliter) four-neck 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 charged, and NMP 10.0 g (0.5 wt) was added to the reaction solution while washing the wall surface of the flask, followed by stirring. Thereafter, the temperature was raised to 100°C, and 35.7 g (2.5 eq) of 4-chlorobutylaldehyde dimethylacetal and 10.0 g (0.5 wt) of NMP were poured into the reaction system while washing the powder adhering to the wall surface of the flask, and 18 It was stirred for an hour and reacted.

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 with 80.0 g (4 wt) of water 3 times. Then, it vacuum-dried at 50 degreeC, and the solvent was distilled off. 30.0 g (1.5 wt) of ethyl acetate was added to the residue, and the mixture was heated to 50°C to dissolve. Then, 140 g (7 wt) of heptane was added dropwise and 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 vacuum dried at 30°C to obtain 38.0 g of RM1-A (yield: 91%, property: 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 added to a 1 liter four-necked flask equipped with a magnetic stirrer, and after confirming that they were dissolved by stirring, tin chloride dihydrate 38.9 g (2.2 eq) and 33.4 g (2.2 eq) of 2-(bromomethyl) ethyl acrylate were sequentially charged, and the temperature was raised to 60°C. Then, after adding 125 g (3.6 wt) of 0.1 M hydrochloric acid dropwise, 245 g (7 wt) of THF was poured into the reaction system while washing off the powder adhering to the wall surface of the flask, and stirred for 14.5 hours to react.

The reaction liquid was cooled at 50 degreeC, 350 g (10 wt) of toluene was added and liquid-separated, and the hydrochloric acid layer was removed. After that, the organic layer was added dropwise to 263 g (7.5 wt) of a 50°C 12.9% by mass aqueous solution of potassium hydroxide over 30 minutes and stirred, then the organic layer was separated. After adding and stirring 262 g (7.5 wt) of 5.2 mass % potassium hydroxide aqueous solution to the obtained organic layer, it liquid-separated at 50 degreeC. To the separated organic layer, 3.49 g (10 wt%) of activated carbon was added, followed by stirring at 50°C for 30 minutes, followed by filtration 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 while 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%, property: 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 the mixture was 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-chlorobutylaldehyde dimethylacetal was added dropwise over 1 hour, and the mixture was stirred for 19.5 hours to react.

After the reaction liquid was added dropwise in 1600 g (20 wt) of water, it was stirred for 0.5 hour, and the precipitated solid was filtered. The filtrate was washed twice with 40.0 g (0.5 wt) of water. Then, the filtrate was dried under reduced pressure at 40°C for 1.5 hours. 880 g (11 wt) of methanol was added to the dried filtrate and stirred in a suspended state to wash crystals (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 resulting residue was subjected to slurry washing 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 of 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, and the mixture was cooled to 0°C to crystallize. To the precipitated solid, 400 g (5 wt) of methanol was added, the slurry was washed, and filtered. The filtrate was dried under reduced pressure at 40°C to obtain RM2-A 33.6 g (yield: 26%, property: white solid).

<Synthesis of RM2-B>

At room temperature, in a 500 ml four-necked flask equipped with a magnetic stirrer, RM2-A 33.6 g (111 mmol) and DMF 169 g (5 wt) were added, stirred to dissolve, and potassium carbonate 20.0 g (1.3 eq ) was added. Then, 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 react.

After the reaction liquid was added dropwise to 672 g (20 wt) of water, it was stirred for 0.5 hour and the precipitated solid was filtered. The filtrate was washed twice with 16.8 g (0.5 wt) of water. Then, the filtrate was vacuum dried at 40°C for 1.5 hours. Toluene 100g (3.0 wt) was added to the filtrate after drying, and it heated up and dissolved at 70 degreeC. Then, heptane 198g (6.0 wt) was dripped, it cooled to 0 degreeC, 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 degreeC, and RM2-B 35.6g was obtained (yield: 75%, property: white solid).

