JP6547565B2 - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal element.

  Conventionally, as liquid crystal elements, various types of liquid crystal having different operation principles have been developed. For example, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, VA (Vertical Alignment) type, IPS type ( BACKGROUND Various liquid crystal elements such as in-plane switching) and fringe field switching (FFS) types are known. These liquid crystal elements have a liquid crystal alignment film for aligning liquid crystal molecules. As a material of a liquid crystal aligning film, a polyamic acid and a polyimide are generally used from the point which various characteristics, such as heat resistance, mechanical strength, and affinity with a liquid crystal, are favorable.

  In recent years, various liquid crystal aligning agents have been proposed to further improve the display performance of liquid crystal display panels. For example, for the purpose of reducing the afterimage, it has been proposed to form a liquid crystal alignment film using a liquid crystal alignment agent containing a polyimide having a nitrogen atom in a portion other than an imide group or a precursor thereof (for example, Patent Document 1) , 2). Patent Documents 1 and 2 propose using a diaminodiphenylamine as a monomer to improve voltage holding characteristics and reduce sticking.

Patent No. 4052307 Patent No. 4052308 gazette

  In recent years, liquid crystal display panels have come to be used in various applications such as liquid crystal televisions, personal computers, car navigation systems, mobile phones, smart phones, information displays, etc., and the demand for display quality is stricter than before. It has become. However, in the cases of Patent Documents 1 and 2, it can not be said that the level required for recent afterimage is sufficiently satisfied. Further, in the recent FFS liquid crystal display panel, the contrast is important, and a liquid crystal alignment film with little coloring is required.

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a liquid crystal aligning agent which can obtain a liquid crystal element having excellent afterimage characteristics and voltage holding ratio and having high transparency and excellent contrast. I assume.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the above subjects, the present inventors find out that the said subject is solvable by making the liquid crystal aligning agent contain the polymer which has a specific structure, and this invention It came to complete. Specifically, the following means are provided by the present disclosure.

（式（１）中、Ｒ^１及びＲ^５は、それぞれ独立にアルカンジイル基であり、Ｒ^２及びＲ^４は、それぞれ独立に、水素原子、炭素数１〜１２の１価の炭化水素基又は保護基である。Ｒ^０は、環式構造を有する２価の有機基（ただし、Ｒ^０が−ＮＲ^２−及び−ＮＲ^４−にカルボニル基で結合している場合を除く。）である。） <1> Liquid crystal alignment containing at least one selected from the group consisting of a polyamic acid, a polyamic acid ester, a polyimide and a polyamide, and a polymer [P] having a partial structure represented by the following formula (1) Agent.

(In formula (1), R ¹ and R ⁵ are each independently an alkanediyl group, and R ² and R ⁴ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or R ⁰ is a divalent organic group having a cyclic structure (except when R ⁰ is bonded to —NR ² — and —NR ⁴ — via a carbonyl group). )

  According to the present disclosure, it is possible to obtain a liquid crystal element having excellent afterimage characteristics and voltage holding ratio, and having high transparency and excellent contrast.

  Below, each component contained in the liquid crystal aligning agent of this indication, and the other component arbitrarily mix | blended as needed are demonstrated.

<Polymer [P]>
The liquid crystal aligning agent of the present disclosure is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyamide, and a partial structure represented by the above formula (1) (hereinafter, “specific partial structure” Containing a polymer [P].

Examples of R ¹ and R ^{5 in} the above formula (1) include methylene group, ethylene group, propylene group, butylene group, pentanediyl group, hexanediyl group and the like, which may be linear or branched. Preferably, they are a methylene group, an ethylene group and a 1,3-propylene group.
Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms of R ² and ^{R 4,} chain hydrocarbon group having 1 to 12 carbon atoms, alicyclic hydrocarbon group having 3 to 12 carbon atoms, 6 carbon atoms 12 aromatic hydrocarbon groups can be mentioned. Here, in the present specification, “a chain hydrocarbon group” means a saturated or unsaturated linear hydrocarbon group and a branched hydrocarbon composed only of a chain structure without containing a cyclic structure in the main chain. Means a group. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. However, it does not need to be comprised only with the structure of alicyclic hydrocarbon, and the thing which has a chain-like structure in the part is also included. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed of only an aromatic ring structure, and a part thereof may contain a chain structure or an alicyclic hydrocarbon structure.

（式（３−１）〜式（３−５）中、Ａｒ^１０は炭素数６〜１０の１価の芳香環基であり、Ｒ^２１は炭素数１〜１２のアルキル基であり、Ｒ^２３はメチレン基又はエチレン基である。「＊」は窒素原子に結合する結合手を示す。） The protective group of R ² and R ⁴ is preferably a group which is released by heat. Specific examples of R ² and R ⁴ include, for example, carbamate-based protecting group, amide-based protecting group, imide-based protecting group, sulfonamide-based protecting group, and each of the following formulas (3-1) to (3-5) And the like.

(In the formulas (3-1) to (3-5), Ar ¹⁰ is a monovalent aromatic ring group having 6 to ¹⁰ carbon atoms, R ²¹ is an alkyl group having 1 to 12 carbon atoms, R ²³ Is a methylene group or an ethylene group, "*" indicates a bond bonded to a nitrogen atom.)

Ar ^{10 in the} above formula (3-2) is a group obtained by removing one hydrogen atom from an aromatic ring having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. Examples of the alkyl group having 1 to 12 carbon atoms R ²¹ of formula (3-4), for example a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like, these are also linear It may be branched. The protective group for R ² and R ⁴ is particularly preferably a tert-butoxycarbonyl group, from the viewpoint of high thermal releasability and the ability to reduce the remaining amount of the deprotected moiety in the film. R ² and R ⁴ are preferably a hydrogen atom, a methyl group, a phenyl group, a tolyl group, a t-butoxycarbonyl group, or a benzyl group.

The cyclic structure R ⁰ has, for example, aromatic hydrocarbon ring, an aliphatic ring, such heterocycles. As specific examples of these, as an aromatic hydrocarbon ring, for example, a benzene ring, biphenyl ring, naphthalene ring, anthracene ring and the like; as an aliphatic ring, for example, a cyclohexylene ring and the like; A piperazine ring, a pyridine ring, a pyrazine ring, a pyrimidine ring and the like can be mentioned respectively. The cyclic structure of R ⁰ is preferably at least one selected from the group consisting of an aromatic hydrocarbon ring and a heterocyclic ring from the viewpoint of orientation, more preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. Is more preferred.
The cyclic structure possessed by R ⁰ may have a substituent at the ring portion. As the said substituent, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc.), an alkyl group, an alkoxy group etc. are mentioned, for example. The number of these rings possessed by R ⁰ may be one or more, preferably one to six, more preferably one to four, and still more preferably two to four.

The divalent organic group of R ⁰ has at least one cyclic structure. R ⁰ is, for example, a hydrocarbon group (including a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group), a heterocyclic group, etc. with respect to —NR ² — and —NR ⁴ — It is preferable that it is linked and is bound to -NR ² -and -NR ⁴ -in a cyclic structure. When R ⁰ is bonded to -NR ² -and -NR ⁴ -in a cyclic structure, it may be bonded to both -NR ² -and -NR ^4-in one cyclic structure. , -NR 2 ^- and ring attached to, -NR 4 ^- may be different from the ring attached to. Preferably it is the latter. -NR 2 ^- and -NR 4 ^- Preferable examples of the cyclic structure bonded to the description of the cyclic structure R ⁰ has applies.

