KR20160114645A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent which improves storage stability as a liquid crystal aligning agent containing a polymerizable compound which improves solubility in a liquid crystal aligning agent and solubility in a liquid crystal. The present invention relates to [I] a compound represented by any of the following general formulas I-1 to I-3: wherein Ar ₁ to Ar ₃ are each independently a divalent organic group containing an aromatic ring having at least one halogen substituent, n ₁ , n ₂ and n ₆ independently represent an integer of 0 to 6, n ₃ , n ₄ and n ₅ each independently represent an integer of 1 to 6, and R ₁ to R ₃ each independently Represents a hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms), at least one polymerizable compound selected from the group consisting of compounds represented by the following formula: And [II] at least one polymer selected from polyimide precursors and polyimides; And a liquid crystal aligning agent.
[Chemical Formula 1]

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment material, a liquid crystal alignment film, and a liquid crystal display device,

The present invention relates to a liquid crystal aligning agent which can be used for producing a liquid crystal display element produced by irradiating ultraviolet rays while applying a voltage to liquid crystal molecules, a liquid crystal alignment film formed with the liquid crystal aligning agent, To a liquid crystal display element.

Among the liquid crystal display elements of the system (also called the vertical alignment (VA) system) in which the liquid crystal molecules vertically aligned with respect to the substrate are caused to respond by an electric field, there is a process of irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules .

In such a vertical alignment type liquid crystal display device, a photopolymerizable compound is added in advance to a liquid crystal composition and used together with a vertical alignment film such as polyimide to irradiate ultraviolet light while applying a voltage to the liquid crystal cell, (See, for example, Patent Document 1 and Non-Patent Document 1) are known (Polymer sustained Aligment (PSA) type liquid crystal display).

Generally, the direction in which the liquid crystal molecules are tilted in response to an electric field is controlled by protrusions formed on the substrate or slits formed on the display electrodes, etc. However, when a voltage is applied to the liquid crystal cell by adding a photopolymerizable compound to the liquid crystal composition Since the polymer structure in which the direction in which the liquid crystal molecules are tilted is formed on the liquid crystal alignment film by irradiating ultraviolet rays, the response speed of the liquid crystal display device is lower than that in the method of controlling the tilt direction of the liquid crystal molecules by only the projections or slits It is known to accelerate.

It has also been reported that the response speed of a liquid crystal display element is also improved by adding a photopolymerizable compound to a liquid crystal alignment film not in a liquid crystal composition (SC-PVA type liquid crystal display) (see, for example, Non-Patent Document 2 ).

Japanese Unexamined Patent Application Publication No. 2003-307720.

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

However, it is desired to further increase the response speed of the liquid crystal display element. Here, it is conceivable to increase the response speed of the liquid crystal display element by increasing the addition amount of the photopolymerizable compound. However, the conventional photopolymerizable compound has a property of being insoluble in the solvent or liquid crystal used in the liquid crystal aligning agent . Therefore, there arises a problem of storage stability that the photopolymerizable compound precipitates when the liquid crystal aligning agent is stored. In addition, when the liquid crystal display element is exposed to a temperature change during its manufacturing process, a part of the polymerizable compound may elute into the liquid crystal from the liquid crystal alignment film, or crystallize in the liquid crystal in some cases. In particular, when the solubility of the polymerizable compound in the liquid crystal is low, it is considered that crystallization in the liquid crystal tends to occur easily. Such crystallization of the polymerizable compound in the liquid crystal becomes a source of light in the display element, leading to a decrease in display quality of the element. Further, when the unpolymerizable photopolymerizable compound remains, it becomes an impurity, which may cause the reliability of the liquid crystal display element to deteriorate. For example, there is a possibility that the liquid crystal display element may be stretched or a residual image may appear, which may degrade display quality.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-described problems of the prior art.

Specifically, it is an object of the present invention to provide a liquid crystal aligning agent having improved storage stability as a liquid crystal aligning agent containing a polymerizable compound having improved solubility in liquid crystal aligning agent and solubility in liquid crystal.

It is also an object of the present invention to provide a liquid crystal alignment film having the liquid crystal aligning agent and a liquid crystal display element having the liquid crystal alignment film.

The present inventors have found the following inventions.

≪ 1 > [I] In general formulas I-1 to I-3

(Wherein Ar ₁ to Ar ₃ are each independently a divalent organic group containing an aromatic ring having at least one halogen substituent, and n ₁ , n ₂ and n ₆ are each independently 0 to 6 N ₃ , n ₄ and n ₅ each independently represent an integer of 1 to 6, and R ₁ to R ₃ each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, which is a linear or branched chain, )

At least one polymerizable compound selected from the group consisting of compounds represented by the following formula:

And

[II] at least one polymer selected from polyimide precursors and polyimides;

And a liquid crystal aligning agent.

[Chemical Formula 1]

≪ 2 > A compound according to < 2 >, wherein Ar ₁ to Ar ₃ each independently represent a group represented by any one of formulas IB-1 to IB-3 wherein X is a halogen group, m ₁ to m ₈ are independently integers , m ₁ + m ₂ is 1 or more and 8 or less, m ₃ + m ₄ + m ₅ is 1 or more and 10 or less, and m ₆ + m ₇ + m ₈ is 1 or more and 12 or less) Is preferably an organic group.

(2)

The group represented by formula IB-1 is preferably represented by formula IB-1a, the group represented by formula IB-2 is preferably represented by formula IB-2a, The group represented by formula IB-3 is preferably represented by formula IB-3a.

(3)

≪ 4 > The liquid crystal display according to any one of < 1 > to < 3 >, wherein the polymer [II] comprises: (I) .

≪ 5 > The positive resist composition according to < 5 >, wherein the polymer [II] .

≪ 6 > A liquid crystal alignment layer formed by the liquid crystal aligning agent of any one of < 1 > to < 5 >

≪ 7 > a liquid crystal display element having the liquid crystal alignment layer of the above < 6 >.

According to the present invention, it is possible to provide a liquid crystal aligning agent having improved storage stability as a liquid crystal aligning agent containing a polymerizable compound having improved solubility in a liquid crystal aligning agent and solubility in a liquid crystal.

Further, according to the present invention, it is possible to provide a liquid crystal alignment film having the liquid crystal aligning agent and a liquid crystal display element having the liquid crystal alignment film.

Hereinafter, the invention described in this application will be described in detail.

The present invention provides a liquid crystal aligning agent containing a polymerizable compound that improves solubility in a liquid crystal aligning agent and solubility in a liquid crystal.

The present invention also provides a liquid crystal alignment film having the liquid crystal aligning agent and a liquid crystal display element having the liquid crystal alignment film.

Hereinafter, a liquid crystal alignment agent, a liquid crystal alignment layer formed with the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment layer will be described in this order.

<Liquid Crystal Aligner>

The present invention provides a liquid crystal aligning agent containing a polymerizable compound that improves solubility in a liquid crystal aligning agent and solubility in a liquid crystal.

The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent comprising: [I] at least one polymerizable compound selected from the group consisting of the compounds represented by the following general formulas I-1 to I-3; And [II] at least one polymer selected from polyimide precursors and polyimides; Lt; / RTI &gt;

In the general formulas I-1 to I-3, Ar ₁ to Ar ₃ are each independently a divalent organic group containing an aromatic ring having at least one halogen substituent, n ₁ , n ₂ and n ₆ are Independently represent an integer of 0 to 6, n ₃ , n ₄ and n ₅ each independently represent an integer of 1 to 6, and R ₁ to R ₃ each independently represent hydrogen or a straight chain having 1 to 4 carbon atoms Chain or branched chain alkyl group.

[Chemical Formula 4]

<< [I] Polymerizable compound >>

The liquid crystal aligning agent of the present invention is at least one polymerizable compound selected from the group consisting of [I] the compounds represented by the above-mentioned general formulas I-1 to I-3; Lt; / RTI &gt;

Ar ₁ to Ar ₃ in the general formulas I-1 to I-3 each independently represent a group represented by the following formulas IB-1 to IB-3 wherein X represents a halogen group, m ₁ to m ₈ each independently represents an integer , m ₁ + m ₂ is less than 1, preferably less than or equal to 8, greater than or equal to 1 4, m ₃ + m ₄ + m ₅ is less than or equal to 10, greater than or equal to 1, and preferably not less than 1 but not more than 6 and also m ₄ + m ₅ Is 2 or less, and m ₆ + m ₇ + m ₈ is 1 or more and 12 or less, preferably 1 or more and 4 or less).

In the liquid crystal aligning agent of the present invention, one kind of polymerizable compound may be used, and plural kinds of polymerizable compounds may be used if necessary.

The amount of the polymerizable compound is preferably from 1 to 30 mass%, more preferably from 3 to 20 mass%, and still more preferably from 5 to 15 mass%, based on the solid content in the liquid crystal aligning agent.

[Chemical Formula 5]

Specific examples of the divalent groups represented by the formulas IB-1 to IB-3 include groups represented by the following formulas, but are not limited thereto.

[Chemical Formula 6]

(7)

As the bivalent groups represented by the formulas IB-1 to IB-3, the following groups are preferred. That is, the group represented by formula IB-1 is preferably a group represented by formula IB-1a, the group represented by formula IB-2 is preferably a group represented by formula IB-2a, Is preferably a group represented by the following formula (IB-3a).

[Chemical Formula 8]

&Lt; [II] At least one polymer selected from polyimide precursor and polyimide &gt;

[II] The at least one polymer selected from the polyimide precursor and polyimide may be a conventionally known or later-known polyimide precursor or polyimide used for the liquid crystal aligning agent. The polyimide precursor is specifically meant to include polyamic acid and polyamic acid ester.

[II] A polyimide precursor or polyimide for a PSA type liquid crystal display, comprising: (I) a side chain for vertically orienting a liquid crystal; .

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

(I) A side chain for vertically orienting a liquid crystal (hereinafter, also referred to as a side chain A) is a side chain having an ability to align liquid crystal molecules perpendicularly to a substrate, and the structure is not limited as long as it has this capability . Examples of such side chains include long-chain alkyl groups and fluoroalkyl groups, cyclic groups having alkyl or fluoroalkyl groups at the ends, steroid groups, and the like, and they are preferably used in the present invention. These groups may be bonded directly to the main chain of the polyimide precursor or polyimide, or may be bonded through a suitable bonding group, as long as they have the above-mentioned capabilities.

The side chain A may be, for example, one represented by the following formula (a).

In formula (a), l, m and n each independently represent an integer of 0 or 1, R ¹ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, R ² , R ³ and R ⁴ each independently represent a phenylene group or a cycloalkylene group, R ⁵ represents a hydrogen atom, an alkylene group having 1 to 3 carbon atoms, An alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a polycyclic substituent composed of them.

[Chemical Formula 9]

R ¹ in the formula (a) is an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH- or an alkylene-ether having 1 to 3 carbon atoms Lt; / RTI &gt; Of these, from the viewpoint of ease of synthesis, -O-, -COO-, -CONH- and an alkylene-ether group having 1 to 3 carbon atoms are preferable.

R ² , R ³ and R ⁴ in formula (a) each independently represent a phenylene group or a cycloalkylene group. A combination of l, m, n, R ² , R ³ and R ⁴ shown in the following table is preferable from the viewpoints of ease of synthesis and ability to orient the liquid crystal vertically.

R ⁵ in the formula (a) represents a hydrogen atom or an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a polycyclic substituent composed of them. When at least one of l, m and n is 1, the structure of R ⁵ is preferably a hydrogen atom or an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, more preferably a hydrogen atom or a hydrocarbon group having 2 to 14 carbon atoms, Lt; / RTI &gt; alkyl group or a fluorine-containing alkyl group.