<Synthesis of RM2>

At room temperature, in a 1 L four-necked flask equipped with a magnetic stirrer, 50.0 g (116 mmol) of RM2-B and 500 g (10 wt) of THF were added, and after confirming that they were dissolved by stirring, tin chloride dihydrate 57.7 g (2.2 eq) and 49.3 g (2.2 eq) of 2-(bromomethyl) ethyl acrylate were sequentially charged, and the temperature was raised to 60°C. Then, 179 g (3.6 wt) of 0.1M hydrochloric acid was added dropwise, stirred for 26 hours, and made to react.

The reaction liquid was cooled at 50 degreeC, 500 g (10 wt) of toluene was added, and it separated and removed the hydrochloric acid layer. The organic layer was added dropwise over 30 minutes to 375 g (7.5 wt) of a 50°C 12.9% by mass aqueous solution of potassium hydroxide, and then the organic layer was separated. 375 g (7.5 wt) of 5.2 mass % potassium hydroxide aqueous solution was added to the organic layer, and liquid separation was carried out at 50 degreeC. The separated organic layer was washed with 375 g (7.5 wt) of water. Activated carbon 5.12g (10 wt%) was added to the washed organic layer, and after stirring at 50°C for 30 minutes, the mixture was 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 degreeC, and RM2 35.6g was obtained (yield: 83%, property: white crystal).

<Synthesis Example 3>

[Formula 39]

<Synthesis of RM3-A>

At room temperature, in a 500 ml four-necked flask equipped with a magnetic stirrer, 50.0 g (269 mmol) of 4,4'-biphenol and 175 g of DMF were charged, stirred to dissolve, and then 48.24 g (1.3 g) of potassium carbonate 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 react. Next, the reaction liquid was added dropwise into 1000 g of water and stirred at room temperature for 0.5 hour, then the precipitated solid was filtered. After adding 550 g of methanol to the filtrate and slurry washing at room temperature, it filtered at 0-5 degreeC. To the residue obtained by distilling off the solvent of the filtrate, 650 g of chloroform was added, followed by slurry washing at room temperature, followed by filtration. After adding and dissolving THF 15g to the residue from which the solvent of the filtrate was distilled off, 37.5 g of toluene was added and it stirred in an ice bath for 0.5 hour. The precipitated crystals were filtered, washed (toluene 12.5 g), and then dried under reduced pressure at 40°C to obtain 9.0 g of RM3-A (yield: 12%, property: gray crystals).

<Synthesis of RM3-B>

At room temperature, in a 500 ml four-necked flask equipped with a magnetic stirrer, 8.31 g (29 mmol) of RM3-A and 12.5 g of NMP were injected, 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 reaction was stirred for 19 hours. Next, 83 g of ethyl acetate was added in the reaction liquid, and the inorganic salt precipitated was filtered. After that, the filtrate was separated and washed three times with 24 g of water, and the solvent of the filtrate was distilled off. After adding 24 g of toluene to the obtained residue and dissolving at 70°C, 48 g of heptane was added and the mixture was stirred in an ice bath for a while. The precipitated crystals were filtered and dried under reduced pressure at 40°C to obtain 12.2 g of RM3-B (yield: 91%, property: white solid).