（式（２）中、Ａｒ^１及びＡｒ^４は、それぞれ独立に、単結合又は環式基である。Ｒ^０、Ｒ^１、Ｒ^２、Ｒ^４及びＲ^５は、上記式（１）と同義である。） The method for obtaining the polymer [P] is not particularly limited, but it is preferable to use the method represented by the following formula (2) (hereinafter, also referred to as "specific diamine").

(In formula (2), Ar ¹ and Ar ⁴ are each independently a single bond or a cyclic group. R ⁰ , R ¹ , R ² , R ⁴ and R ⁵ are as defined in the above formula (1) Is)

In Ar ¹ and Ar ^{4 in} the above formula (2), the cyclic group is an n-valent group obtained by removing n hydrogen atoms from the ring part of the cyclic structure. The description of R ^{0 in} the above formula (1) applies to specific examples of the cyclic structure. The cyclic group of Ar ¹ and Ar ⁴ may have a substituent such as a halogen atom, an alkyl group or an alkoxy group in the ring portion.
Ar ¹ and Ar ⁴ are preferably a phenylene group, a biphenylene group, a naphthalene group or a pyridylene group.

（式（０−ＤＡ）中、Ａｒ^５及びＡｒ^６は、それぞれ独立に環式基であり、Ｒ^６は、２価の炭化水素基、複素環を有する基、アゾ基、−Ｃ_ｍＨ_２ｍ−ＮＨＣＯＮＨ−Ｃ_ｍＨ_２ｍ−、又は−Ｏ−Ｃ_ｍＨ_２ｍ−Ｏ−である。ｒは０又は１であり、ｍは１〜２０の整数である。Ｒ^１、Ｒ^２、Ｒ^４及びＲ^５は、上記式（１）と同義であり、Ａｒ^１及びＡｒ^４は、上記式（２）と同義である。）

（式（１−ＤＡ）中、Ａｒ^７及びＡｒ^８は、それぞれ独立に環式基であり、Ｒ^７は、水素原子、炭素数１〜１２の１価の炭化水素基又は保護基である。ｔは１〜３の整数である。ｔが２又は３の場合、式中の複数のＡｒ^８、複数のＲ^７は、それぞれ独立して上記定義を有する。Ｒ^１、Ｒ^２、Ｒ^４及びＲ^５は、上記式（１）と同義であり、Ａｒ^１及びＡｒ^４は、上記式（２）と同義である。） Preferred specific examples of the specific diamine include, for example, a compound represented by the following formula (0-DA) and a compound represented by the following formula (1-DA).

In the formula (0-DA), Ar ⁵ and Ar ⁶ each independently represent a cyclic group, and R ⁶ represents a divalent hydrocarbon group, a group having a heterocycle, an azo group, —C _m H _{2m -NHCONH-C m H 2m} -, or _{-O-C m} H 2m -O- in which .r is 0 or 1, m is an integer of ^{1~20 .R 1, R 2, R} 4 and R ⁵ has the same meaning as the above formula (1), and Ar ¹ and Ar ⁴ have the same meaning as the above formula (2).

In Formula (1-DA), Ar ⁷ and Ar ⁸ are each independently a cyclic group, and R ⁷ is a hydrogen atom, a monovalent hydrocarbon group of 1 to 12 carbon atoms, or a protecting group. t is an integer of 1 to 3. When t is 2 or 3, a plurality of Ar ⁸ and a plurality of R ⁷ in the formula each independently have the above-mentioned definition. R ¹ , R ² , R ⁴ and R ⁵ has the same meaning as the above formula (1), and Ar ¹ and Ar ⁴ have the same meaning as the above formula (2).

With regard to formula (0-DA), the descriptions of Ar ¹ and Ar ^{4 in} the above formula (2) apply to Ar ⁵ and Ar ⁶ . Examples of the divalent hydrocarbon group of R ⁶ include a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. When R ⁶ is a group having a heterocycle, examples of the heterocycle include pyridine, pyrazine, piperidine, piperazine and the like.
With regard to formula (1-DA), the descriptions of the cyclic groups of Ar ¹ and Ar ⁴ of the above formula (2) apply to Ar ⁷ and Ar ⁸ . The description of R ² and R ^{4 in} the above formula (1) is applied to R ⁷ .

（式（０−１）〜式（０−１４）及び式（１−１）〜式（１−２１）中、「Ｂｏｃ」は、ｔｅｒｔ−ブトキシカルボニル基を示す。ｎは１〜３の整数であり、ｍは１〜２０の整数である。） As a specific example of a specific diamine, the compound etc. which are represented, for example with each of following formula (0-1)-formula (0-14) and Formula (1-1)-formula (1-21) are mentioned.

(In the formulas (0-1) to (0-14) and formulas (1-1) to (1-21), “Boc” represents a tert-butoxycarbonyl group. N is an integer of 1 to 3) And m is an integer of 1 to 20.)

Among the above, the specific diamines include, among the above, the above formulas (0-1) to (0-6), formulas (0-8) to (0-13) and formulas (1-1) to (1 3), and the compound represented by each of Formula (1-15)-Formula (1-17) are preferable. In addition, specific diamine can be used individually by 1 type or in combination of 2 or more types.
In the synthesis of the polyamic acid, the proportion of the specific diamine used is at least 5 mol% with respect to the total amount of diamine used in the synthesis of the polyamic acid, from the viewpoint of reducing afterimage, high voltage holding ratio and high contrast. Is preferably 5 to 80 mol%, and more preferably 10 to 70 mol%.

Specific diamines can be synthesized by combining conventional methods of organic chemistry as appropriate. Specifically, for example, as shown in the following scheme 1, a diamine represented by the above formula (2) is reacted with nitrobenzaldehyde to form a Schiff salt using a diamine having a group R ⁰ as a starting material, and then reduced. Can be synthesized. Alternatively, as shown in Scheme 2, a diamine having a group R ⁰ may be used as a starting material, reacted with nitrobenzyl alcohol and then reduced for synthesis. Alternatively, as shown in Scheme 3, the amino group of the diamine having a group R ⁰ may be protected with t-butoxycarbonyl or the like, and then the compound may be synthesized by condensing nitrobenzyl bromide in the presence of a base, reducing and deprotecting. it can. In addition, the synthesis | combining method of specific diamine is not limited above.

<Polyamic acid>
When the polymer [P] is a polyamic acid, the polyamic acid can be obtained by reacting tetracarboxylic acid dianhydride with a diamine containing a specific diamine.
(Tetracarboxylic acid dianhydride)
Examples of tetracarboxylic acid dianhydrides used in the synthesis of polyamic acids include aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aromatic tetracarboxylic acid dianhydrides. . Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as butane tetracarboxylic acid dianhydride;

Examples of alicyclic tetracarboxylic acid dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane -2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- Without 1,2-dicarboxylic acid 3,5,6-Tricarboxy-2-carboxymethyl norbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-dianhydride, 4,9-di anhydride Oxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, bicyclo [2.2.2 Oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, ethylene glycol bis (anhydrotrimellitate), 1 , 3-Propylene glycol bis (an Hydrotrimellitate), p-phenylene bis (trimellitic acid monoester anhydride) and the like;
Examples of the aromatic tetracarboxylic acid dianhydride include, for example, pyromellitic acid dianhydride and the like, and besides, tetracarboxylic acid dianhydride described in JP-A-2010-97188 can be used. Other tetracarboxylic acid dianhydrides can be used singly or in combination of two or more.