When l, m and n are all 0, the structure of R ⁵ is preferably an alkyl group or a fluorine-containing alkyl group having 12 to 22 carbon atoms, an aromatic ring, an aliphatic ring, a heterocyclic ring or a polycyclic substituent More preferably an alkyl group having 12 to 20 carbon atoms or a fluorine-containing alkyl group.

The ability to align the liquid crystal vertically differs depending on the structure of the side chain A described above. Generally, the larger the amount of the side chain A contained in the polymer, the higher the ability to vertically align the liquid crystal, and the lower it becomes. Further, the side chain A containing the cyclic structure tends to align the liquid crystal vertically even with a small content, as compared with the side chain A of the long chain alkyl group.

The amount of side chain A present in the polyimide precursor or polyimide used in the present invention is not particularly limited as long as the liquid crystal alignment film can orient the liquid crystal vertically. However, in the liquid crystal display device having the above-described liquid crystal alignment film, when the response speed of the liquid crystal is to be made faster, the amount of the side chain A present is preferably as small as possible within a range in which the vertical alignment can be maintained.

[II] The polyimide precursor or polyimide is for a SC-PVA type liquid crystal display, and is a side chain for vertically orienting the liquid crystal (I) described above; (II) photoreactive side chains; .

&Lt; (II) Side chain of photoreactive &gt;

The photoreactive side chain (hereinafter also referred to as side chain B) refers to a crosslinkable side chain having a functional group capable of reacting by irradiation with ultraviolet light to form a covalent bond (hereinafter also referred to as a photo crosslinking group) The side chain is a side of an optical radical generating side having a functional group capable of generating a radical by irradiation with ultraviolet rays.

Among such side chains, for example, a side chain containing a vinyl group, an acryl group, a methacryl group, an anthracenyl group, a cinnamyl group, a carnonyl group, a coumarin group, a maleimide group, Are known, and they are preferably used in the present invention. Further, a specific structure that generates a radical by ultraviolet irradiation is also preferably used. These groups may be bonded directly to the main chain of the polyimide precursor or polyimide, or may be bonded through a suitable bonding group, as long as they have the above-mentioned capabilities.

The side chain B may be represented by, for example, the following formulas (b-1) to (b-3). The group represented by the formula (b-2) has a structure having a cinnamoyl group and a methacryl group, and the group represented by the formula (b-3) has a structure that generates radicals by ultraviolet irradiation. In the formula, Ar ₄ , Q, R ⁶ to R ¹⁷ , S, T ₁ and T ₂ will be described later.

[Chemical formula 10]

In formula (b-1), R ⁶ represents -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ ) -, -CON (CH ₃ ) -, -N (CH ₃ ) CO-, and R ⁷ represents a cyclic, unsubstituted or fluorine-substituted alkylene , In which arbitrary -CH ₂ - of alkylene may be substituted with -CF ₂ - or -CH═CH-, and in the case where any of the groups shown below are not adjacent to each other, these groups may be substituted ; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a carbon ring, a heterocyclic ring. R ⁸ is _{-CH 2 -, -O-, -COO-,} -OCO-, -NHCO-, -NH-, -N (CH 3) -, -CON (CH 3) -, -N (CH 3) CO-, a carbon ring, or a heterocyclic ring, and R ⁹ represents a vinylphenyl group, a -CR ¹⁰ ═CH ₂ group, a carbon ring, a heterocyclic ring or a structure represented by the following formulas R9-1 to R9-34, R ¹⁰ represents a hydrogen atom or a methyl group which may be substituted with a fluorine atom.

(11)

[Chemical Formula 12]

[Chemical Formula 13]

In formula (b-1), R ⁶ represents -CH ₂ -, -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ ) -, and -N (CH ₃ ) CO-. These coupling groups can be formed by a common organic synthetic method, but from the viewpoint of ease of synthesis, -CH ₂ -, -O-, -COO-, -NHCO-, -NH-, -CH ₂ O- are preferable Do.

In the formula (b-1), R ⁷ represents an alkylene of 1 to 20 carbon atoms which is substituted by a cyclic, unsubstituted or fluorine atom, wherein any -CH ₂ - of the alkylene is -CF ₂ - Or -CH = CH-, and in the case where any of the groups shown below are not adjacent to each other, they may be substituted with these groups; -O-, -COO-, -NHCO-, -NH-, a carbon ring, a heterocyclic ring.

Specific examples of the carbon ring and the heterocyclic ring include the following structures, but the present invention is not limited thereto.

[Chemical Formula 14]

In formula (b-1), R ⁸ represents -CH ₂ -, -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, _{-OCO-, -CON (CH 3) -} , -N (CH 3) CO-, a carbon ring, and coupler is selected from the heterocyclic ring. Among them, it is preferably -CH ₂ -, -O-, -COO-, -OCO-, NHCO-, -NH-, a carbon ring or a heterocyclic ring from the viewpoint of ease of synthesis. Specific examples of the carbon ring and the heterocyclic ring are as described above.

In the formula (b-1), R ⁹ is a styryl group, -CR ¹⁰ = CH _2, carbon ring, represents a heterocyclic ring or a structure represented by the formula R9-1 ~ R9-31, R ¹⁰ is a hydrogen atom or a fluorine atom Or a methyl group which may be substituted.

Among them, from the viewpoint of photoreactivity, it is more preferable that R ⁹ is styryl, -CH = CH ₂ , -C (CH ₃ ) = CH ₂ , or R 9-2, R 9-12 or R 9-15.

[Chemical Formula 15]

In formula (b-2), R ¹⁰ represents a group selected from -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, and -CO-.

R ¹¹ is an alkylene group, a divalent carbon ring or a heterocyclic ring formed from 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group, divalent carbon ring or heterocyclic ring may be substituted with a fluorine atom or an organic group Or may be substituted. Further, R ¹¹ is, in the case of any group are not adjacent to each other, illustrated in the following, -CH ₂ - or may have been substituted with the foregoing; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-.

R ¹² represents any of -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, and single bond.

R ¹³ represents a photo-crosslinkable group such as a cinnamoyl group, a chalconic group, and a coumarin group.

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

R ¹⁵ represents a photopolymerizable group selected from an acryl group and a methacryl group.

Of the side chain represented by the formula (b-2), specific examples of the group represented by -R ¹³ -R ¹⁴ -R ¹⁵ include the following structures, but are not limited thereto. In the following structures, R represents a hydrogen atom or a methyl group.

[Chemical Formula 16]

[Chemical Formula 17]

In the formula (b-3), Ar ₄ represents an aromatic hydrocarbon group selected from phenylene, naphthylene and biphenylene, which may be substituted with an organic group, and the hydrogen atom may be substituted with a halogen atom.

R ₁₆ and R ₁₇ are each independently an alkyl group, an alkoxy group, a benzyl group or a phenethyl group having 1 to 10 carbon atoms, and in the case of an alkyl group or an alkoxy group, R ₁₆ and R ₁₇ may form a ring.

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

S represents an alkylene group having 1 to 20 carbon atoms (in which the -CH ₂ - or -CF ₂ - of the alkylene group is optionally substituted with -CH = CH-, which is unsubstituted or substituted by an unsubstituted or fluorine atom -OCO-, -OCO-, -NHCO-, -CONH-, -NH-, and divalent groups may be substituted with these groups in the case where any of the groups shown below are not adjacent to each other. Carbon ring, divalent heterocyclic ring).

Q represents a structure represented by the following formula (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-) .

[Chemical Formula 18]

Of the side chain represented by the formula (b-3), specific examples of the group represented by -Ar ₄ -CO-CQR ¹⁶ R ¹⁷ include the following structures, but are not limited thereto.

[Chemical Formula 19]

The amount of side chain B present is not particularly limited as long as the response speed of the liquid crystal in the liquid crystal display element can be increased. In the case where the response speed of the liquid crystal in the liquid crystal display element is to be made faster, it is preferable that the response speed is as large as possible within a range that does not affect other characteristics.

<Polyimide precursor>

As described above, the polyimide precursor is meant to include polyamic acid and polyamic acid ester. Hereinafter, in particular, polyamic acid is described in detail, but the polyamic acid ester can also be prepared by a conventionally known method or by the same or similar method as the polyamic acid described later.

<Polyamic acid>

The polyamic acid having the side chain A can be obtained by reacting the raw material either of the diamine and the tetracarboxylic acid anhydride having the side chain A or having both side chains A as the raw material. Of these, a method of using a diamine compound having a side chain A is preferable for ease of synthesis of raw materials and the like.

The polyamic acid having the side chain A and the side chain B can be obtained either when either one of the diamine and the tetracarboxylic acid anhydride as the raw material has the side chain A and the side chain B or only one side has the side chain A, Either side chain B alone or both side chain A and side chain B and the other side chain A, either side has side chain A and side chain B and the other side has side chain B , Or by reacting the raw material by having the side chain A and the side chain B in the both sides. Of these, a method using a diamine compound having a side chain A, a diamine compound having a side chain B, and a tetracarboxylic acid having no side chain A or side chain B is preferred for ease of raw material synthesis and the like.

Hereinafter, the diamine compound having the side chain A will be described, and then the diamine compound having the side chain B will be described.

&Lt; Diamine compound having side chain A &gt;

Examples of the diamine compound having a side chain A (hereinafter also referred to as diamine A) include diamines having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, . Specifically, diamines having a side chain represented by the above formula (a) can be mentioned. More specifically, examples thereof include diamines represented by the following formulas (1), (3), (4) and (5), but the present invention is not limited thereto. The definitions of 1, m, n and R ¹ to R ⁵ in the formula (1) are the same as those in the formula (a).

[Chemical Formula 20]

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

[Chemical Formula 21]

Equation (5) of, A ₁₄ is an alkyl group, having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₁₅ is 1,4-cyclohexyl, and xylene group, or a 1,4-phenylene group, A ₁₆ is (combines hand provided with an end, "*" is bonded and a ₃₎ an oxygen atom, -COO- or * a, a ₁₇ is a bond hand provided with an oxygen atom, -COO- or - (However, "*" (CH ₂ ) a ₂ ). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.)

The bonding position of two amino groups (-NH ₂ ) in the formula (1) is not limited. Specifically, with respect to the bonding group of the side chain, positions 2 and 3, positions 2 and 4, positions 2 and 5, positions 2 and 6, positions 3 and 4, positions 3 and 5 on the benzene ring . Among them, from the viewpoint of reactivity in the synthesis of polyamic acid, positions 2 and 4, positions 2 and 5, and positions 3 and 5 are preferable. When the ease of synthesis of the diamine compound is also considered, positions 2 and 4, or positions 3 and 5 are more preferable.

Specific examples of the formula (1) include, but are not limited to, diamines represented by the following formulas [A-1] to [A-24].

[Chemical Formula 22]

Formula [A-1] ~ formula [A-5] of, A ₁ are each independently, a carbon number of 2 or higher alkyl group or fluorine-containing alkyl group of 24 or less.

Formula [A-6] and the formula [A-7] of, A ₂ are each _{independently, -O-, -OCH 2 -, -CH} 2 O-, -COOCH 2 -, or represents a -CH ₂ OCO- , And A ₃ each independently represent an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.

In the formulas [A-8] to [A-10], A ₄ independently represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, CH ₂ O-, -OCH ₂ -, or -CH ₂ -, and A ₅ each independently represents an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.

(23)

In the formulas [A-11] and [A-12], A ₆ is each independently selected from the group consisting of -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, _{CH 2 O-, -OCH 2 -,} -CH 2 -, -O-, or represents a -NH-, a ₇ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl An acetoxy group, or a hydroxyl group.

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

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

&Lt; EMI ID =

Specific examples of the diamine represented by the formula (3) include the following formulas [A-25] to [A-30] (wherein A ₁₂ represents -COO-, -OCO-, -CONH-, -NHCO-, CH ₂ -, -O-, -CO-, or -NH-, and A ₁₃ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group). However, no.