<Synthesis of RM3>

At room temperature, in a 500 ml four-necked flask equipped with a magnetic stirrer, 11.0 g (26.5 mmol) of RM3-B and 110 g of THF were charged, stirred to dissolve, and then 14.4 g (2.4 eq) of tin chloride dihydrate , and 49.3 g (2.2 eq) of 2-(bromomethyl)ethyl acrylate were sequentially added. Then, 38.5 g of 10 mass % hydrochloric acid was dripped and it was made to react for 120 hours. After the reaction solution was concentrated under reduced pressure to about 1/3, it was cooled to 15°C, and the precipitated crystals were filtered and washed (44 g of water 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 to 82.5 g of a 12.9% by mass potassium hydroxide aqueous solution at room temperature, and the aqueous layer was separated and removed. 82.5 g of 5.2 mass % potassium hydroxide aqueous solution was added to the obtained organic layer at room temperature, and the aqueous layer was separated and removed. Then, the organic layer was washed 5 times with 82.5 g of water, 0.55 g (5% by mass) of specially made white rose activated carbon was added, stirred at room temperature for 1 hour, and filtered. Then, the filtrate was concentrated under reduced pressure to about 15 g, and stirred at 5°C for a while. 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%, property: 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, in a 1 L four-necked flask equipped with a magnetic stirrer, 55.8 g (300 mmol) of 4,4'-biphenol, 62.7 g of 2-(4-bromobutyl)-1,3-dioxolane ( 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 wall surface of the flask. While washing the powder, it was poured into the reaction system. Then, it heated up at 60 degreeC, stirred for 41.5 hours, and made it react.

Then, after standing to cool to room temperature, the reaction liquid was dripped in 3013 g (54 wt) of water, and it stirred for 30 minutes. Subsequently, 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 and stirred to perform slurry washing. Then, it filtered and the obtained filtrate was concentrated. To the obtained residue, 725 g (13 wt) of chloroform was added and stirred to perform slurry washing. Then, the obtained filtrate was concentrated under reduced pressure. THF 72.5 g (1.3 wt) was added to the obtained residue, and heptane 273 g (4.9 wt) was added dropwise and cooled to 0°C. After filtering the precipitated solid and washing|cleaning with heptane, it was made to dry under reduced pressure and obtained RM6-A 31.6g (yield: 34%, property: white solid).

<Synthesis of RM6-B>

At room temperature, in a 500 ml four-neck flask equipped with a magnetic stirrer, RM6-A 19.7 g (62.6 mmol), potassium carbonate 43.1 g (5.0 eq), potassium iodide 1.04 g (10 mol%), and DMF 148 g ( 7.5 wt) was sequentially injected, stirred, and the temperature was raised to 100°C. Furthermore, 4.80 g (1.8 eq) of 4-chloro-1-butanol was added dropwise, stirred for 27 hours, and allowed to react. On the way, since the reaction became slow, 2.40 g (0.3 eq) of 4-chloro-1-butanol was added twice.

Then, 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 into 400 g (20 wt) of water to precipitate crystals. 197 g (10 wt) of THF was added to the obtained crystal, it was dissolved at 40°C, and 197 g (10 wt) of heptane was added dropwise to precipitate the crystal. Thereafter, 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%, property: light brown solid).

<Synthesis of RM6-C>

Under room temperature, after confirming that THF 155g (8.0 wt) was added to RM6-B 19.4g (50.3mmol) and dissolved while stirring, BHT 55.4mg (0.5mol%) and tin chloride dihydrate 20.4g (1.8eq ), and 17.5 g (1.8 eq) of 2-(bromomethyl)ethyl acrylate were sequentially injected. Then, it heated up at 60 degreeC, 0.1M hydrochloric acid 69.4g (3.6 wt) was dripped, and it stirred and made it react for 18 hours.

Then, after temperature-regulating at 50 degreeC, toluene 194g (10 wt) was added and liquid-separated. Although the organic layer was dripped at 150 g (7.5 wt) of 50 degreeC 12.9 mass % potassium hydroxide aqueous solution over 30 minutes, insoluble matter precipitated. Therefore, 637 g (32.8 wt) of 12.9% by mass potassium hydroxide aqueous solution was added to dissolve the insoluble matter, and then liquid separation was performed at 50°C. Subsequently, the separated organic layer was washed with 150 g (7.5 wt) of a 5.2% by mass aqueous solution of potassium hydroxide and further 150 g (7.5 wt) of water. To the washed organic layer, 2.00 g of activated carbon (specially made white roe, 10 wt%) was added, stirred at 50°C for 30 minutes, and filtered while hot. 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. Then, 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 degreeC, and RM6-C 3.2g was obtained (yield: 16%, property: white solid).