(Diamine)
In the synthesis of the polyamic acid, the specific diamine may be used alone, but diamines other than the specific diamine (hereinafter, abbreviated as "other diamines") may be used.

  Examples of other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, diamino organosiloxanes and the like. Specific examples thereof include aliphatic diamines such as m-xylylene diamine, 1,3-propane diamine, pentamethylene diamine, hexamethylene diamine and the like; and alicyclic diamines such as 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine) and the like;

（式（Ｅ−１）中、Ｘ^I及びＸ^IIは、それぞれ独立に、単結合、−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−であり、Ｒ^Ｉは炭素数１〜３のアルカンジイル基であり、Ｒ^ＩＩは単結合又は炭素数１〜３のアルカンジイル基であり、ａは０又は１であり、ｂは０〜２の整数であり、ｃは１〜２０の整数であり、ｄは０又は１である。但し、ａ及びｂが同時に０になることはない。）
で表される化合物などの配向性基含有ジアミン： As aromatic diamines, for example, dodecanoxydiaminobenzene, tetradecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, cholesteryloxydiaminobenzene, cholestanyl diaminobenzoate, cholesteryl diaminobenzoate, diaminobenzoic acid Lanostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butyl Cyclohexane, the following formula (E-1)

(In formula (E-1), X ^I and X ^II are each independently a single bond, -O-, -COO- or -OCO-, and R ^I is an alkanediyl group having 1 to 3 carbon atoms R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1. However, a and b can not simultaneously be 0.)
Orientation group-containing diamine such as a compound represented by

p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis (4-amino) Phenoxy) pentane, bis [2- (4-aminophenyl) ethyl] hexanedioic acid, N, N-bis (4-aminophenyl) methylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, 4,4 '-(p-phenylenediisopropylidene) bisaniline 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4 4'-bis (4-aminophenoxy) biphenyl, N, N'-bis (4-aminophenyl) -benzidine, 1,4-bis- (4-aminophenyl) -piperazine, 4- (4-aminophenoxycarbonyl) ) -1- (4-aminophenyl) piperidine, 4,4 ′-[4,4′-propane-1,3-diylbis (piperidine-1,4-diyl)] dianiline, 3,5-diaminobenzoic acid and the like Non-side chain type diamines, etc .;
Examples of diaminoorganosiloxanes include, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and besides, diamines described in JP-A-2010-97188 can be used. Other diamines may be used singly or appropriately in combination of two or more of these compounds.

(Synthesis of polyamic acid)
The polyamic acid can be obtained by reacting the above-mentioned tetracarboxylic acid dianhydride and diamine with a molecular weight modifier as required. The ratio of tetracarboxylic acid dianhydride and diamine used in the synthesis reaction of the polyamic acid is 0.2 to 2 acid anhydride groups of tetracarboxylic acid dianhydride to 1 equivalent of amino group of diamine. The ratio which becomes equivalent is preferable. In the synthesis of the polyamic acid as the polymer [P], the use ratio of the specific diamine is the total amount of the specific diamine with respect to the total amount of the monomers used in the synthesis, from the viewpoint of sufficiently enhancing the reduction effect of the afterimage. The amount is preferably 10 mol% or more, more preferably 20 to 80 mol%, and still more preferably 25 to 70 mol%.

  Examples of molecular weight modifiers include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. It can be mentioned. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less based on 100 parts by mass of the total of tetracarboxylic acid dianhydride and diamine to be used.

The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C. The reaction time is preferably 0.1 to 24 hours. Examples of the organic solvent used for the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like. Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol It is preferable to use, as a solvent, one or more selected from the group consisting of halogenated phenols and a mixture of one or more thereof and another organic solvent. The amount (a) of organic solvent used is such that the total amount (b) of tetracarboxylic acid dianhydride and diamine is 0.1 to 50% by mass with respect to the total amount (a + b) of the reaction solution. Is preferred.
As described above, a reaction solution in which the polyamic acid is dissolved is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, or may be used for preparation of a liquid crystal aligning agent after the polyamic acid contained in the reaction solution is isolated.

<Polyamic acid ester>
The polyamic acid ester as the polymer [P] can be obtained, for example, by a method of reacting tetracarboxylic acid diester dihalide and diamine.
The tetracarboxylic acid diester dihalide used can be obtained by reacting the tetracarboxylic acid diester with a suitable chlorinating agent such as thionyl chloride. The tetracarboxylic acid diester can be obtained, for example, by reacting the tetracarboxylic acid dianhydride exemplified in the synthesis of polyamic acid with an alcohol such as methanol or ethanol. As a diamine, a specific diamine may be used independently and other diamine may be used together. Specific examples of the diamine used include the specific diamines and other diamines exemplified in the description of the synthesis of polyamic acid.

  The use ratio of the tetracarboxylic acid diester dihalide and the diamine to be subjected to the synthesis reaction of the polymer [P] is the group “—COX (X is a tetracarboxylic acid diester dihalide) with respect to 1 equivalent of the amino group of the diamine. The ratio by which "a halogen atom)" is set to 0.2-2 equivalent is preferable. The reaction of the tetracarboxylic acid diester dihalide with the diamine is preferably carried out in an organic solvent in the presence of a base. The reaction temperature at this time is preferably -30 ° C to 150 ° C. The reaction time is preferably 0.1 to 48 hours. As the organic solvent used for the reaction, the description of the organic solvent that can be used for the synthesis reaction of polyamic acid can be applied. Examples of the base used in the above reaction include tertiary amines such as pyridine, triethylamine, N-ethyl-N, N-diisopropylamine, etc .; sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, potassium hydroxide, sodium, potassium etc. The alkali metals of the following can preferably be used. The amount of the base used is preferably 2 to 4 moles relative to 1 mole of diamine.

  As described above, a reaction solution obtained by dissolving the polyamic acid ester is obtained. The reaction solution may be used as it is for the preparation of a liquid crystal aligning agent, or the polyamic acid ester contained in the reaction solution may be isolated for the preparation of a liquid crystal aligning agent. The polyamic acid ester may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. In addition, the polyamic acid ester as polymer [P] is not limited to said synthetic method, For example, the method of making polyamic acid as polymer [P], alcohol, or halogenated alkyl react, tetracarboxylic-acid diester It can also be obtained by a method of reacting a diamine with a diamine.

<Polyimide>
The polyimide as the polymer [P] can be obtained, for example, by dehydration ring closure and imidization of the polyamic acid synthesized as described above. When polyamic acid is subjected to dehydration ring closure to form a polyimide, the reaction solution of polyamic acid may be subjected to dehydration ring closure reaction as it is, or the polyamic acid contained in the reaction solution is isolated and then subjected to dehydration ring closure reaction. It is also good.

  The polyimide may be a completely imidized product obtained by dehydrating and ring closing all of the amic acid structure of the precursor polyamic acid, and only a part of the amic acid structure may be dehydrating and ring closing, and the amic acid structure and the imide. It may be a partial imidate coexisting with a ring structure. It is preferable that the imidation ratio is 20% or more, and, as for the polyimide used for reaction, it is more preferable that it is 30 to 99%. The imidation ratio is a percentage representing the ratio of the number of imide ring structures to the total number of amic acid structures of polyimide and the number of imide ring structures. Here, part of the imide ring may be an isoimide ring.