(25)

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

(26)

Among these, [A-1], [A-2], [A-3], [A-7], [A- A-16], [A-21] and [A-22] are preferred.

The above-mentioned diamine compound may be used alone or in combination of two or more thereof depending on the properties such as liquid crystal alignability, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

It is preferable that the diamine A is contained in an amount of 5 to 70 mol%, preferably 10 to 50 mol%, more preferably 20 to 50 mol% in 100 mol% of the diamine component used in the synthesis of the polyamic acid having the side chain A Do.

&Lt; Diamine compound having side chain B &gt;

Examples of the diamine compound having a side chain B (hereinafter also referred to as diamine B) include a vinyl group, an acryl group, a methacryl group, an anthracenyl group, a cinnamyl group, a carnonyl group, a coumarin group, A diamine having a photo-crosslinking group such as a stilbene group, or a diamine having a specific structure generating a radical by ultraviolet irradiation. Specific examples include diamines having side chains represented by the above formulas (b-1) to (b-3). Specific examples include diamines represented by the following formula (2) (wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the formula (2) are the same as in the formula (b-1) However, the present invention is not limited to this.

(27)

The bonding position of two amino groups (-NH ₂ ) in the formula (2) is not limited. Specifically, with respect to the bonding group of the side chain, positions 2 and 3, positions 2 and 4, positions 2 and 5, positions 2 and 6, positions 3 and 4, positions 3 and 5 on the benzene ring . Among them, from the viewpoint of reactivity in the synthesis of polyamic acid, positions 2 and 4, positions 2 and 5, and positions 3 and 5 are preferable. When the ease of synthesis of the diamine compound is also considered, positions 2 and 4, or positions 3 and 5 are more preferable.

Specifically, the following compounds are exemplified, but the present invention is not limited thereto. In addition, of the following compounds, X is independently a single bond, an ether, a benzyl ether, represents a bonding group selected from the group consisting of esters, amides, and amino, R is a hydrogen atom or a methyl group, S ₁ is a single bond, or An alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom. Further, l, m, and n each independently represent an integer of 0 to 20.

(28)

[Chemical Formula 29]

The above-mentioned diamine compound may be used singly or in combination of two or more kinds depending on the properties such as liquid crystal alignability, pretilt angle, voltage holding property, and accumulated charge when used as a liquid crystal alignment film, response speed of liquid crystal when the liquid crystal display device is used They may be used in combination.

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

&Lt; Other diamine compounds &gt;

The polyamic acid to be used in the present invention may be used in combination with other diamine compounds other than diamine A and diamine B as a diamine component so long as the effect of the present invention is not impaired. Specific examples thereof are given below.

p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- Diaminodiphenol, 3,5-diaminophenol, 3,5-diaminobenzyl, 2,4-diaminophenol, 3,5-diaminophenol, Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diamino Biphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'- diaminobiphenyl, Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl Methane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diamino Phenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, Bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl- bis (3-aminophenyl) silane, Aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 2,3-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3, (2,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 ' - diaminobenzophenone, 2,3'-diaminobenzophenone, Diaminonaphthalene, 1,6-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,6-diaminonaphthalene, Bis (4-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) ) Propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1, (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, Phenylene bis (methylene)] dianiline, 4,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ , 4'- [1,3-phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenylenebis (methylene)] dianiline, Phenylenebis [(3-amino)] phenanthrene [(4-aminophenyl) methanone] Phenylenemethanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [ Aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate) Bis (3-aminophenyl) isophthalate, bis (4-aminophenyl) isophthalate, N, N ' Bis (4-aminobenzamide), N, N '- (1,4-phenylene) bis (3-aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminobenzamide), N, N'- Bis (3-aminophenyl) terephthalamide, N, N'-bis (4-amino (4-aminophenoxy) anthracene, 4,4'-bis (4-aminophenoxy) diphenyl Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis [ Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (3-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, Bis (4-aminophenoxy) ethane, 1,3-bis (4-aminophenoxy) propane, 1,6-diaminobenzoic acid, Bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) propane, 1,4-bis Pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6- Bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,7- , 1,9-bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) 1,1- (4-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11 Aromatic diamines such as 1 - (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane and 1,12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl Alicyclic diamines such as methane, bis (4-amino-3-methylcyclohexyl) methane and the like, 1,3-diaminopropane, Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12- Aliphatic diamines such as diaminododecane.

The other diamine compounds may be used alone or in combination of two or more thereof depending on the properties such as liquid crystal alignability, pretilt angle, voltage holding characteristics, and accumulated charge when used as a liquid crystal alignment film.

&Lt; Tetracarboxylic acid dianhydride &gt;

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

Naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, Anthracene tetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4 ' -Biphenyl tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4- (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-pyridine tetracarboxylic acid, (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1 , 3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid, oxydi Tetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic 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, Dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, Cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentyl acetic 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 [ , 4,0] 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-butane Dicarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, bicyclo [ , 2] octo-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane- Tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxy norbornane-2 : 3,5-dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and the like.

The tetracarboxylic acid dianhydride can be used alone or in combination of two or more, depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

<Synthesis of polyamic acid>

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

The organic solvent used in the reaction is not particularly limited as long as it dissolves the produced polyamic acid. In addition, an organic solvent which does not dissolve polyamic acid may be used in combination with the solvent insofar as the produced polyamic acid does not precipitate. In addition, since moisture in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable that the organic solvent is dehydrated and dried.

Specific examples of the organic solvent are given below.

N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N- , 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, But are not limited to, sulfone, hexamethyl sulfoxide,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, But are not limited to, 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, Propyleneglycol 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, , Butyl butylate, butyl ether, di N-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, isobutyl ketone, methyl ethyl ketone, But are not limited to, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, Propionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol. These organic solvents may be used alone or in combination.

When the diamine component and the tetracarboxylic acid dianhydride component are reacted in the organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred and the tetracarboxylic acid dianhydride component is dispersed or dissolved in the organic solvent A method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid dianhydride component and a diamine component, and the like Any of these methods may be used. When the diamine component or the tetracarboxylic acid dianhydride component is composed of a plurality of compounds, they may be reacted in a preliminarily mixed state, or they may be reacted individually in a sequential manner, or the low molecular weight compounds reacted individually may be mixed and reacted, May be used.

The temperature at which the diamine component is reacted with the tetracarboxylic acid dianhydride component can be selected from any temperature and is, for example, in the range of -20 ° C to 150 ° C, preferably -5 ° C to 100 ° C. The reaction can be carried out at any concentration, for example, 1 to 50 mass%, preferably 5 to 30 mass%.

The ratio of the total molar amount of the tetracarboxylic acid dianhydride component to the total molar amount of the diamine component in the above polymerization reaction can be selected according to the molecular weight of the polyamic acid to be obtained. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyamic acid. The preferable range is 0.8 to 1.2.

The method for synthesizing the polyamic acid to be used in the present invention is not limited to the above method. Instead of the above tetracarboxylic acid dianhydride, a tetracarboxylic acid or tetra The corresponding polyamic acid can also be obtained by using a tetracarboxylic acid derivative such as a carboxylic acid dihalide in accordance with a known method.

<Polyimide>

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

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

The temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and it is preferable to carry out the removal while removing the water generated by the imidization reaction out of the system.

The catalyst imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferred because it has an appropriate basicity for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, use of acetic anhydride is preferred because purification after completion of the reaction is facilitated. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

When the polyimide precursor or polyimide is recovered from the reaction solution of the polyimide precursor or polyimide, the reaction solution may be put into a poor solvent and precipitated. Examples of poor solvents to be used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried at normal temperature or under reduced pressure or by heating. Further, when the polymer precipitated and recovered is redissolved in an organic solvent and the operation of re-precipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be exemplified, and when three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention comprises the above-mentioned [I] polymerizable compound; And [II] the polyimide precursor or polyimide; , But in addition to the [I] and [II] components, a resin component for forming a resin coating film may be contained. The content of the total resin component is preferably 1% by mass to 20% by mass, preferably 3% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass in 100% by mass of the liquid crystal aligning agent.

In the liquid crystal aligning agent used in the present invention, the above resin component may be either a polyimide precursor or polyimide having side chain A, a polyimide precursor having side chain A and side chain B, or polyimide , Or a mixture thereof, and further, other polymers may be mixed. At this time, the content of such another polymer in the resin component is preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass.

Examples of such another polymer include, but are not limited to, a polyimide precursor or polyimide having no side chain B, a polyimide precursor having no side chain A and side chain B simultaneously, or polyimide .

The molecular weight of the polymer of the resin component is preferably from 5,000 to 1,000,000 as measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the coating film obtained therefrom, the workability in forming the coating film, , And more preferably from 10,000 to 150,000.

<Solvent>

The organic solvent used in the liquid crystal aligning agent of the present invention is not particularly limited as long as it is an organic solvent capable of dissolving the above-mentioned resin component. The organic solvent may be one kind of solvent or two or more kinds of mixed solvents. Examples of the organic solvent include organic solvents exemplified in the above-mentioned polyamic acid synthesis. Among them, N-methyl-2-pyrrolidone,? -Butyrolactone, N-ethyl-2-pyrrolidone, Dimethyl propanamide is preferable from the viewpoint of the solubility of the resin component.

In addition, the following solvents are preferable to be mixed with a solvent having a high solubility of the resin component to improve the uniformity and smoothness of the coating film.

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol , Ethylcarbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether , Propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene Glycol monomethyl ether, propylene glycol monome 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 But are not limited to, ether, 3-methyl-3-methoxybutanol, diisopropylether, ethylisobutylether, diisobutylene, amyl acetate, butylbutylate, butylether, diisobutylketone, methylcyclohexene, Butyl acetate, propyleneglycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-ethylhexyl acetate, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, Methyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy- Propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- Propoxypropanol), lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, lactic acid isoamyl ester, 2-ethyl-1-hexanol and the like. These solvents may be mixed with a plurality of kinds. When these solvents are used, it is preferably 5 to 80 mass%, more preferably 20 to 60 mass%, of the total solvent contained in the liquid crystal aligning agent.

The liquid crystal aligning agent may contain components other than those described above. Examples thereof include a compound which improves film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, a compound which improves the adhesion between the liquid crystal alignment film and the substrate, and the like.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent. More specifically, for example, EF301, EF303, and EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals Inc.), Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Inc. SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and the like. When these surfactants are used, the use ratio thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of the resin component contained in the liquid crystal aligning agent.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment layer and the substrate include a functional silane-containing compound and an epoxy group-containing compound. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, 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- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N', -tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxy Silane, 3- (N, N-diglycidyl) And the like can be mentioned diamino trimethoxysilane. In order to further increase the rub resistance of the resin using the present invention, a phenol compound such as 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol may be added do. When these compounds are used, the amount is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, based on 100 parts by mass of the resin component contained in the liquid crystal aligning agent.

The liquid crystal aligning agent for use in the present invention may contain a dielectric or conductive material for the purpose of changing electric characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effect of the present invention is not impaired.

&Lt; Liquid crystal alignment film &

The cured film obtained by applying the liquid crystal aligning agent of the present invention to a substrate, drying it if necessary, and baking it may be used as it is as a liquid crystal alignment film. In addition, this cured film may be rubbed, irradiated with polarized light, light of a specific wavelength or the like, treated with an ion beam or the like, or irradiated with UV light while a voltage is applied to the liquid crystal display element after liquid crystal filling as an alignment film for SC- It is also possible.

In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency and may be a glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyallylate, polyurethane, polysulfone, polyether, , Trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetylcellulose, diacetylcellulose, cellulose acetate butyrate, and the like. In addition, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for liquid crystal driving is formed from the viewpoint of simplifying the process. Further, in a reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used only for a substrate on one side, and a material for reflecting light such as aluminum can be used as the electrode in this case.