<Synthesis of RM6>

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

Then, 217 g (70 wt) of water was added, triethylamine hydrochloride was dissolved, and 208 g (67 wt) of toluene was further added to separate the liquid. The separated organic layer was washed twice with 151 g (49 wt) of water. Then, in order to avoid polymerization reaction, it distilled off under reduced pressure at 25 degreeC until the amount of solvent became 10 g (3.3 wt). After heptane 40.3g (13 wt) was dripped at the obtained residue, it cooled at 0 degreeC 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 degreeC, and RM6 2.4g was obtained (yield: 67%, property: white crystal).

In addition, hydrogen nuclear magnetic resonance ( ¹ HNMR) of the Synthesis Example was measured in a deuterated dimethyl sulfoxide (DMSO-d6) solvent using an NMR measuring instrument (JNDA Datum Co., Ltd., JNW-ECA500), and the chemical shift was It is expressed as a δ value (ppm) when tetramethylsilane is used as an internal standard.

<Measurement of molecular weight of polyimide>

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

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

Column temperature: 50 ℃,

Eluent: N,N'-dimethylformamide (As an additive, lithium bromide-hydrate (LiBr H ₂ O) is 30 mmol/L, phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran ( THF) is 10 ml / ℓ),

Flow rate: 1.0 ml/min;

Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weights of about 9000,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weights of about 12,000, 4,000, and 1,000) manufactured by Polymer Laboratories.

<Measurement of imidization rate>

20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Scientific Co., Ltd.), 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% by mass TMS mixture) was added, and ultrasonic waves were applied to completely dissolved 500 MHz proton NMR was measured for this solution with the NMR measuring machine (The JEOL datum company make, JNW-ECA500). For the imidation rate, a proton derived from a structure that does not change before and after imidation is determined 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. and obtained by the following formula. In addition, in the following formula, x is the proton peak integration value derived from the NH group of the amic acid, y is the peak integration value of the standard proton, and α is the NH of the amic acid in the case of polyamic acid (imidation rate is 0%) It is the ratio of the number of standard protons to one proton of the group.

Imidization 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 melt|dissolved and it was made to react at 60 degreeC for 3 hours. Then, CBDA (11.5 g, 58.6 mmol) and NMP (54.8 g) were added, and it was made to react at 40 degreeC for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (250g) and diluting to 6.5 mass %, acetic anhydride (46.4g) and pyridine (14.4g) were added as an imidation catalyst, and it was made to react at 70 degreeC for 3 hours. This reaction solution was injected|thrown-in to methanol (2900g), 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 A. The imidation ratio of this polyimide was 73%, Mn was 13000, and Mw was 39000.

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

<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); It was made to react at 60 degreeC for 3 hours. Then, PMDA (10.1 g, 46.3 mmol) and NMP (57.8 g) were added, and it was made to react at room temperature for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (250g) and diluting to 10 mass %, acetic anhydride (52.6g) and pyridine (40.8g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 4 hours. This reaction solution was injected|thrown-in to methanol (2900g), 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 B. The imidation rate of this polyimide was 77%, Mn was 12000, and Mw was 35000. Except having used the polyimide powder B (10.0g) instead of the polyimide powder A, it carried out similarly to the synthesis example 7, and obtained liquid crystal aligning agent B1.

<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. Then, CBDA (19.9 g, 101.5 mmol) and NMP (55.1 g) were added, and it was made to react at 40 degreeC for 12 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (250g) and diluting to 6.5 mass %, acetic anhydride (59.7g) and pyridine (18.5g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was injected|thrown-in to methanol (2900g), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder D. The imidation rate of this polyimide was 75%, Mn was 12000, and Mw was 32000. Except having used the polyimide powder D (10.0g) instead of the polyimide powder A, it carried out similarly to the synthesis example 7, and obtained the liquid crystal aligning agent D1.