The dehydration ring closure of polyamic acid is preferably performed by a method of heating polyamic acid or a method of dissolving polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to this solution, and heating as necessary. . Among these, the latter method is preferred. In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to a solution of polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride and the like can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 moles relative to 1 mole of the polyamic acid's amic acid structure. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydrating ring closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. As an organic solvent used for a dehydration ring-closing reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C. The reaction time is preferably 1.0 to 120 hours.
Thus, a reaction solution containing a polyimide is obtained. The reaction solution may be used as it is for the preparation of a liquid crystal aligning agent, or may be used for the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring closure catalyst from the reaction solution. You may use for preparation of an orientation agent.

<Polyamide>
The polyamide as the polymer [P] can be obtained, for example, by a method of reacting a dicarboxylic acid dihalide and a diamine.
The dicarboxylic acid dihalide used in the synthesis of the polyamide can be obtained by reacting the dicarboxylic acid with a suitable chlorinating agent such as thionyl chloride.
The dicarboxylic acid to be used here is not particularly limited, and examples thereof include aliphatic dicarboxylic acids such as succinic acid, adipic acid, 3,3-diethyl succinic acid, sebacic acid, fumaric acid and muconic acid; cyclobutane dicarboxylic acid, 1- Dicarboxylic acids having an alicyclic structure such as cyclobutenedicarboxylic acid, cyclopentanedicarboxylic acid and cyclohexanedicarboxylic acid; Phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid 4,4'-Diphenyletherdicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3 '-[4,4'-(methylenedi-p-phenylene] )] Dipropionic acid, 4,4 ′-[4,4 ′-(oxydi-p-phenylene)] dibutyric acid Dicarboxylic acids having aromatic ring; and the like. In addition, dicarboxylic acid dihalide can be used individually by 1 type or in combination of 2 or more types.
In the synthesis of polyamide, a specific diamine may be used alone as the diamine, or other diamine may be used in combination. Specific examples of the diamine used include the specific diamines and other diamines exemplified in the description of the synthesis of polyamic acid. Also, the amino group of the diamine may be t-butoxycarbonylated to impart the solubility of the polyamide. In addition, diamine can be used individually by 1 type or in combination of 2 or more types.

The ratio of dicarboxylic acid dihalide and diamine to be used in the synthesis reaction of the polymer [P] is the group "-COX (X is a halogen atom)" of the dicarboxylic acid dihalide relative to one equivalent of the amino group of diamine. A ratio of 0.2 to 2 equivalents is preferred. The reaction of the dicarboxylic acid dihalide with the diamine is preferably carried out in an organic solvent in the presence of a base. The reaction temperature at this time is preferably 0 ° C to 200 ° C. The reaction time is preferably 0.5 to 48 hours.
As the organic solvent used for the reaction, it is preferable to use an organic solvent, for example, preferably using tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and the like. it can. The amount of the organic solvent used is preferably 400 to 900 parts by mass with respect to 100 parts by mass of the total amount of the dicarboxylic acid dihalide and the diamine.
Examples of the base used in the above reaction include tertiary amines such as pyridine, triethylamine and N-ethyl-N, N-diisopropylamine; alkali metals such as sodium hydride, potassium hydride and potassium hexamethyldisilazane; It can be used preferably. The amount of the base used is preferably 2 to 4 moles relative to 1 mole of diamine.

  As described above, the reaction solution in which the polyamide is dissolved is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, or may be used for preparation of a liquid crystal aligning agent after the polyamide contained in the reaction solution is isolated. In addition, the polyamide as a polymer [P] can also be obtained by reaction of dicarboxylic acid and diamine other than said synthetic | combination method, for example.

The solution viscosity and weight average molecular weight (Mw) of the polymer [P] can be appropriately selected according to the main skeleton. For example, in the case of polyamic acid, polyamic acid ester, polyimide, and polyamide, the solution viscosity of the polymer is that having a solution viscosity of 10 to 800 mPa · s when this is a solution having a concentration of 10% by mass. Is preferred, and more preferred is one having a solution viscosity of 15 to 500 mPa · s. In addition, the solution viscosity (mPa · s) of the polymer [P] is 10% by mass of concentration prepared using a good solvent of the polymer [P] (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) It is the value measured at 25 ° C. using a type E rotational viscometer for the polymer solution.
The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) for the polymer [P] is preferably 1,000 to 500,000, more preferably 2,000 to 300, It is 000. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.

<Other ingredients>
The liquid crystal aligning agent of this indication may contain other components other than polymer [P]. Examples of such other components include other polymers having no specific partial structure, and compounds having at least one epoxy group in the molecule (hereinafter, also referred to as "epoxy group-containing compounds").

  The above-mentioned other polymers can be used to improve various properties such as electric characteristics such as afterimage and transparency and the like, or for the purpose of cost reduction. Such other polymers include, for example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, or poly (meth) acrylate. Examples thereof include polymers having a main skeleton and having no specific partial structure. Among these, at least one polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane and polyamide can be preferably used as the other polymer.

  An epoxy group containing compound can be used in order to improve the adhesiveness with the substrate surface in a liquid crystal aligning film, and an electrical property. As such epoxy group-containing compounds, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl [4,4′- Methylenebisaniline], N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine etc. can be mentioned as a preferable thing. In addition, as an example of an epoxy-group containing compound, the epoxy-group-containing polyorganosiloxane of WO2009 / 096598 can be used. When the epoxy group-containing compound is blended in the liquid crystal aligning agent, the blending ratio is preferably 40 parts by mass or less with respect to a total of 100 parts by mass of the polymer contained in the liquid crystal aligning agent. More preferably, it is 30 parts by mass.

  As other components, in addition to the above, functional silane compounds, compounds having at least one oxetanyl group in the molecule, antioxidants, metal chelate compounds, curing accelerators, surfactants, fillers, dispersants And photosensitizers. These compounding ratios can be suitably selected according to each compound in the range which does not impair the effect of this invention.

  In the liquid crystal aligning agent of the present disclosure, the compounding ratio of the polymer [P] can be appropriately selected at 100 parts by mass or less with respect to 100 parts by mass of the total amount of the polymer [P] and the other polymers. From the viewpoint of achieving cost reduction while sufficiently enhancing the reduction effect of the residual image by the polymer [P], the voltage holding ratio and the contrast characteristic, the total amount of the polymer [P] and the other polymer is 100 parts by mass The amount is preferably 5 to 99 parts by mass, and more preferably 10 to 90 parts by mass.

（式（ｐ−１）〜式（ｐ−３）中、Ｒ^５１は４価の有機基であり、Ｒ^５５は２価の有機基であり、Ｒ^５２及びＲ^５３は、それぞれ独立に、水素原子又は１価の有機基であり、Ｒ^５４は、上記式（１）で表される部分構造を有する２価の有機基である。） The polymer [P] preferably has a partial structure derived from a specific diamine. Specifically, a group consisting of a partial structure represented by the following formula (p-1), a partial structure represented by the following formula (p-2), and a partial structure represented by the following formula (p-3) And polymers having at least one partial structure selected from

(In the formulas (p-1) to (p-3), R ⁵¹ is a tetravalent organic group, R ⁵⁵ is a divalent organic group, and R ⁵² and R ⁵³ are each independently hydrogen) R ⁵⁴ is an atom or a monovalent organic group, and R ⁵⁴ is a divalent organic group having a partial structure represented by the above formula (1).