The method of applying the liquid crystal aligning agent is not particularly limited, and examples thereof include a printing method such as screen printing, offset printing and flexographic printing, an ink jet method, a spray method, a roll coating method, a dip, a roll coater, a slit coater, have. From the viewpoint of productivity, the transfer printing method is widely used industrially and is preferably used in the present invention.

The coating film formed by applying the liquid crystal aligning agent by the above method may be fired to form a cured film. The drying step after coating the liquid crystal aligning agent is not necessarily required, but it is preferable to carry out the drying step when the time from the application to the firing is not constant for each substrate or when the firing is not carried out immediately after application. The drying may be carried out as long as the solvent is removed to such an extent that the coating film shape is not deformed by, for example, conveyance of the substrate, and the drying means is not particularly limited. For example, a method of drying on a hot plate at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C, for 0.5 minutes to 30 minutes, preferably for 1 minute to 5 minutes.

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

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

&Lt; Liquid Crystal Display Device Having Liquid Crystal Alignment Film &

The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method, and then manufacturing a liquid crystal cell by a known method. As a specific example of the liquid crystal display element, there are two substrates arranged so as to face each other, a liquid crystal layer formed between the substrate and the liquid crystal layer, and a liquid crystal cell having the liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention The liquid crystal display device of the vertical alignment type is a liquid crystal display device having a vertical alignment method. Specifically, the liquid crystal aligning agent of the present invention is coated on two substrates and baked to form a liquid crystal alignment film. Two substrates are arranged so that the liquid crystal alignment films face each other, and a liquid crystal layer That is, a liquid crystal cell that is formed by contacting a liquid crystal alignment film to form a liquid crystal layer, and irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. As described above, by using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, ultraviolet rays are irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer to polymerize the polymerizable compound, and the photoreactive side chains Alternatively, by reacting the polymerizable compound with the photoreactive side chain of the polymer, the alignment of the liquid crystal is more efficiently fixed, and the liquid crystal display element is remarkably excellent in the response speed.

The substrate used in the liquid crystal display of the present invention is not specifically limited as long as it is a substrate having high transparency, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed. Specific examples include the same substrates as those described in the liquid crystal alignment film. A substrate on which a conventional electrode pattern or a projection pattern is formed may be used. In the liquid crystal display element of the present invention, since the liquid crystal aligning agent of the present invention is used as the liquid crystal aligning agent forming the liquid crystal alignment film, For example, a structure in which a line / slit electrode pattern of 1 to 10 mu m is formed, and a slit pattern or a projection pattern is not formed on the counter substrate, and the liquid crystal display element of this structure can be used for a manufacturing process And a high transmittance can be obtained.

Further, in a high-performance device such as a TFT-type device, a device such as a transistor is formed between an electrode for liquid crystal driving and a substrate.

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

The liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on the substrate and then firing the liquid crystal alignment film, and the details are the same as described above.

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited and liquid crystal materials used in conventional vertical alignment methods such as MLC-6608 and MLC-6609 manufactured by Merck & Liquid crystal can be used.

As a method of sandwiching this liquid crystal layer between two substrates, known methods can be mentioned. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers such as beads are dispersed on a liquid crystal alignment film of one of the substrates, and the other side of the substrate is coated with a liquid crystal alignment film And the liquid crystal is injected under reduced pressure to seal the liquid crystal. In addition, a pair of substrates on which liquid crystal alignment films are formed is prepared, liquid crystal is dropped after dispersing a spacer such as beads on the liquid crystal alignment film of one of the substrates, and then, A liquid crystal cell can also be manufactured by a method in which one substrate is bonded and encapsulated. The thickness of the spacer at this time is preferably 1 to 30 占 퐉, more preferably 2 to 10 占 퐉.

The step of forming the liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer is performed by applying an electric field to the liquid crystal alignment film and the liquid crystal layer by applying a voltage between the electrodes provided on the substrate, And a method of irradiating ultraviolet rays while maintaining the electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The dose of the 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. The smaller amount of ultraviolet radiation is preferable because it can suppress the decrease in reliability caused by the destruction of the liquid crystal or the member constituting the liquid crystal display element and the manufacturing efficiency is improved by reducing the ultraviolet ray irradiation time.

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

The liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for producing a vertical alignment type liquid crystal display element such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, It is also possible to use it as a liquid crystal alignment film.

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples.

Example

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

(Acid anhydride)

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

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

PMDA: pyromellitic dianhydride.

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

The diamine represented by the following formula DA-1 was synthesized by the method described in Japanese Patent No. 4085206.

The diamine represented by the following formula DA-2 was synthesized by the method described in Japanese Patent No. 4466373.

The diamine represented by the following formula DA-3 was synthesized by the method described in Japanese Patent No. 5273035.

The diamine represented by the following formula DA-4 was purchased from Tokyo Chemical Industry Co., Ltd.

The diamine represented by the following formula DA-5 was synthesized by the method described in WO2009 / 093704.

The diamine represented by the following formula DA-6 was prepared by the method described in Japanese Patent Application No. 2013-132874.

The diamine represented by the following formula DA-7 was purchased from Wako Pure Chemical Industries, Ltd.

The diamine represented by the following formula DA-8 was prepared by the method described in Japanese Patent Application No. 2013-182351.

The diamine represented by the following formula DA-9 was prepared by the method described later (synthesis of raw material synthesis: DA-9 synthesis).

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<Solvent>

NMP: N-methyl-2-pyrrolidone.

BCS: butyl cellosolve.

<Additives>

3AMP: 3-picolylamine.

<Polymerizable compound>

A polymerizable compound represented by the following formulas RM1 to RM10 and RM11.

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The conditions for measuring the molecular weight of the polyimide are as follows.

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

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

Column temperature: 50 캜,

Eluent: 30 mmol / l of lithium bromide · hydrate (LiBr · H ₂ O), 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid) as an additive, N, N'-dimethylformamide Furan (THF) of 10 ml / l),

Flow rate: 1.0 ml / min,

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

The imidization rate of the polyimide was measured as follows. 20 mg of the polyimide powder was placed in an NMR sample tube (NMR sampling tube standard 5 manufactured by Kusano Scientific Co., Ltd.), 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture) was added, . This solution was subjected to proton NMR measurement at 500 MHz using an NMR meter (JNW-ECA500) manufactured by Nippon DATUM Co., The proton derived from the structure that does not change before and after the imidization is determined as the reference proton and the proton peak integrated value derived from the NH group of the amic acid appearing in the vicinity of 9.5 to 10.0 ppm By using the following formula. In the following formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and? Is the NH of amic acid when the polyamic acid (imidization ratio is 0% Is the ratio of the number of reference protons to one proton of the group.

Imidization ratio (%) = (1 -? X / y) x 100

The products described in Synthesis Examples below were identified by ¹ H-NMR analysis (analysis conditions are as follows).

Apparatus: Varian NMR System 400 NB (400 MHz)

Measurement solvents: CDCl ₃ , DMSO-d ₆

Reference material: tetramethylsilane (TMS) (0.0 ppm for ¹ H)

(Synthesis of raw material synthesis example: DA-9)

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<Synthesis of DA-9-1>

120 g (310 mmol, 1.0 eq) of cholesterol and 33.3 g (329 mmol, 1.1 eq) of triethylamine were charged into a 1,000-mL four-necked flask and 600 g of 3,5-dinitrobenzoyl chloride 69.2 g (300 mmol) was added over 1 hour. After the addition, the mixture was stirred at room temperature overnight, and then reprecipitated with water. The obtained solid was recrystallized from IPA and ethyl acetate, respectively, to obtain 179 g of crude DA-9-1 (crude yield: 100%).

<Synthesis of DA-9>

146 g (251 mmol) of DA-9-1 and 284 g (1497 mmol, 6.0 eq) of tin chloride in 750 g of THF and 750 g of pure water were introduced into a 2000 ml four-necked flask, Lt; / RTI &gt; After completion of the reaction, neutralization was carried out, and the precipitated tin was removed by filtration. Thereafter, recrystallization was carried out with the liquid and IPA to obtain 76.3 g of DA-9 (the yield: 58%).

&Lt; Synthesis Example 1-Synthesis of RM1- &gt;

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<Synthesis of RM1-A>

To a 1 L four-necked flask equipped with a magnetic stirrer were added 58.3 g (305 mmol) of 4-bromo-2-fluorophenol and 4- (4,4,5,5 67.2 g (1.0 eq) of potassium carbonate, 2.0 eq of potassium carbonate and 7.42 g (8 mol%) of tri (o-tolyl) ), 10.9 g (5 mol%) of bis (triphenylphosphine) palladium (II) chloride was added after nitrogen replacement, and the mixture was reacted at 65 ° C for 15 hours.

After completion of the reaction, the THF was distilled off under reduced pressure and the residue was diluted with 466 g of ethyl acetate. 268 g of 3.0 M HCl aqueous solution was added. Insoluble materials such as Pd were removed by filtration, and 233 g of ethyl acetate And the flask or the filtrate was washed using the flask. Subsequently, the water phase was separated, and the organic phase was recovered. The recovered organic phase was washed three times with 350 g of pure water, dehydrated with magnesium sulfate, and then activated carbon (item: manufactured by Tokuyama Shirasagi dry product, g, and the mixture was stirred at room temperature for about 30 minutes, followed by filtration and drying to obtain crude product. The crude product was recurfied twice with 292 g of toluene at room temperature, followed by filtration and drying to obtain 42.0 g of RM1-A (yield: 67%, property: pale pink crystals).

<Synthesis of RM1-B>

To a 200 ml four-necked flask equipped with a magnetic stirrer were added 6.00 g (24.5 mmol) of the compound (RM1-A) obtained above and 80 mg of 2- (4-bromobutyl) 12.0 g (2.2 eq) of oxolane, and 13.8 g (4.0 eq) of potassium carbonate were charged and reacted at 60 DEG C for 24 hours. Thereafter, the reaction solution was poured into pure water to precipitate crystals, followed by filtration and drying, to obtain 10.4 g of RM1-B (yield: 92%).

<Synthesis of RM1>

To a 100 ml four-necked flask equipped with a magnetic stirrer were added 2.90 g (6.30 mmol) of the compound (RM1-B) obtained above and 2.5 g (2.4 eq) of 2- (bromomethyl) 2.8 g (2.4 eq) of tin chloride (anhydrous) was poured, 12 ml of 10% aqueous HCl solution was added, and the mixture was reacted at 70 ° C for 20 hours. Thereafter, the reaction solution was poured into pure water to precipitate crystals, which were then filtered and dried to obtain crude crystals. The obtained crude product was recrystallized in THF / EtOH to obtain 2.2 g of RM1 (yield: 69%).

&Lt; Synthesis Example 2-Synthesis of RM2- &gt;

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<Synthesis of RM2-A>

70.2 g (539 mmol) of 2-hydroxyethyl methacrylate and 76.4 g (1.4 eq) of triethylamine in 281 g of THF were charged into a 1 L four-necked flask equipped with a magnetic stirrer, And 74.6 g (1.2 eq) of methanesulfonyl chloride diluted with 35.1 g of THF were added dropwise, followed by stirring at room temperature for 2 hours. Thereafter, the salt precipitated from the reaction solution was filtered, and 0.35 g of dibutylhydroxytoluene was added to the filtrate, followed by concentration and drying. Then, 281 g of ethyl acetate was added to the concentrate residue, and 210 g of pure water was added. As insoluble matter was generated, 3.5 g of activated carbon (item: manufactured by Tokushisha Shirasagi dry product, manufactured by Nihon Enbilo Chemical Co., Ltd.) And the mixture was stirred at room temperature for 30 minutes. Subsequently, this was filtered to confirm that the insolubles were removed, and then the water phase was removed. The organic phase was washed twice with 210 g of pure water, dehydrated with magnesium sulfate, and then concentrated to dryness to obtain 99.0 g of RM2-A (yield: 86%, property: yellow liquid).