<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. Then, CBDA (11.5 g, 58.6 mmol) and NMP (57.0 g) were added, and it was made to react at 40 degreeC for 12 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (250g) and diluting to 6.5 mass %, acetic anhydride (44.5g) and pyridine (13.8g) were added as an imidation catalyst, and it was made to react at 70 degreeC for 3 hours. This reaction solution was injected|thrown-in to methanol (2900g), 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 F. The imidation rate of this polyimide was 73%, Mn was 14000, and Mw was 38000. Except having used the polyimide powder F (10.0g) instead of the polyimide powder A, it carried out similarly to the synthesis example 7, and obtained the liquid crystal aligning agent F1.

<Synthesis Example 13>

30.0 g of liquid crystal aligning agent B1 obtained in synthesis example 8 was added to 70.0 g of liquid crystal aligning agent F1 obtained in synthesis example 12, and it stirred at room temperature for 5 hours to obtain liquid crystal aligning agent G1.

<Synthesis Example 14>

Dissolve 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) in NMP (163.7 g) and reacted at 60°C for 3 hours. Then, CBDA (11.5 g, 58.6 mmol) and NMP (54.6 g) were added, and it was made to react at 40 degreeC for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (250g) and diluting to 6.5 mass %, acetic anhydride (46.5g) and pyridine (14.4g) were added as an imidation catalyst, and it was made to react at 70 degreeC for 3 hours. This reaction solution was injected|thrown-in to methanol (2900g), 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 H. The imidation ratio of this polyimide was 74%, Mn was 16000, and Mw was 45000. Except having used the polyimide powder H (10.0g) instead of the polyimide powder A, it carried out similarly to the synthesis example 7, and obtained the liquid crystal aligning agent H1.

<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. Then, CBDA (1.74 g, 8.9 mmol) and NMP (8.3 g) were added, and it was made to react at room temperature for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (36g) and diluting to 6 mass %, acetic anhydride (4.0g) and pyridine (2.1g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (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 (44.0g) was added to the obtained polyimide powder I (6.0g), and it stirred and dissolved at 50 degreeC for 5 hours. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0g), and BCS (30.0g) were added to this solution, and it stirred at room temperature for 5 hours and obtained 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. Then, CBDA (2.27 g, 11.6 mmol) and NMP (11.5 g) were added, and it was made to react at room temperature for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (50g) and diluting to 6 mass %, acetic anhydride (5.3g) and pyridine (2.7g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (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 J. The imidation rate of this polyimide was 60%, Mn was 17000, and Mw was 35000. Except having used polyimide powder J (10.0g) instead of polyimide powder I, it carried out similarly to the synthesis example 15, and obtained liquid crystal aligning agent J1.

<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. Then, CBDA (1.43 g, 7.3 mmol) and NMP (7.8 g) were added, and it was made to react at room temperature for 10 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (36g) and diluting to 6 mass %, acetic anhydride (3.6g) and pyridine (1.9g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (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. Except having used polyimide powder K (10.0g) instead of polyimide powder I, it carried out similarly to the synthesis example 15, and obtained liquid crystal aligning agent K1.

(Example 1)

With respect to 10.0 g of liquid crystal aligning agent C1 obtained in synthesis example 9, 0.042 g (7 mass % with respect to solid content) of polymeric compound RM1 obtained in synthesis example 1 was added, stirred at room temperature for 3 hours to dissolve, liquid crystal aligning agent L1 prepared

(Example 2)

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

(Example 3)

Instead of polymeric compound RM1, liquid crystal aligning agent L3 was prepared by the method similar to Example 1 except having used RM2 obtained by the synthesis example 2.

(Example 4)

Instead of polymeric compound RM1, liquid crystal aligning agent L4 was prepared by the method similar to Example 1 except having used RM3 obtained by the synthesis example 3.

(Example 5)

Instead of liquid crystal aligning agent C1, liquid crystal aligning agent M1 was prepared by the method similar to Example 1 except having used liquid crystal aligning agent A1 obtained in the synthesis example 7.