Examples of the monovalent organic group represented by R ⁵² and R ⁵³ in the above formula (p-1) include a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a group having a cinnamic acid structure. The tetravalent organic group of R ⁵¹ is a residue obtained by removing two acid anhydride groups from tetracarboxylic acid dianhydride. Specific examples of the tetracarboxylic acid dianhydride include the tetracarboxylic acid dianhydride exemplified above. R ⁵⁴ has a partial structure represented by the above formula (1), and specifically, is a residue obtained by removing two primary amino groups from the above specific diamine. The divalent organic group of R ⁵⁵ is a residue obtained by removing two carboxyl groups from the dicarboxylic acid exemplified in the description of the polyamide.

<Solvent>
The liquid crystal aligning agent of the present disclosure is prepared as a liquid composition in which the polymer [P] and the other components optionally used are preferably dispersed or dissolved in a suitable solvent.

  As an organic solvent to be used, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol i-propyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether Ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, Propylene carbonate etc. can be mentioned. These can be used alone or in combination of two or more.

  The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc. It is the range of 1-10 mass%. That is, a liquid crystal aligning agent is apply | coated on the substrate surface so that it may mention later, Preferably by heating, the coating film which is a liquid crystal aligning film, or the coating film used as a liquid crystal aligning film is formed. At this time, when the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coatability decreases. There is a tendency.

<Liquid crystal element>
The liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited. For example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB (Optically Compensated Bend) It can be applied to various modes such as a mold. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. Step 1 differs in the substrate used according to the desired operation mode. Steps 2 and 3 are common to each operation mode.

[Step 1: Formation of a Coating]
First, a liquid crystal aligning agent is applied on a substrate, and then a coating film is formed on the substrate by heating the coated surface. As the substrate, for example, glass such as float glass and soda glass; transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and poly (alicyclic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc. It can be used. In the case of manufacturing a TN type, STN type or VA type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. In the case of manufacturing a liquid crystal element of IPS type or FFS type, a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape is used, and a counter substrate not provided with an electrode is used. . For example, a film made of a metal such as chromium can be used as the metal film. The application to the substrate is carried out preferably on the electrode forming surface by offset printing, spin coating, roll coater method or inkjet printing.

  After the application of the liquid crystal alignment agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal alignment agent. The pre-bake temperature is preferably 30 to 200 ° C. The pre-bake time is preferably 0.25 to 10 minutes. Thereafter, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and optionally thermally imidizing the amic acid structure present in the polymer. The baking temperature (post-baking temperature) at this time is preferably 80 to 300 ° C., and the post-baking time is preferably 5 to 200 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 μm. After the liquid crystal aligning agent is applied onto the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film to be the liquid crystal alignment film.

[Step 2: Alignment Treatment]
In the case of producing a TN type, STN type, IPS type or FFS type liquid crystal element, a treatment (alignment treatment) for imparting liquid crystal alignment ability to the coating film formed in the above step 1 is carried out. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. As the alignment treatment, for example, a rubbing treatment for imparting a liquid crystal alignment ability to a coating film by rubbing the coating film in a fixed direction with a roll wound with a cloth made of fibers such as nylon, rayon, cotton, etc. And photo-alignment treatment to impart liquid crystal alignment ability to the coating film. On the other hand, in the case of producing a vertical alignment type liquid crystal element, the coating film formed in the above step 1 can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to alignment treatment.

[Step 3: Construction of Liquid Crystal Cell]
(3-A) A liquid crystal cell is manufactured by preparing two substrates on which the liquid crystal alignment film is formed as described above, and disposing a liquid crystal between two substrates disposed opposite to each other. As a method of manufacturing a liquid crystal cell, (1) two substrates are disposed opposite to each other with a gap (cell gap) such that the respective liquid crystal alignment films face each other, and the peripheral portion of the two substrates is sealed. Liquid crystal is injected and filled into a cell gap partitioned by a substrate surface and a sealing agent, and then the injection hole is sealed, (2) one of two substrates on which a liquid crystal alignment film is formed For example, an ultraviolet curable sealing agent is applied to a predetermined position on the substrate, and liquid crystal is dropped on a predetermined number of positions on the liquid crystal alignment film surface, and then the other substrate is made to face the liquid crystal alignment film. While spreading the liquid crystal over the entire surface of the substrate and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealing agent.
As the sealing agent, for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals Biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals, and the like can be used. In addition, cholesteric liquid crystals such as colestil chloride, cholesteryl nonaate, cholesteryl carbonate, and the like; and chiral agents such as those sold under the trade names "C-15" and "CB-15" (manufactured by Merck). And ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate may be added and used.

  Subsequently, if necessary, a polarizing plate is attached to the outer surface of the liquid crystal cell to obtain a liquid crystal element. Examples of the polarizing plate include a polarizing plate in which a polarizing film called “H film” obtained by absorbing iodine while stretching and orienting polyvinyl alcohol is sandwiched by a cellulose acetate protective film or a polarizing plate consisting of the H film itself.

  The liquid crystal element of the present disclosure can be effectively applied to various devices. For example, clocks, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors It can be used for various display devices such as liquid crystal televisions and information displays, retardation films, light control films and the like.

  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples.

In the following examples, the imidation ratio of the polymer and the solution viscosity of the polymer solution were measured by the following methods. Hereinafter, the compound represented by the formula X may be simply referred to as “compound X”.
[Imidation rate of polymer]
A solution containing a polyimide is introduced into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature and then dissolved in deuterated dimethyl sulfoxide to measure ¹ H-NMR at room temperature using tetramethylsilane as a reference substance. did. The imidation ratio was determined from the obtained ¹ H-NMR spectrum using the following formula (1).
Imidation ratio (%) = (1−A ¹ / A ² × α) × 100 (1)
(In the formula (1), A ¹ is a proton-derived peak area of an NH group appearing in the vicinity of a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a precursor of a polymer (polyamic acid It is the number ratio of other protons to one proton of NH group in).
Solution viscosity of polymer solution
The solution viscosity (mPa · s) of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer.

<Synthesis of Compound>
Synthesis Example 1: Synthesis of Compound (0-6-1)
The compound (0-6-1) was synthesized according to the following scheme 4.