<Synthesis of RM2-B>

To a 300 ml four-necked flask equipped with a magnetic stirrer were added 10.4 g (54.4 mmol) of 4-bromo-2-fluorophenol and 72 mg of 6-hydroxy-2-naphthaleneboronic acid (Triphenylphosphine) palladium (II) chloride (1.0 g) was added to the reaction solution after the nitrogen substitution, followed by the addition of 9.68 g (1.0 eq) of potassium carbonate, 15.1 g 1.91 g (5 mol%) was added, and the mixture was reacted at 65 DEG C for 2 hours. Thereafter, the THF was removed by concentration under reduced pressure, and after diluting with 104 g of ethyl acetate, 47.8 g of 3.0 M aqueous HCl solution was added and stirred. Subsequently, Pd was removed by filtration, the filtrate and the like were further washed with 52.0 g of ethyl acetate, and the water phase was separated. The recovered organic phase was washed three times with 72.8 g of pure water, dehydrated with magnesium sulfate, and then added with 0.52 g of activated carbon (product: Tokushisha Shirasagi dry product, Nihon Enbilo Chemical Co., Ltd.) , Filtered and dried. The crude product was repulped with 72.8 g of toluene and purified by silica gel column chromatography (ethyl acetate / toluene / hexane = 1/1/2 vol) to obtain 6.47 g of RM2-B (yield: 49% , Appearance: white solid).

<Synthesis of RM2>

6.07 g (23.9 mmol) of the compound (RM2-B) obtained above and 11.1 g (2.2 eq) of the polymerizable side chain (RM2-A) in 48.6 g of DMF were placed in a 200- And 9.93 g (3.0 eq) of potassium carbonate, and the mixture was allowed to react at 65 deg. C in a nitrogen atmosphere for 22 hours.

Thereafter, the reaction solution was diluted with 48.6 g of ethyl acetate, and the inorganic salt was removed by filtration. The filtrate was washed with 42.5 g of ethyl acetate. The recovered organic phase was washed with 48.6 g of pure water three times, the organic phase was dehydrated with magnesium sulfate, and then concentrated to dryness. After drying, 12.1 mg of 2,6-di-tert-butyl-p-cresol was added to the recovered crude product, 5.77 g of THF was added and completely dissolved by heating at 45 캜, and 35.8 g of methanol was added to 5.0 Lt; 0 &gt; C. However, since the impurities were confirmed, 4.89 g of THF was added to the recovered solid and completely dissolved by heating at 45 캜. 24.9 g of methanol was added and recrystallization was carried out at room temperature to obtain 6.37 g of RM2 (Yield: 56% White crystals).

&Lt; Synthesis Example 3-Synthesis of RM3- &gt;

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<Synthesis of RM3-A>

To a 2 L four-necked flask equipped with a mechanical stirrer were added 25.5 g (101 mmol) of 1,4-dibromo-2-fluorobenzene, 4- (4,4,4- 45.5 g (2.0 eq) of 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenol, 41.7 g (3.0 eq) of potassium carbonate, bis (triphenylphosphine) palladium Chloride (2.12 g), and the mixture was stirred at 65 占 폚 in a nitrogen atmosphere for 24 hours. Thereafter, the THF was distilled off under reduced pressure, the reaction solution was diluted with 255 g of ethyl acetate, 99.5 g of 3.0 M aqueous HCl solution was added, and insolubles such as Pd were removed by filtration. After removing the water phase from the filtrate, the obtained organic phase was washed three times with pure water (179 g). The recovered organic phase was dehydrated with magnesium sulfate, and 1.30 g of activated carbon (product: manufactured by Tokushu Shirasagi dry Co., Ltd., product of Nihon Enbilo Chemical Co., Ltd.) was added and stirred for about 30 minutes at room temperature, followed by filtration and drying to obtain crude product . The recovered crude product was suspended in 153 g of toluene, washed twice at 60 캜 for 1 hour, and then filtered and dried to obtain 22.4 g of RM3-A (yield: 79%, property: pale pink crystal).

<Synthesis of RM3>

23.0 g (2.2 eq) of the polymerizable side chain (RM2-A) and 14.1 g (50.2 mmol) of the compound (RM3-A) obtained above were added to a 500 ml four-necked flask equipped with a mechanical stirrer, And 20.9 g (3.0 eq) of potassium carbonate, and the mixture was stirred at 65 占 폚 for 18 hours under a nitrogen atmosphere. After 18 hours, the polymerizable side chain (RM2-A) (0.2 eq / 2) was further added for reaction for 4 hours because the raw material remained. Thereafter, the reaction solution was diluted with 113 g of ethyl acetate, and the inorganic salt was removed by filtration. The filtrate was washed with 70.5 g of ethyl acetate. The recovered organic phase was washed with pure water (141 g). As a result, a slight amount of white crystals were generated. Therefore, 70.5 g of ethyl acetate was further added and the mixture was washed twice with 141 g of pure water. The organic phase was dehydrated with magnesium sulfate, Lt; / RTI &gt; 0.71 g of activated carbon (manufactured by Tokushu Shirasagi dry Co., Ltd., product of Nihon Enbilo Chemical Co., Ltd.) was added to the recovered crude product, stirred for about 30 minutes at room temperature, filtered and dried, and 222 g of ethyl acetate was added thereto. , And 98.2 g of hexane was added thereto, followed by recrystallization at 2 캜 to obtain 15.0 g of RM3 (yield: 59%, property: white crystal).

<Synthesis Example 4-Synthesis of RM4>

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<Synthesis of RM4>

To a 300 ml four-necked flask equipped with a magnetic stirrer were added 9.18 g (45.0 mmol) of F-containing biphenol compound (RM1-A), 18.6 g (3.0 eq) of potassium carbonate, RM2-A), and the mixture was reacted at 62 占 폚 under a nitrogen atmosphere for 15 hours. Thereafter, the reaction solution was diluted with 138 g of ethyl acetate, and the inorganic salt was removed by filtration. To the recovered filtrate was added 45.9 g of ethyl acetate, washed three times with 91.8 g of pure water, and dehydrated with sodium sulfate. Subsequently, 0.46 g of activated carbon (product: manufactured by Tokushu Shirasagi dry Co., Ltd., product of Nihon Enbilo Chemical Co., Ltd.) was added and stirred at room temperature for about 30 minutes, followed by filtration, and the filtrate was concentrated to dryness. 9.2 mg of 2,6-di-tert-butyl-p-cresol was added to the concentrate, 184 g of IPA was added and the mixture was completely dissolved by heating to 57 DEG C and recrystallization was conducted at room temperature to obtain 13.4 g of RM4 (Yield: 70%, characteristic: pale yellow crystals).

&Lt; Synthesis Example 5-Synthesis of RM5- &gt;

The above-described RM5 was synthesized by the method described in WO2012 / 002513.

&Lt; Synthesis Example 6-Synthesis of RM6- &gt;

The above-described RM6 was synthesized by the method described in WO2012 / 133820 (particularly paragraph No. [0163]).

&Lt; Synthesis Example 7-Synthesis of RM7 &gt;

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<Synthesis of RM7-A>

In a 200 ml four-necked flask equipped with a magnetic stirrer, 9.00 g (44.1 mmol) of the F-containing biphenol compound (RM1-A), 22.4 g (3.0 eq) of bromoacetaldehyde dimethylacetal, 24.4 g (4.0 eq) of potassium and 2.2 g (0.30 eq) of potassium iodide were charged, and the mixture was stirred at 120 DEG C for 18 hours. After 18 hours, 7.45 g (1.0 eq) of bromoacetaldehyde dimethylacetal and 1.4 g (0.2 eq) of potassium iodide were added and stirred for further 8 hours. After completion of the reaction, the reaction solution was diluted with 99.0 g of THF, the inorganic salt was filtered, and the filtrate was concentrated under reduced pressure. Next, the residue was diluted with ethyl acetate (198 g), washed twice with pure water (99.0 g), and dehydrated with magnesium sulfate. Thereafter, 0.45 g of activated carbon (product: manufactured by Tokushu Shirasagi dry Co., Ltd., product of Nihon Enbilo Chemical Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 hour. The mixture was filtered and the filtrate was concentrated under reduced pressure. Subsequently, 19.8 g of THF was added to the obtained crude product and dissolved at 50 占 폚, 60.3 g of IPA was added, and the mixture was stirred under ice cooling. The precipitated crystals were collected by filtration and dried to give 11.5 g of RM7-A (yield: 62%, property: pale brown crystals).

<Synthesis of RM7>

10.4 g (27.2 mmol) of the compound (RM7-A) obtained above and 11.6 g (2.2 eq) of ethyl 2- (bromomethyl) acrylate in 103 g of THF were placed in a 500-ml four-necked flask equipped with a magnetic stirrer, , 12.4 g (2.4 eq) of tin chloride, and 36.2 g of a 10 wt% aqueous solution of HCl were charged and stirred at 70 캜 for 39 hours. After completion of the reaction, 30 mg of 2,6-di-tert-butyl-p-cresol was added, and the THF was distilled off under reduced pressure, and diluted with 104 g of ethyl acetate. After removing the separated water phase, the organic phase was washed three times with 62.4 g of pure water at 40 ° C. Next, after the organic phase was dehydrated with magnesium sulfate, 0.52 g of activated carbon (item: manufactured by TOKUSHISHI SHIRASAGI dry product, manufactured by Nihon Enviro Chemical Co., Ltd.) was added and the mixture was stirred at room temperature for 1 hour. The mixture was filtered, And concentrated. Subsequently, 52 g of THF was added to the obtained crude product and dissolved at 60 DEG C. Then, 156 g of EtOH was added, and the mixture was stirred under ice cooling. Thereby, the precipitated crystals were filtered and dried to obtain 3.42 g of RM7 (yield: 30%, property: white crystals).

&Lt; Synthesis Example 8-Synthesis of RM8- &gt;

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<Synthesis of RM8-A>

10.0 g (53.7 mmol) of the F-containing biphenol compound (RM1-A), 20.4 g (3.0 eq) of potassium carbonate and 1.61 g of potassium iodide in 15.3 g of NMP were added to a 200- 0.20 eq), and 16.6 g (2.2 eq) of 4-chlorobutylaldehyde dimethylacetal diluted with 5.30 g of NMP were added dropwise over 3 hours at 80 deg. C in a nitrogen atmosphere. After 19 hours of dropwise addition, 2.25 g (0.3 eq) of 4-chlorobutylaldehyde dimethylacetal and 1.61 g (0.2 eq) of potassium iodide were added and the reaction was further continued for 25 hours. After completion of the reaction, the reaction solution was diluted with 80.0 g of ethyl acetate, and potassium carbonate was removed by filtration. Further, 20.0 g of ethyl acetate was further added, washed three times with 60.0 g of pure water, and dehydrated with magnesium sulfate. Thereafter, the solvent was removed by concentration under reduced pressure to obtain a crude product. 10 g of the obtained crude product and 70 g of MeOH were added, and the mixture was heated at 50 캜 and ice-cooled to precipitate crystals, which were then filtered and dried to obtain 11.7 g of RM8-A (yield: 55%, characteristic: white solid). The filtrate was concentrated under reduced pressure to remove the solvent. The crude product was heated at 40 占 폚 with addition of 5 g of THF and 70 g of IPA, and crystals were precipitated by cooling on ice to obtain 3.0 g of RM8-A (yield: 14% , Appearance: light yellow solid).