(Example 6)

Liquid crystal aligning agent N1 was prepared by the method similar to Example 1 except having used liquid crystal aligning agent E1 obtained in the synthesis example 11 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 having used liquid crystal aligning agent G1 obtained in the synthesis example 13.

(Example 8)

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

(Example 9)

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

(Example 10)

Instead of liquid crystal aligning agent C1, liquid crystal aligning agent R1 was prepared by the method similar to Example 1 except having used liquid crystal aligning agent J1 obtained by the synthesis example 16.

(Example 11)

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

(Comparative Example 1)

Instead of polymeric compound RM1, liquid crystal aligning agent L5 was prepared by the method similar to Example 1 except having used RM4 obtained by the synthesis example 4.

(Comparative Example 2)

Instead of polymeric compound RM1, liquid crystal aligning agent L6 was prepared by the method similar to Example 1 except having used RM5 obtained by the synthesis example 5.

(Comparative Example 3)

Instead of polymeric compound RM1, liquid crystal aligning agent L7 was prepared by the method similar to Example 2 except having used RM5 obtained by the synthesis example 5.

(Comparative Example 4)

Instead of polymeric compound RM1, liquid crystal aligning agent L8 was prepared by the method similar to Example 1 except having used RM6 obtained by the synthesis example 6.

(Comparative Example 5)

Instead of polymeric compound RM1, liquid crystal aligning agent L9 was prepared by the method similar to Example 2 except having used RM6 obtained by the synthesis example 6.

<Manufacture 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.

The liquid crystal aligning agent L1 is spin-coated on the IZO surface of an IZO electrode substrate of 4 pixels on which an IZO electrode pattern (fish bone) having a pixel size of 87 μm × 89 μm and a line / space of 3 μm is formed, 80 It was made to dry for 90 second with the degreeC hot plate. Then, in a 200 degreeC hot-air circulation type oven, it baked for 20 minutes and formed the liquid crystal aligning film of 100 nm in film thickness.

Furthermore, the liquid crystal aligning agent L1 was spin-coated on the ITO surface of the ITO electrode substrate in which the electrode pattern was not formed, and it was made to dry with an 80 degreeC hot plate for 90 second. Then, it baked in a 200 degreeC hot-air circulation type oven for 20 minutes, and formed the liquid crystal aligning film with a film thickness of 100 nm.

About said two board|substrates, after spread|dispersing a 3.3 micrometer bead spacer on the liquid crystal aligning film of one board|substrate, the sealing compound (solvent-type thermosetting type epoxy resin) was printed from it. Then, after turning the surface of the other board|substrate on the side where the liquid crystal aligning film was formed inside, and bonding together with the previous board|substrate, the sealing compound was hardened and the empty cell was produced. Liquid crystal MLC-6608 (manufactured by Merck, Inc.) was injected into this empty cell by a vacuum injection method. Then, it put in a 120 degreeC hot-air circulation type oven for 1 hour, the liquid crystal reorientation process was performed, and the liquid crystal cell 1 was produced.

"Observation of a bright spot in a liquid crystal cell"

The luminescent point in the obtained liquid crystal cell 1 was observed by the following method. The liquid crystal cell 1 immediately after said reorientation process was left to stand at room temperature for 2 days, and the liquid crystal cell was observed under a polarization microscope after that. When the solubility of a polymeric compound to a liquid crystal is low, it is considered that it becomes easy to precipitate in a liquid crystal cell and a luminescent point arises. A case where a bright spot does not occur is regarded as good, and a case where a bright spot occurs is regarded as defective.