Synthesis of Compound (0-6-1A) In a 300 mL three-necked flask equipped with a nitrogen introduction tube and a thermometer, 14.3 g of 1,5-bis (4-aminophenoxy) pentane, 100 mL of methylene chloride, and 16.6 g of triethylamine The reaction mixture was slowly added with 32.7 g of t-butyl dicarbonate and allowed to react at room temperature for 4 hours. After completion of the reaction, 500 mL of ethyl acetate is added, and after liquid separation washing three times with water, the organic layer is dried with magnesium sulfate and concentrated, and the precipitated white crystals are filtered, washed with hexane and dried. 19.5 g of compounds (0-6-1A) were obtained.
Synthesis of Compound (0-6-1B) 19.5 g of Compound (0-6-1A) is charged into a 1 L three-necked flask equipped with a dropping funnel, a nitrogen introducing tube and a thermometer, and vacuum / nitrogen substitution is repeated three times. The water in the system was removed. Next, 200 mL of tetrahydrofuran is added, and after cooling to -78 ° C, 97 mL of 0.91 M potassium hexamethylene disilazane solution is slowly added, and 200 mL of 19.0 g of 4-nitrobenzyl bromide is added using a dropping funnel. After a solution dissolved in tetrahydrofuran was dropped over 10 minutes, the temperature was returned to room temperature, and 200 mL of saturated aqueous sodium carbonate solution was added. Next, the aqueous layer was removed using a separatory funnel, 500 mL of ethyl acetate was added, and the mixture was washed three times with water and then dried over magnesium sulfate. Next, concentration under reduced pressure was performed, and the precipitated yellow crystals were filtered and dried to obtain 24.2 g of a compound (0-6-1B).
Synthesis of compound (0-6-1) 24.2 g of compound (0-6-1B), 200 mL of tetrahydrofuran, 200 mL of ethanol, and 1.2 g of 5% palladium carbon were charged in a 1 L autoclave equipped with a hydrogen inlet tube . Then, after hydrogen gas was blown in to make 1.4 kg / cm ² , the reaction was carried out at room temperature for 20 hours. After completion of the reaction, the filtrate obtained by removing the catalyst by celite filtration was concentrated under reduced pressure, and white crystals obtained were filtered and dried to obtain 20.1 g of a compound (0-6-1).

Synthesis Example 2: Synthesis of Compound (0-12-1)
The compound (0-12-1) was synthesized according to the following scheme 5.

Synthesis of compound (0-12-1B) After adding 14.9 g of compound (0-12-1A), 150 mL of methylene chloride and 16.6 g of triethylamine to a 300 mL three-necked flask equipped with a nitrogen introduction tube and a thermometer Then, 32.7 g of t-butyl dicarbonate was slowly added and allowed to react at room temperature for 4 hours. After completion of the reaction, 500 mL of ethyl acetate is added, and after liquid separation washing three times with water, the organic layer is dried with magnesium sulfate and concentrated, and the precipitated white crystals are filtered, washed with hexane and dried. 19.5 g of compounds (0-12-1B) were obtained.
Synthesis of Compound (0-12-1C) 19.5 g of Compound (0-12-1B) is charged into a 1 L three-necked flask equipped with a dropping funnel, a nitrogen inlet tube and a thermometer, and vacuum / nitrogen substitution is repeated three times. The water in the system was removed. Next, 200 mL of tetrahydrofuran was added and cooled to −78 ° C., and then 97 mL of 0.91 M potassium hexamethylene disilazane solution was slowly added. Subsequently, using a dropping funnel, a solution of 19.0 g of 4-nitrobenzyl bromide in 200 mL of tetrahydrofuran was added dropwise over 10 minutes, and then the temperature was returned to room temperature and 200 mL of saturated aqueous sodium carbonate solution was added. Next, the aqueous layer was removed using a separatory funnel, 500 mL of ethyl acetate was added, and the mixture was washed three times with water and then dried over magnesium sulfate. Next, concentration under reduced pressure was performed, and the precipitated yellow crystals were filtered and dried to obtain 24.6 g of a compound (0-12-1C).
Synthesis of Compound (0-12-1) In a 1 L autoclave equipped with a hydrogen introduction tube, 24.6 g of the compound (0-12-1C), 200 mL of tetrahydrofuran, 200 mL of ethanol and 1.2 g of 5% palladium carbon were charged. Then, after hydrogen gas was blown in to make 1.4 kg / cm ² , the reaction was carried out at room temperature for 20 hours. After completion of the reaction, the filtrate obtained by removing the catalyst by celite filtration was concentrated under reduced pressure, and white crystals obtained were filtered and dried to obtain 20.4 g of a compound (0-12-1).

Synthesis Example 3: Synthesis of Compound (1-1-1)
The compound (1-1-1) was synthesized according to the following scheme 6.

Synthesis of Compound (1-1-1A) After adding 10.0 g of 4,4'-diaminodiphenylamine, 100 mL of methylene chloride and 16.6 g of triethylamine to a 300 mL three-necked flask equipped with a nitrogen introduction tube and a thermometer, 32.7 g of t-butyl dicarbonate was slowly added and allowed to react at room temperature for 4 hours. After completion of the reaction, 500 mL of ethyl acetate is added, and after liquid separation washing three times with water, the organic layer is dried with magnesium sulfate and concentrated, and the precipitated white crystals are filtered, washed with hexane and dried. 16.0 g of compounds (1-1-1A) were obtained.
Synthesis of Compound (1-1-1B) 16.0 g of Compound (1-1-1A) is charged into a 1 L three-necked flask equipped with a dropping funnel, a nitrogen introduction tube and a thermometer, and vacuum / nitrogen substitution is repeated three times. The water in the system was removed. Next, after adding 200 mL of tetrahydrofuran and cooling to -78 ° C, 97 mL of 0.91 M potassium hexamethylene disilazane solution is slowly added, and then 200 mL of 22.3 g of 4-nitrophenethyl bromide is added using a dropping funnel. The solution in tetrahydrofuran was added dropwise over 10 minutes. Then, it returned to room temperature and added 200 mL of saturated sodium carbonate aqueous solution. Next, the aqueous layer was removed using a separatory funnel, 500 mL of ethyl acetate was added, and the mixture was washed three times with water and then dried over magnesium sulfate. Next, concentration under reduced pressure was performed, and the precipitated yellow crystals were filtered and dried to obtain 22.3 g of a compound (1-1-1 B).
Synthesis of Compound (1-1-1C) 22.3 g of Compound (1-1-1B), 100 mL of methylene chloride and 100 mL of trifluoroacetic acid are added to a 500 mL eggplant flask equipped with a nitrogen introduction tube, and reacted at room temperature for 2 hours I did. After completion of the reaction, the reaction solution is concentrated to dryness under reduced pressure, added with 200 mL of ethyl acetate and 200 mL of tetrahydrofuran, washed with water 10 times, dried over magnesium sulfate and concentrated under reduced pressure, and the precipitated yellow crystals are filtered and dried. By doing this, 14.4 g of a compound (1-1-1C) was obtained.
-Synthesis of compound (1-1-1) After charging 14.4 g of compound (1-1-1 C), 150 mL of tetrahydrofuran, 150 mL of ethanol and 0.72 g of 5% palladium carbon in a 1 L autoclave equipped with a hydrogen introduction tube After bubbling hydrogen gas to 1.4 kg / cm ² , the reaction was carried out at room temperature for 20 hours. After completion of the reaction, the filtrate obtained by removing the catalyst by celite filtration was concentrated under reduced pressure, and brown crystals obtained thereby were filtered and dried to obtain 11.3 g of a compound (1-1-1).

Synthesis Example 4: Synthesis of Compound (1-2-1)
The compound (1-2-1) was synthesized according to the following scheme 7.