<Synthesis of RM8>

13.2 g (30.3 mmol) of the compound (RM8-A) obtained above and 12.9 g (2.2 eq) of ethyl 2- (bromomethyl) acrylate were dissolved in 133 g of THF in a 300 ml four-necked flask equipped with a magnetic stirrer, 13.8 g (2.4 eq) of tin chloride, and 46.3 g of a 10 wt% aqueous solution of HCl were introduced and reacted at 50 DEG C for 5 hours. After 5 hours, 13.2 g of a 20 wt% HCl aqueous solution was added and reacted for 19 hours. After completion of the reaction, the THF was distilled off under reduced pressure, diluted with ethyl acetate (106 g), and then washed three times with 52.8 g of pure water. Subsequently, 26.4 g of ethyl acetate and 79.2 g of pure water were further added, and sodium bicarbonate was added to neutralize the solution. After the neutralization, the salt was removed by filtration, and 0.70 g of activated carbon (product: Tokuyama Shirasagi dry product, manufactured by Nihon Enbilo Chemical Co., Ltd.) was added, and the mixture was stirred at room temperature and filtered. The obtained solution was washed twice with pure water (66 g), and the solvent was removed by concentration under reduced pressure. 79.2 g of THF and 158 g of IPA were added and the mixture was heated at 50 캜 and ice-cooled to precipitate crystals and recover the crystals by filtration . 46.2 g of THF and 92.4 g of MeOH were added to the obtained crystals, and the mixture was heated at 50 占 폚 and ice-cooled to precipitate crystals. The crystals were collected by filtration and dried to obtain 8.92 g of RM8 (yield: 61%;

&Lt; Synthesis Example 9-Synthesis of &lt; RTI ID = 0.0 &gt;

[Chemical Formula 39]

<Synthesis of RM9-A>

To a 300 ml four-necked flask equipped with a magnetic stirrer were added 20.0 g (107 mmol) of 4,4'-biphenol, 44.6 g (3.0 eq) of potassium carbonate and 1.82 g (0.1 eq) of potassium iodide in 50.0 g of DMF, 39.8 g (2.2 eq) of 2-bromomethyl-1,3-dioxolane diluted with 10.0 g of DMF was added dropwise at 100 캜 and stirred at the same temperature for 6 hours. After 6 hours, 5.38 g (0.3 eq) of 2-bromomethyl-1,3-dioxolane was further added and the mixture was stirred for 18 hours. After completion of the reaction, the reaction solution was added to 400 g of pure water to precipitate crystals, and the precipitate was filtered. The slurry was washed with 60.0 g of MeOH and filtered again to obtain a white solid. The resultant white solid was suspended in 500 g of THF, and 1.00 g of activated carbon (product: Tokushisha Shirasagi dry product, manufactured by Nihon Enviro Chemical Co., Ltd.) was added and stirred at 60 캜 for 30 minutes and then filtered (45 캜). The filtrate was cooled, and white crystals precipitated. The precipitate was filtered and dried, yielding 13.0 g of RM9-A (Yield: 34%, characteristic: white solid).

<Synthesis of RM9>

9.95 g (27.8 mmol) of the compound (RM9-A) obtained above and 11.8 g (2.2 eq) of ethyl 2- (bromomethyl) acrylate in 99.5 g of THF were placed in a 300 ml four- necked flask equipped with a magnetic stirrer, , 12.6 g (2.4 eq) of tin chloride, and 34.8 g of a 10 wt% hydrochloric acid aqueous solution were charged and stirred at 60 DEG C for 1.5 hours. After 1.5 hours, 9.95 g of a 20 wt% hydrochloric acid aqueous solution was added, followed by further stirring for 21 hours to complete the reaction. Thereafter, THF was distilled off under reduced pressure, and 199 g of ethyl acetate was added to remove the water phase. Next, the organic layer was washed twice with 59.7 g of pure water. The organic phase was recovered, and ethyl acetate was distilled off under reduced pressure, and then 149 g of THF was added and the mixture was refluxed and stirred. Subsequently, 0.48 g of activated carbon (product: manufactured by Tokushu Shirasagi dry Co., Ltd., product of Nihon Enviro Chemical Co., Ltd.) was added and stirred for 1 hour. After dehydration treatment with magnesium sulfate, this was filtered to obtain a uniform filtrate. Subsequently, this was concentrated under reduced pressure to adjust the amount of THF to 79.6 g, to which 159 g of MeOH was added at 55 占 폚, and the mixture was stirred for an ice bath for a while. The crystals thus precipitated were filtered and dried to obtain 8.4 g of RM9 (yield: 74%, property: white crystals).

&Lt; Synthesis Example 10-Synthesis of RM10- &gt;

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<Synthesis of RM10-A>

In a 200 ml four-necked flask equipped with a magnetic stirrer, 10.0 g (53.7 mmol) of 4,4'-biphenol, 18.4 g (2.2 eq) of 4-chlorobutylaldehyde dimethyl acetal and 22.3 g g (3.0 eq) of potassium iodide and 1.78 g (0.2 eq) of potassium iodide, and the mixture was stirred at 80 占 폚 for 3 hours. Then, 2.45 g (0.3 eq) of 4-chlorobutylaldehyde dimethyl acetal was added, and the mixture was further stirred for 16 hours. After the reaction, the reaction solution was diluted with 50.0 g of ethyl acetate, and the inorganic salt was filtered. The filtrate was diluted with 50.0 g of ethyl acetate and washed three times with 50.0 g of pure water at 50 캜. The organic phase was then dehydrated with sodium sulfate, concentrated to a total weight of 68.0 g, and the precipitated crystals were filtered. 5.0 g of THF and 20.0 g of MeOH were added to the crude product, dissolved at 50 캜, cooled and stirred briefly. The precipitated crystals were filtered and dried to obtain 15.8 g of RM10-A (Yield: 70%, Appearance: white solid).

<Synthesis of RM10>

14.8 g (35.4 mmol) of the compound (RM10-A) obtained above and 15.0 g (2.2 eq) of ethyl 2- (bromomethyl) acrylate were dissolved in 56.4 g of THF in a 500 ml four-necked flask equipped with a magnetic stirrer. , 16.9 g (2.4 eq) of tin chloride, 0.39 g (5 mol%) of 2,6-di-tert-butyl-p-cresol and 51.8 g of a 20 wt% aqueous solution of HCl were introduced and stirred at 60 ° C for 3 hours. After the reaction, the reaction solution was concentrated under reduced pressure, and 148 g of pure water was added. The precipitated crystals were filtered and washed twice with 148 g of pure water. Subsequently, 118 g of THF and 118 g of MeOH were added to this crystal, dissolved at 50 DEG C, and then cooled to room temperature and stirred for a while. The crystals thus obtained were filtered to obtain a crude product. Further, 237 g of THF and 237 g of IPA were added to the crude product and dissolved at 60 DEG C, followed by cooling to room temperature and stirring for a while. The precipitated crystals were collected by filtration, washed with 74.0 g of THF three times, and then dried under reduced pressure to obtain 7.20 g of RM10 (yield: 44%, property: white crystals).

&Lt; Synthesis Example 11 - Synthesis of liquid crystal aligning agent D1 &gt;

DA-6 (1.77 g, 3.8 mmol), DA-4 (0.94 g, 6.2 mmol), DA-2 (2.40 g, 6.0 mmol) CBDA (2.27 g, 11.6 mmol) and NMP (10.7 g) were added to the reaction mixture, and the mixture was reacted at room temperature for 10 hours To obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (50 g) to dilute to 6 mass%, acetic anhydride (5.7 g) and pyridine (2.9 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (A) -1. The imidization ratio of the polyimide was 60%, the number average molecular weight was 12,000, and the weight average molecular weight was 33,000.

NMP (44.0 g) was added to the obtained polyimide powder (A) -1 (6.0 g), and the mixture was stirred and dissolved at 50 캜 for 5 hours. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent D1.

Synthesis Example 12 - Synthesis of liquid crystal aligning agent D2 -

(2.00 g, 8.0 mmol), DA-8 (3.30 g, 10.0 mmol) and DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (34.8 g) and reacted at 60 ° C for 3 hours , CBDA (2.27 g, 11.6 mmol) and NMP (11.6 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (50 g) to dilute to 6 mass%, acetic anhydride (5.3 g) and pyridine (2.7 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (A) -2. The imidization rate of the polyimide was 60%, the number average molecular weight was 15,000, and the weight average molecular weight was 41,000.

NMP (44.0 g) was added to the obtained polyimide powder (A) -2 (6.0 g) and dissolved by stirring at 50 캜 for 5 hours. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent D2.

&Lt; Synthesis Example 13 - Synthesis of liquid crystal aligning agent D3 &gt;

DA-2 (4.00 g, 10.0 mmol) was dissolved in NMP (38.9 g) and reacted at 60 ° C for 3 hours. Then, CBDA (2.27 g, 11.6 mmol) and NMP (13.0 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (50 g) to dilute to 6 mass%, acetic anhydride (3.1 g) and pyridine (12.1 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (A) -3. The imidization ratio of the polyimide was 60%, the number average molecular weight was 15,000, and the weight average molecular weight was 36,000.

NMP (44.0 g) was added to the obtained polyimide powder (A) -3 (6.0 g) and dissolved by stirring at 50 캜 for 5 hours. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent D3.

&Lt; Synthesis Example 14 - Synthesis of liquid crystal aligning agent D4 &gt;

(2.00 g, 8.0 mmol), DA-7 (2.64 g, 10.0 mmol) and DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (32.8 g) and reacted at 60 ° C for 3 hours Then, CBDA (2.27 g, 11.6 mmol) and NMP (10.9 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (50 g) to dilute to 6 mass%, acetic anhydride (3.7 g) and pyridine (14.4 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (A) -4. The imidization rate of the polyimide was 60%, the number average molecular weight was 25,000, and the weight average molecular weight was 45,000.

NMP (44.0 g) was added to the resulting polyimide powder (A) -4 (6.0 g) and dissolved by stirring at 50 占 폚 for 5 hours. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent D4.

&Lt; Synthesis Example 15-Synthesis of liquid crystal aligning agent D5 &gt;

DA-1 (2.28 g, 6.0 mmol) and DA-8 (2.97 g, 9.0 mmol) were dissolved in NMP (24.9 g) and reacted at 80 ° C for 3 hours , CBDA (1.74 g, 8.9 mmol) and NMP (8.3 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (36 g) to dilute to 6 mass%, acetic anhydride (4.0 g) and pyridine (2.1 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (A) -5. The imidization ratio of the polyimide was 60%, the number average molecular weight was 20,000, and the weight average molecular weight was 43,000.

NMP (44.0 g) was added to the resulting polyimide powder (A) -5 (6.0 g) and dissolved by stirring at 50 캜 for 5 hours. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent D5.

Synthesis Example 16 - Synthesis of liquid crystal aligning agent D6 -

D-8 (4.63 g, 14.0 mmol) and DA-3 (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 reacted at room temperature for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (50 g) to dilute to 6 mass%, acetic anhydride (5.3 g) and pyridine (2.7 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (A) -6. The polyimide had an imidization rate of 60%, a number average molecular weight of 17,000, and a weight average molecular weight of 35,000.

NMP (44.0 g) was added to the obtained polyimide powder (A) -6 (6.0 g) and dissolved by stirring at 50 占 폚 for 5 hours. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent D6.

&Lt; Synthesis Example 17 - Synthesis of liquid crystal aligning agent D7 &gt;

DA-9 (2.09 g, 3.9 mmol) and DA-8 (3.00 g, 9.1 mmol) were dissolved in NMP (23.5 g) and reacted at 60 ° C for 3 hours After that, CBDA (1.43 g, 7.3 mmol) and NMP (7.8 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (36 g) to dilute to 6 mass%, acetic anhydride (3.6 g) and pyridine (1.9 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (A) -7. The polyimide had an imidization rate of 60%, a number average molecular weight of 16,000, and a weight average molecular weight of 36,000.