"Evaluation of afterimages derived from AC"

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

6 J/cm<2> of UV which passed through the 365 nm band-pass filter was irradiated from the outer side of this liquid crystal cell 1 in the state which applied the DC voltage of 15V to liquid crystal cell 1. In addition, the UV illuminance was measured using UV-MO3A manufactured by ORC. Thereafter, in a state where no voltage was applied, UV (UV lamp: FLR40SUV32/A-1) was irradiated for 30 minutes using a UV-FL irradiation device manufactured by Toshiba Lightec Co., Ltd. The polarizing film was affixed on both sides of the liquid crystal cell 1 in a crossed Nicols state so that the polarization axis of the polarizing film and the director of the liquid crystal formed 45 degrees. Of the four pixels, a rectangular wave of 30 Hz and 20 Vpp was applied to only one arbitrary pixel and one pixel on the opposite side thereof for 70 hours. After disconnecting the voltage, the electrodes of the liquid crystal cell were connected and shorted. Thereafter, this liquid crystal cell was placed on a backlight, and the luminance of the voltage-applied pixel and the non-voltage-applied pixel was visually compared. When the afterimage characteristic was good, it was considered that the difference in luminance between the voltage-applied pixel and the non-voltage-applied pixel was reduced, and the cells were observed from the front, and those in which the luminance difference could not be visually recognized were regarded as good, and those that could be visually recognized were regarded as poor.

"Measurement of pretilt angle"

In the preparation of the liquid crystal cell 1, instead of the 4-pixel IZO electrode substrate, an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm was formed was used, and 3.3 The liquid crystal cell 2 was produced by the method similar to preparation of the liquid crystal cell 1 except having used the 4 micrometer bead spacer instead of the micrometer bead spacer.

6 J/cm<2> of UV which passed through the 365 nm band pass filter was irradiated from the outer side of this liquid crystal cell 2 in the state which applied the DC voltage of 15V to the obtained liquid crystal cell 2. In addition, the UV illuminance was measured using UV-MO3A manufactured by ORC. Thereafter, UV (UV lamp: FLR40SUV32/A-1) was irradiated for 30 minutes using a UV-FL irradiation device (manufactured by Toshiba Lightex Co., Ltd.) in a state where no voltage was applied.

The pretilt angle of the pixel part after UV irradiation was measured using LCD analyzer LCA-LUV42A (made by Mayyo Technica).

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

Instead of liquid crystal aligning agent L1, except having used each liquid crystal aligning agent shown in Table 2, operation similar to Example 12 was performed, the liquid crystal cell was produced, and the said evaluation was performed about each liquid crystal cell. These results are collectively shown in Table 2.

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

Further, from the comparison between Examples 12, 14, and 15 and Comparative Examples 7 and 8, the method for asymmetricalization of the molecular structure of the polymerizable compound of the present invention (above-mentioned methods 1 and 2) is such that the benzene ring becomes asymmetrical. Compared with the method of introducing a substituent (Method 4), it can be seen that the afterimage characteristic derived from AC is excellent.

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

This is considered to be because the resulting polymer network is more rigid because the stacking of the cyclic structure is stronger than that of a methacrylic compound in which the polarization of the polymerizable group is not a cyclic structure.

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 liquid crystal display element of a vertical alignment system such as a PSA type liquid crystal display.

In addition, all the content of the Japanese Patent Application No. 2015-22123, the claim, and the abstract for which it applied on February 6, 2015 is referred here, and it takes in as an indication of the specification of this invention.

Claims (15)

delete delete delete delete delete delete delete delete delete delete delete delete A polymeric compound represented by the following formula (1).
[Formula 3]

(Wherein, X ¹ and X ² each independently represent a bonding group selected from an ether bond and an ester bond, and S ¹ and S ² each independently represent a linear alkylene group having 2 to 9 carbon atoms; Further, S ¹ , X ¹ , X ² and S ² are selected such that the molecule is left-right asymmetric.) According to claim 13,
In Formula (1), the polymeric compound which is an alkylene group in which ^S1 and ^S2 have mutually different carbon number. According to claim 13 or 14,
In Formula (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 X ² is S ² on the oxygen atom side. An ester bond bonded to, a polymerizable compound.