Synthesis of Compound (1-2-1B) After adding 10.7 g of Compound (1-2-1A), 100 mL of methylene chloride and 16.6 g of triethylamine to a 300 mL three-necked flask equipped with a nitrogen introduction tube and a thermometer Then, 32.7 g of t-butyl dicarbonate was slowly added and allowed to react at room temperature for 4 hours. After completion of the reaction, 500 mL of ethyl acetate is added, and after liquid separation washing three times with water, the organic layer is dried with magnesium sulfate and concentrated, and the precipitated white crystals are filtered, washed with hexane and dried. 16.5 g of compounds (1-2-1 B) were obtained.
Synthesis of Compound (1-2-1C) 16.5 g of Compound (1-2-1B) is charged into a 1 L three-necked flask equipped with a dropping funnel, a nitrogen introducing tube and a thermometer, and vacuum / nitrogen substitution is repeated three times. The water in the system was removed. Next, after adding 200 mL of tetrahydrofuran and cooling to -78 ° C, 97 mL of 0.91 M potassium hexamethylene disilazane solution is slowly added, and then 200 mL of 22.3 g of 4-nitrophenethyl bromide is added using a dropping funnel. The solution in tetrahydrofuran was added dropwise over 10 minutes. Thereafter, the temperature was returned to room temperature, and 200 mL of a saturated aqueous solution of sodium carbonate was added. Next, the aqueous layer was removed using a separatory funnel, 500 mL of ethyl acetate was added, and the mixture was washed three times with water and then dried over magnesium sulfate. Next, concentration under reduced pressure was carried out, and the precipitated yellow crystals were filtered and dried to obtain 22.8 g of a compound (1-2-1C).
Synthesis of Compound (1-2-1D) 22.8 g of Compound (1-2-1C), 100 mL of methylene chloride and 100 mL of trifluoroacetic acid are added to a 500 mL eggplant flask equipped with a nitrogen introduction tube, and reacted at room temperature for 2 hours I did. After completion of the reaction, the reaction solution is concentrated to dryness under reduced pressure, added with 200 mL of ethyl acetate and 200 mL of tetrahydrofuran, washed with water 10 times, dried over magnesium sulfate and concentrated under reduced pressure, and the precipitated yellow crystals are filtered and dried. Thus, 14.7 g of a compound (1-2-1D) was obtained.
-Synthesis of compound (1-2-1) After charging 14.7 g of compound (1-2-1 D), 150 mL of tetrahydrofuran, 150 mL of ethanol, and 0.72 g of 5% palladium carbon in a 1 L autoclave equipped with a hydrogen introduction tube After bubbling hydrogen gas to 1.4 kg / cm ² , the reaction was carried out at room temperature for 20 hours. After completion of the reaction, the filtrate obtained by removing the catalyst by celite filtration was concentrated under reduced pressure, and brown crystals obtained were filtered and dried to obtain 12.0 g of a compound (1-2-1).

Synthesis Example 5 Synthesis of Compound (1-3-1)
The compound (1-3-1) was synthesized according to the following scheme 8.

Synthesis of compound (1-3-1B) After adding 13.8 g of compound (1-3-1A), 150 mL of methylene chloride and 16.6 g of triethylamine to a 300 mL three-necked flask equipped with a nitrogen introduction tube and a thermometer Then, 32.7 g of t-butyl dicarbonate was slowly added and allowed to react at room temperature for 4 hours. After completion of the reaction, 500 mL of ethyl acetate is added, and after liquid separation washing three times with water, the organic layer is dried with magnesium sulfate and concentrated, and the precipitated white crystals are filtered, washed with hexane and dried. 19.0 g of compounds (1-3-1 B) were obtained.
Synthesis of Compound (1-3-1C) 19.0 g of Compound (1-3-1B) is charged into a 1 L three-necked flask equipped with a dropping funnel, a nitrogen introducing tube and a thermometer, and vacuum / nitrogen substitution is repeated three times. The water in the system was removed. Next, after adding 200 mL of tetrahydrofuran and cooling to -78 ° C, 97 mL of 0.91 M potassium hexamethylene disilazane solution is slowly added, and then 200 mL of 22.3 g of 4-nitrophenethyl bromide is added using a dropping funnel. The solution in tetrahydrofuran was added dropwise over 10 minutes. Then, the temperature was returned to room temperature and 200 mL of saturated aqueous sodium carbonate solution was added. Next, the aqueous layer was removed using a separatory funnel, 500 mL of ethyl acetate was added, and the mixture was washed three times with water and then dried over magnesium sulfate. Next, the solution was concentrated under reduced pressure, and the precipitated yellow crystals were filtered and dried to obtain 24.8 g of a compound (1-3-1C).
Synthesis of compound (1-3-1D) 24.8 g of compound (1-3-1C), 200 mL of methylene chloride and 200 mL of trifluoroacetic acid are added to a 500 mL eggplant flask equipped with a nitrogen introduction tube and reacted for 2 hours at room temperature I did. After completion of the reaction, the reaction solution is concentrated to dryness under reduced pressure, added with 200 mL of ethyl acetate and 200 mL of tetrahydrofuran, washed with water 10 times, dried over magnesium sulfate and concentrated under reduced pressure, and the precipitated yellow crystals are filtered and dried. Thus, 16.5 g of compound (1-3-1D) was obtained.
Synthesis of Compound (1-3-1) In a 1 L autoclave equipped with a hydrogen introduction tube, 16.5 g of Compound (1-3-1D), 200 mL of tetrahydrofuran, 200 mL of ethanol and 0.83 g of 5% palladium carbon were charged. Next, hydrogen gas was blown in to make 1.4 kg / cm ^2, and then the reaction was performed at room temperature for 20 hours. After completion of the reaction, the filtrate obtained by removing the catalyst by celite filtration was concentrated under reduced pressure, and brown crystals obtained were filtered and dried to obtain 13.3 g of a compound (1-3-1).

<Synthesis of polymer>
[Polymerization Example 1]
50 moles of 1R, 2S, 4S, 5R-1,2,4,5-cyclohexanetetracarboxylic acid dianhydride as tetracarboxylic dianhydride, 30 moles of 2-methyl-4,4'-diaminobenzanilide as diamine Part and Compound (0-6-1) 20 mol parts were dissolved in N-methyl-2-pyrrolidone (NMP) and reacted at room temperature for 6 hours to obtain a solution containing 20 mass% of polyamic acid. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 105 mPa · s. The polyamic acid obtained here was used as a polymer (PPA-1).

[Polymerization Examples 2 to 11, Comparative Polymerization Examples 1 and 2]
Polyamic acids were synthesized in the same manner as in Polymerization Example 1 except that the type and amount of tetracarboxylic acid dianhydride and diamine used were changed as shown in Table 1 below. Moreover, about polymerization example 2, 100 mol parts of pyridine and 100 mol parts of acetic anhydride were added to the obtained polyamic acid solution, and chemical imidation was performed over 8 hours at 90 degreeC. The reaction solution after chemical imidization was concentrated and prepared with NMP so that the concentration was 10% by mass.

In Table 1, the numerical value of the monomer composition indicates the use ratio [mol%] of each compound to the total amount of monomers used for polymerization. The abbreviation of the compound is as follows.
<Tetracarboxylic acid dianhydride>
A-1: 1R, 2S, 4S, 5R-1, 2, 4, 5-cyclohexanetetracarboxylic acid dianhydride A-2: 2,3,5-tricarboxycyclopentylacetic acid dianhydride <diamine>
D-1: 2-Methyl-4,4′-diaminobenzanilide D-2: Compound represented by the following formula (D-2) D-3: 3,5-diaminobenzoic acid D-4: Compound Represented by D-4) D-5: Para-phenylenediamine D-6: Compound Represented by the Following Formula (E-1-4) D-7: Compound Represented by the Following Formula (D-7) In addition, (0-6-1), (0-12-1), (1-1-1), (1-2-1), (1-3-1) use diamine of the corresponding number Indicates that it was done.