To the resulting polyimide powder (A) -7 (6.0 g), NMP (44.0 g) was added and dissolved by stirring at 50 占 폚 for 5 hours. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent D7.

&Lt; Synthesis Example 18 - Synthesis of liquid crystal aligning agent D8 &gt;

D-8 (3.96 g, 12.0 mmol) and DA-1 (3.04 g, 8.0 mmol) were dissolved in NMP (33.9 g) and reacted at 60 ° C for 3 hours Then, CBDA (2.27 g, 11.6 mmol) and NMP (11.3 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (50 g) to dilute to 6 mass%, acetic anhydride (5.4 g) and pyridine (2.8 g) were added as imidation catalysts and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (A) -8. The imidization ratio of the polyimide was 60%, the number average molecular weight was 18,000, and the weight average molecular weight was 40000.

To the resulting polyimide powder (A) -8 (6.0 g), NMP (44.0 g) was added and dissolved by stirring at 50 占 폚 for 5 hours. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent D8.

&Lt; Synthesis Example 19 - Synthesis of liquid crystal aligning agent D9 &gt;

DA-5 (1.45 g, 6.0 mmol) was added to a solution of BODA (2.00 g, 8.0 mmol), DA-1 (2.28 g, 6.0 mmol), DA-4 (1.22 g, 8.0 mmol) After reacting at 60 占 폚 for 3 hours, PMDA (2.53 g, 11.6 mmol) and NMP (9.5 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (50 g) to dilute to 6 mass%, acetic anhydride (6.4 g) and pyridine (3.3 g) were added as an imidation catalyst and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (A) -9. The imidization ratio of the polyimide was 60%, the number average molecular weight was 10,000, and the weight average molecular weight was 31,000.

NMP (44.0 g) was added to the obtained polyimide powder (A) -9 (6.0 g), and the mixture was stirred and dissolved at 50 캜 for 5 hours. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent D9.

&Lt; Synthesis Example 20 - Synthesis of liquid crystal aligning agent D10 &gt;

3.0 g of the liquid crystal aligning agent D9 obtained in Synthesis Example 19 was added to 7.0 g of the liquid crystal aligning agent D8 obtained in Synthesis Example 18, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D10.

&Lt; Synthesis Example 21 - Synthesis of liquid crystal aligning agent D11 &gt;

DA-8 (2.64 g, 8.0 mmol), DA-4 (1.22 g, 8.0 mmol), DA-1 (1.52 g, 4.0 mmol), BODA (2.00 g, 8.0 mmol) ), And reacted at 60 DEG C for 3 hours. Then, PMDA (2.53 g, 11.6 mmol) and NMP (9.9 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (50 g) to dilute it to 6 mass%, acetic anhydride (6.1 g) and pyridine (3.2 g) were added as an imidation catalyst and reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (A) -10. The polyimide had an imidization rate of 60%, a number average molecular weight of 9,000, and a weight average molecular weight of 25,000.

NMP (44.0 g) was added to the resulting polyimide powder (A) -10 (6.0 g), and the mixture was stirred and dissolved at 50 占 폚 for 5 hours. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent D11.

&Lt; Synthesis Example 22-Synthesis of liquid crystal aligning agent D12 &gt;

3.0 g of the liquid crystal aligning agent D11 obtained in Synthesis Example 21 was added to 7.0 g of the liquid crystal aligning agent D8 obtained in Synthesis Example 18, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D12.

&Lt; Synthesis Example 23-Synthesis of liquid crystal aligning agent D13 &gt;

(3.81 g, 10.0 mmol) and DA-4 (1.52 g, 10.0 mmol) were dissolved in NMP (30.0 g) and reacted at 80 ° C for 5 hours , CBDA (0.94 g, 4.8 mmol) and NMP (10.0 g) were added and reacted at 40 ° C for 10 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (50 g) to dilute to 6 mass%, acetic anhydride (4.7 g) and pyridine (3.7 g) were added as imidation catalysts and reacted at 80 ° C for 3 hours. The 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 占 폚 to obtain a polyimide powder (A) -11. The imidization ratio of the polyimide was 55%, the number average molecular weight was 20,000, and the weight average molecular weight was 40,000.

To the resulting polyimide powder (A) -11 (6.0 g), NMP (44.0 g) was added and dissolved by stirring at 50 占 폚 for 5 hours. 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added to this solution and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent D13.

&Lt; Synthesis Example 24 - Synthesis of liquid crystal aligning agent D14 &gt;

DA-6 (6.53 g, 14.0 mmol) and DA-2 (2.40 g, 6.0 mmol) were dissolved in NMP (26.4 g) and reacted at 60 ° C for 3 hours Then, CBDA (2.27 g, 11.6 mmol) and NMP (13.2 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. This polyamic acid solution had a number average molecular weight of 20,000 and a weight average molecular weight of 40000.

NMP (40.0 g) and BCS (30.0 g) were added to the polyamic acid solution (30 g) and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent D14.

&Lt; Synthesis Example 25-Synthesis of &lt; RTI ID = 0.0 &gt;

(41)

<Synthesis of RM11-A>

9.0 g (44.1 mmol) of RM1-A in 18.1 g of NMP was poured into a 300 ml four-necked flask equipped with a magnetic stirrer, and 18.3 g (3.0 eq) of potassium carbonate was added thereto And prewashed with 18.0 g of NMP. 17.6 g (2.2 eq) of 2- (2-bromoethyl) -1,3-dioxolane was added dropwise over 30 minutes while stirring at 80 DEG C, and the mixture was stirred for 18 hours. After 18 hours, 2.4 g (0.3 eq) of 2- (2-bromoethyl) -1,3-dioxolane was further added and the reaction was further performed for 3.5 hours to confirm disappearance of the intermediate. After completion of the reaction, a large amount of water was added to the reaction solution at room temperature, and crystals of the objective substance were precipitated while potassium carbonate was dissolved, followed by filtration. The recovered crystals were subjected to slurry washing twice with pure water and then filtered and dried to obtain 17.8 g of a crude product of RM11-A (yield: 100%, property: pale brown crystals).

<Synthesis of RM11>

To a 500 ml four-necked flask equipped with a magnetic stirrer were added 15.0 g (37.1 mmol) of RM11-A, 16.9 g (2.4 eq) of tin (II) chloride anhydride, After adding 15.9 g (2.2 eq) of ethyl, 52.5 g of a 10 wt% HCl aqueous solution was added dropwise at 20 to 30 DEG C over 45 minutes. Thereafter, the mixture was stirred at room temperature for 7 days, and the raw material and the intermediate were eliminated. Next, 300 g of toluene was added to the reaction solution to divide into two phases, and the hydrochloric acid phase was removed by heating at 50 DEG C under heating. The organic phase was once recovered in the flask and added dropwise into a separable flask equipped with a jacket with 300 g of 6 wt% KOH aqueous solution and stirring at 50 캜. Since insoluble matter occurred at the interface, 150 g of 6 wt% KOH aqueous solution was added. Next, after the alkali phase was removed, the organic phase was washed three times with 300 g of pure water, and then the organic phase was recovered. 0.75 g of activated carbon (item: manufactured by Tokushu Shirasagi dry product, manufactured by Nihon Enviro Chemical), 30.0 g of sodium sulfate and 105 g of THF were added and stirred at room temperature for 30 minutes, followed by solid-liquid separation, Respectively. This was concentrated to dryness, and 45.0 g of MeOH was added, followed by slurry cleaning at room temperature for 1 hour. After filtration, the obtained filtrate was washed with 7.5 g of MeOH, and then dried under reduced pressure to obtain 7.6 g of RM11 (yield: 45%, property: white crystal).

Example 1

0.06 g (10% by mass with respect to solid content) of the polymerizable compound RM1 obtained in Synthesis Example 1 was added to 10.0 g of the liquid crystal aligning agent D1 obtained in Synthesis Example 11 and dissolved by stirring at room temperature for 3 hours to obtain a liquid crystal aligning agent D15 Lt; / RTI &gt;

The obtained liquid crystal aligning agent D15 was stored in a freezer at -20 占 폚 for 1 day and allowed to stand at room temperature for 3 hours. As a result, no precipitate was observed.

Example 2

A liquid crystal aligning agent D16 was prepared in the same manner as in Example 1 except that the amount of the polymerizable compound RM1 in Example 1 was changed to 0.09 g (15 mass% based on the solid content).

The obtained liquid crystal aligning agent D16 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours and thawed. As a result, no precipitate was observed.

Example 3

A liquid crystal aligning agent D17 was prepared in the same manner as in Example 1 except that the polymerizable compound RM2 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1.

The obtained liquid crystal aligning agent D17 was stored in a freezer at -20 占 폚 for 1 day and allowed to stand at room temperature for 3 hours. As a result, no precipitate was observed.

Example 4

A liquid crystal aligning agent D18 was prepared in the same manner as in Example 2 except that the polymerizable compound RM2 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1.

The obtained liquid crystal aligning agent D18 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours and thawed. As a result, no precipitate was observed.

Example 5

A liquid crystal aligning agent D19 was prepared in the same manner as in Example 1 except that the polymerizable compound RM3 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1.

The obtained liquid crystal aligning agent D19 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours and thawed. As a result, no precipitate was observed.

Example 6

A liquid crystal aligning agent D20 was prepared in the same manner as in Example 2 except that the polymerizable compound RM3 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1.

The obtained liquid crystal aligning agent D20 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours and thawed. As a result, no precipitate was observed.

Example 7

A liquid crystal aligning agent D21 was prepared in the same manner as in Example 1 except that the polymerizable compound RM4 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1.

The obtained liquid crystal aligning agent D21 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours, and thawed. As a result, no precipitate was observed.

Example 8

A liquid crystal aligning agent D22 was prepared in the same manner as in Example 2 except that the polymerizable compound RM4 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1.

The obtained liquid crystal aligning agent D22 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours and thawed. As a result, no precipitate was observed.

Example 9

A liquid crystal aligning agent D23 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D2 obtained in Synthesis Example 12 was used instead of the liquid crystal aligning agent D1.

The obtained liquid crystal aligning agent D23 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours and thawed. As a result, no precipitate was observed.

Example 10

A liquid crystal aligning agent D24 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D3 obtained in Synthesis Example 13 was used instead of the liquid crystal aligning agent D1.

The obtained liquid crystal aligning agent D24 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours and thawed. As a result, no precipitate was observed.

Example 11

A liquid crystal aligning agent D25 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D4 obtained in Synthesis Example 14 was used instead of the liquid crystal aligning agent D1.

The obtained liquid crystal aligning agent D25 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours and thawed. As a result, no precipitate was observed.

Example 12

A liquid crystal aligning agent D26 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D5 obtained in Synthesis Example 15 was used instead of the liquid crystal aligning agent D1.

The obtained liquid crystal aligning agent D26 was stored in a freezer at -20 캜 for 1 day and left at room temperature for 3 hours to be thawed. As a result, no precipitate was observed.

Example 13

A liquid crystal aligning agent D27 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D6 obtained in Synthesis Example 16 was used instead of the liquid crystal aligning agent D1.

The obtained liquid crystal aligning agent D27 was stored in a freezer at -20 占 폚 for 1 day and allowed to stand at room temperature for 3 hours. As a result, no precipitate was observed.

Example 14

A liquid crystal aligning agent D28 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D7 obtained in Synthesis Example 17 was used instead of the liquid crystal aligning agent D1.

The obtained liquid crystal aligning agent D28 was stored in a freezer at -20 캜 for 1 day and left at room temperature for 3 hours to be thawed. As a result, no precipitate was observed.

Example 15

A liquid crystal aligning agent D29 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D10 obtained in Synthesis Example 20 was used instead of the liquid crystal aligning agent D1.

The liquid crystal aligning agent D29 thus obtained was stored in a freezer at -20 DEG C for 1 day, left at room temperature for 3 hours, and thawed. As a result, no precipitate was observed.

Example 16

A liquid crystal aligning agent D30 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D12 obtained in Synthesis Example 22 was used instead of the liquid crystal aligning agent D1.

The obtained liquid crystal aligning agent D30 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours, and thawed. As a result, no precipitate was observed.

Example 17

A liquid crystal aligning agent D31 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D13 obtained in Synthesis Example 23 was used instead of the liquid crystal aligning agent D1.

The obtained liquid crystal aligning agent D31 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours, and thawed. As a result, no precipitate was observed.

Example 18

A liquid crystal aligning agent D32 was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent D14 obtained in Synthesis Example 24 was used instead of the liquid crystal aligning agent D1.

The obtained liquid crystal aligning agent D32 was stored in a freezer at -20 캜 for 1 day and left at room temperature for 3 hours to be thawed. As a result, no precipitate was observed.

Example 19

A liquid crystal aligning agent D33 was prepared in the same manner as in Example 1 except that the polymerizable compound RM7 obtained in Synthesis Example 7 was used instead of the polymerizable compound RM1 in Example 1.

The obtained liquid crystal aligning agent D33 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours and thawed. As a result, no precipitate was observed.

Example 20

A liquid crystal aligning agent D34 was prepared in the same manner as in Example 1 except that the polymerizable compound RM8 obtained in Synthesis Example 8 was used instead of the polymerizable compound RM1.

The obtained liquid crystal aligning agent D34 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours and thawed. As a result, no precipitate was observed.

(Comparative Example 1)

A liquid crystal aligning agent D35 was prepared in the same manner as in Example 1 except that the polymerizable compound RM5 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1 in Example 1.

The obtained liquid crystal aligning agent D35 was stored in a freezer at -20 캜 for 1 day and left at room temperature for 3 hours to be thawed. As a result, no precipitate was observed.

(Comparative Example 2)

A liquid crystal aligning agent D36 was prepared in the same manner as in Example 2 except that the polymerizable compound RM5 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1.

The obtained liquid crystal aligning agent D36 was stored in a freezer at -20 占 폚 for 1 day and allowed to stand at room temperature for 3 hours and thawed. As a result, a precipitate was observed.

(Comparative Example 3)

A liquid crystal aligning agent D37 was prepared in the same manner as in Example 1 except that the polymerizable compound RM6 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1 in Example 1.

The obtained liquid crystal aligning agent D37 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours and thawed. As a result, a precipitate was observed.

(Comparative Example 4)

A liquid crystal aligning agent D38 was prepared in the same manner as in Example 2 except that the polymerizable compound RM6 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1.

The obtained liquid crystal aligning agent D38 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours, and thawed. As a result, a precipitate was observed.

(Comparative Example 5)

A liquid crystal aligning agent D39 was prepared in the same manner as in Example 1 except that the polymerizable compound RM9 obtained in Synthesis Example 9 was used instead of the polymerizable compound RM1 in Example 1.

The liquid crystal aligning agent D39 thus obtained was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours and thawed. As a result, no precipitate was observed.

(Comparative Example 6)

A liquid crystal aligning agent D40 was prepared in the same manner as in Example 1 except that the polymerizable compound RM10 obtained in Synthesis Example 10 was used instead of the polymerizable compound RM1.

The obtained liquid crystal aligning agent D40 was stored in a freezer at -20 占 폚 for 1 day, left at room temperature for 3 hours, and thawed. As a result, no precipitate was observed.

Example 21

&Lt; Production of liquid crystal cell &

Using the liquid crystal aligning agent D15 obtained in Example 1, a liquid crystal cell of the SC-PVA system was produced in the same manner as described below.

The liquid crystal aligning agent D15 obtained in Example 1 was spin-coated on the ITO surface of the ITO electrode substrate on which the ITO electrode pattern having a pixel size of 100 mu m x 300 mu m and a line / space of 5 mu m was formed, The plate was dried for 90 seconds, and then fired in a hot air circulating oven at 200 DEG C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.

The liquid crystal aligning agent D1 was spin-coated on the ITO surface on which no electrode pattern was formed, dried for 90 seconds on a hot plate at 80 DEG C and then fired in a hot air circulating oven at 200 DEG C for 30 minutes to obtain a film thickness A liquid crystal alignment film of 100 nm was formed.

A bead spacer of 4 mu m was dispersed on the liquid crystal alignment film of one of the two substrates, and a sealing agent (solvent type thermosetting type epoxy resin) was printed thereon from above. Subsequently, the other side of the substrate on which the liquid crystal alignment film was formed was inwardly bonded to the substrate, and then the sealant was cured to prepare an empty cell. A liquid crystal cell was prepared by injecting liquid crystal MLC-6608 (trade name, manufactured by Merck Ltd.) into this empty cell by a low pressure injection method. The produced liquid crystal cell was then placed in a hot-air circulating oven at 120 ° C for 1 hour, and subjected to redistribution treatment of liquid crystal.

The response speed of the obtained liquid crystal cell was measured by the following method. Thereafter, in a state in which a DC voltage of 15 V was applied to the liquid crystal cell, UV from the outside of the liquid crystal cell through a band-pass filter of 365 nm was irradiated at 10 J / cm2. Thereafter, the response speed was again measured, and the response speeds before and after the UV irradiation were compared.

Further, the pretilt angle of the pixel portion was measured with respect to the cell after UV irradiation.

Further, the cells not irradiated with UV were allowed to stand for one day, and then the polarizing microscope observation of the liquid crystal cell was carried out. When the solubility of the polymerizable compound in the liquid crystal is low, it is considered that precipitation easily occurs in the liquid crystal cell and bright spots are generated. The results are shown in Table 2.

<Measurement method of response speed>

First, a liquid crystal cell was disposed between a set of polarizers in a measuring apparatus comprising a pair of polarizers in the state of backlight, Cross-Nicol, and a light quantity detector in this order. At this time, the pattern of the ITO electrode in which the line / space was formed was made to have an angle of 45 degrees with respect to Cross-Nicol. Then, a rectangular wave having a voltage of + 6V and a frequency of 1 kHz was applied to the above-mentioned liquid crystal cell, a change until the luminance observed by the light amount detector was saturated was injected into the oscilloscope, and when the voltage was not applied The time required for the luminance to change from 10% to 90% was defined as the response speed, with a voltage of 0% and a voltage of +4 V being applied and the saturated luminance value being 100%.

<Measurement of Pretilt Angle>

LC analyzer LCA-LUV42A manufactured by Meier Technology Co., Ltd. was used.

(Examples 22 to 40)

The same operation as in Example 21 was performed except that the liquid crystal aligning agent described in Table 1 was used in place of the liquid crystal aligning agent D15, and the response speeds before and after UV irradiation were compared. Further, the measurement of the pretilt angle and the observation of the bright spot in the liquid crystal cell were also carried out.

In Examples 23, 24, 27 and 28, a hot air circulating oven at 140 캜 was used instead of the hot air circulating oven at 200 캜.

(Example 41)

The liquid crystal aligning agent D9 (3.0 g) obtained in Synthesis Example 19 was added to the liquid crystal aligning agent D8 (7.0 g) obtained in Synthesis Example 18, and the mixture was stirred at room temperature for 5 hours to prepare 10.0 g of the liquid crystal aligning agent D10. To this liquid crystal aligning agent D10 (10.0 g), 0.06 g (10 mass% based on the solid content of liquid crystal aligning agent D10) of RM11 synthesized in Synthesis Example 25 was added and dissolved by stirring at room temperature for 3 hours to obtain liquid crystal aligning agent D41 Was prepared.

The obtained liquid crystal aligning agent D41 was stored in a freezer at -20 캜 for 1 day and left at room temperature for 3 hours to be thawed. As a result, no precipitate was observed.

(Example 42)

The liquid crystal aligning agent D41 prepared in Example 41 was subjected to the same operations as those in Example 21, and the response speeds before and after UV irradiation were compared. Further, the measurement of the pretilt angle and the observation of the bright spot in the liquid crystal cell were carried out.

(Comparative Examples 7 to 12)

The same operations as in Example 21 were carried out except that the liquid crystal aligning agents D35 to D40 were used instead of the liquid crystal aligning agent D15, and the response speeds before and after UV irradiation were compared. Further, the measurement of the pretilt angle and the observation of the bright spot in the liquid crystal cell were also carried out.

Comparing Examples 21 and 22 with Comparative Examples 7 and 8, in particular, comparing Example 22 and Comparative Example 8, it can be seen that when RM1 and RM5 have the same skeleton (RM1 and RM5) , The solubility in the varnish is improved by the introduction of the halogen group. It is also seen that the solubility of the polymerizable compound in the liquid crystal is improved by observation of the bright spot in the liquid crystal cell.

From the same point of view, it was confirmed that in Example 39 and Comparative Example 11 (difference between RM7 and RM9 in F substitution (RM7) and no RM9)), Example 40 and Comparative Example 12 (RM8 and RM10 have F substitution (Difference between RM8 and RM10), it is found that the solubility of the polymerizable compound in the liquid crystal is improved by observing the bright spot in the liquid crystal cell.

From Example 25 and Example 26, it was confirmed that introduction of a halogen group improves the solubility of the polymerizable compound in the liquid crystal aligning agent even when it has a terphenyl skeleton that is stiffer than the biphenyl skeleton and has low solubility, And the storage stability is also improved.

Similarly, from Examples 23, 24, 27, and 28, high solubility of the polymerizable compound in the liquid crystal aligning agent was also confirmed.

Thus, it can be seen that the halogen-substituted polymerizable compound has improved solubility in the liquid crystal aligning agent of the polymerizable compound, exhibits high storage stability of the liquid crystal aligning agent, and improved solubility in the liquid crystal.

Further, it was confirmed that the liquid crystal aligning agent to which the halogen-substituted polymerizable compound was added exhibited a tilt angle similarly to the liquid crystal aligning agent to which the polymerizable compound not substituted with halogen was added in the liquid crystal cell of the SC-PVA system .

Claims (7)

[I] General formula I-1 to I-3
(Wherein Ar ₁ to Ar ₃ are each independently a divalent organic group containing an aromatic ring having at least one halogen substituent, and n ₁ , n ₂ and n ₆ are each independently 0 to 6 N ₃ , n ₄ and n ₅ each independently represent an integer of 1 to 6, and R ₁ to R ₃ each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, which is a linear or branched chain, And at least one polymerizable compound selected from the group consisting of compounds represented by the following formula: And
[II] at least one polymer selected from polyimide precursors and polyimides;
And a liquid crystal aligning agent.
[Chemical Formula 1]

The method according to claim 1,
Wherein Ar ₁ ~ Ar ₃ is in each independently represent the following formula (Formula IB-1 ~ IB-3, X represents a halogen, m ₁ ~ m ₈ are each independently an integer, m ₁ + m ₂ is greater than or equal to 1 8 or less, m ₃ + m ₄ + m ₅ is 1 or more and 10 or less, and m ₆ + m ₇ + m ₈ is 1 or more and 12 or less).
(2)

3. The method of claim 2,
The group represented by the formula IB-1 is a group represented by the formula IB-1a, the group represented by the formula IB-2 is a group represented by the formula IB-2a, and the group represented by the formula IB- A liquid crystal aligning agent which is a group represented by-3a.
(3)

4. The method according to any one of claims 1 to 3,
The [II] polymer may be (I) a side chain that vertically aligns the liquid crystal; And a liquid crystal aligning agent. 5. The method of claim 4,
Wherein the polymer [II] comprises: (II) a photoreactive side chain; And a liquid crystal aligning agent. A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of claims 1 to 5. A liquid crystal display element having the liquid crystal alignment film according to claim 6.