Example 1
<Preparation of Liquid Crystal Alignment Agent>
20 parts by mass of the polymer (PPA-1) obtained in the above polymerization example 1 as a polymer, 80 parts by mass of the polymer (PPA-7) obtained in the polymerization example 8 and N, N, N 'as an epoxy additive NMP and butyl cellosolve (BC) as an organic solvent are added to 5 parts by mass (the amount based on the total of 100 parts by mass of the polymer) of N, -N'-tetraglycidyl [4,4'-methylenebisaniline], and the solvent composition is It was set as the solution of NMP: BC = 50: 50 (mass ratio) and solid content concentration 4.0 mass%. The solution was filtered using a filter with a pore size of 1 μm to prepare a liquid crystal aligning agent (G-1).

<Production of liquid crystal cell by rubbing treatment>
The liquid crystal aligning agent (G-1) prepared above is coated by a spinner on a glass substrate having on one side two metal electrodes (electrode A and electrode B) made of ITO patterned in a comb-tooth shape as a substrate After prebaking for 1 minute on a hot plate at 80 ° C., post-baking was carried out for 10 minutes on a hot plate at 230 ° C. to form a coating having a film thickness of about 0.08 μm. Using a rubbing machine having a roll of nylon cloth wound on the coated film surface, the number of revolutions of the roll is 1,000 rpm, the moving speed of the stage is 25 mm / sec, and the length of the hair is 0.4 mm. A rubbing treatment was performed to impart liquid crystal alignment ability. Further, the substrate was ultrasonically cleaned in ultrapure water for 1 minute and dried in a clean oven at 100 ° C. for 10 minutes to produce a substrate having a liquid crystal alignment film on the surface having the comb-like chromium electrode. The substrate having the liquid crystal alignment film is referred to as “substrate A”.
Separately, a coating film using a liquid crystal aligning agent (G-1) is formed and rubbed in the same manner as described above on one surface of a 1 mm-thick glass substrate not having an electrode, washed and dried. A substrate having a liquid crystal alignment film on one side was manufactured. The substrate having the liquid crystal alignment film is referred to as “substrate B”.
Subsequently, an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 μm is applied to the outer edge of the surface of the substrate having the rubbed liquid crystal alignment film, so that the rubbing directions in each liquid crystal alignment film become antiparallel. The two substrates A and B were disposed opposite to each other with a gap, and the outer edges were brought into contact with each other and pressed to cure the adhesive. Next, a nematic liquid crystal (MLC-2042, manufactured by Merck) is filled between a pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive to obtain a liquid crystal cell in a transverse electric field mode. Manufactured.

<Evaluation of afterimage characteristics (image sticking characteristics)>
The liquid crystal cell of the lateral electric field type manufactured above is placed in an environment of 25 ° C. and 1 atmospheric pressure, and no voltage is applied to the electrode B, and a synthetic voltage of 3.5 V AC and 5 V DC is applied to the electrode A for 2 hours Applied. Immediately after that, a voltage of 4 V AC was applied to both of the electrode A and the electrode B. The time until it became impossible to visually confirm the difference in the light transmittance of the electrode A and the electrode B from when the voltage of 4 V AC was started to be applied to both electrodes was measured. If the time is less than 50 seconds, "good (優良)", if it is 50 seconds or more and less than 100 seconds, the afterimage characteristic "good (○)", if it is 100 seconds or more and less than 150 seconds The characteristics “good (Δ)” and the afterimage characteristics when exceeding 150 seconds were evaluated as “defect (x)”. As a result, in this example, it was evaluated as "excellent".
<Evaluation of voltage holding ratio>
After applying a voltage of 5 V for 60 microseconds and applying a span of 167 milliseconds to the liquid crystal cell manufactured above, the voltage retention was measured 167 milliseconds after the release of the application. When the voltage holding ratio is 99.0% or more as “good (○)”, 98.0% or more and less than 99.0% as “OK (Δ)”, and less than 98.0% as “defect (×)” The voltage holding ratio was determined to be "good". In addition, as a measuring apparatus of a voltage holding ratio, the model name "VHR-1" made from Toyo-Technica Co., Ltd. was used.
<Evaluation of contrast>
The liquid crystal cell manufactured above was examined for the contrast after driving at AC 5 V for 30 hours. Evaluation was carried out as follows.
Using a device in which a polarizer and an analyzer are installed between a light source and a light quantity detector, the liquid crystal cell manufactured above is disposed between a polarizer and an analyzer, and light transmission under cross nicol The amount β was examined, and these values were substituted into the following equation (2) to calculate the minimum relative transmittance (%).
Minimum relative transmittance (%) = (β-B0) / (B100-B0) × 100 (2)
(In formula (2), B0 is the light transmission of the blank under cross nicol, B100 is the light transmission of the blank under para nicol, and β is the liquid crystal between the polarizer and the analyzer under cross nicol It is the amount of light transmission measured with the cells arranged.)
The minimum relative transmittance calculated by the equation (2) indicates the degree of the black level in the dark state, and the smaller the value of the minimum relative transmittance, the better the contrast can be evaluated. When the above minimum relative transmittance is less than 0.5%, the contrast is "good (o)" and when it is 0.5 or more and 1.0% or less, the contrast is "good (?)", 1.0% The case where it exceeded was evaluated as contrast "defect (defect) (x)", and contrast was judged to be "good."

[Examples 2 to 8, Comparative Example 1]
A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the type and amount of the polymer used were changed as shown in Table 2 below, and a liquid crystal cell was manufactured and evaluated. The results are shown in Table 2 below.

[Example 9]
<Preparation of Liquid Crystal Alignment Agent>
NMP and butyl cellosolve (BC) as an organic solvent are added to the polymer (PPA-8) obtained in the above polymerization example 9 as a polymer, and the solvent composition is NMP: BC = 50: 50 (mass ratio), solid content concentration 4 .0% by weight solution. This solution was filtered using a filter with a pore size of 1 μm to prepare a liquid crystal aligning agent (G-9).
<Production of liquid crystal cell by photo alignment method>
Using the spinner, the liquid crystal aligning agent (G-9) prepared above was coated on each of the substrate surfaces of a pair of substrates similar to those used in Example 1 so as to have a film thickness of 0.1 μm. Then, it was heated (prebaked) at 80 ° C. for 1 minute. Next, after heating (post-baking) in a clean oven at 230 ° C. for 1 hour, each coated film surface is irradiated with 1,000 mJ / cm ² of ultraviolet light of polarized light including a 254 nm bright line using an Hg-Xe lamp The liquid crystal alignment films were formed on two (pair) substrates by heating (post-baking) in a clean oven at 230 ° C. for 30 minutes after irradiation in the direction normal to the substrate.
Next, for one of the above pair of substrates, an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 μm is screen printed on the outer peripheral edge of the surface on which the liquid crystal alignment film is formed, leaving the liquid crystal injection port. After coating, a pair of substrates are superposed and pressure bonded so that the formation surface of the liquid crystal alignment film faces each other and the projection direction of the polarization plane to the substrate surface at the time of light irradiation matches, and one hour at 150 ° C. The heat was applied to heat cure the adhesive.
Next, nematic liquid crystal (manufactured by Merck, MLC-7028) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, the liquid crystal cell was manufactured by heating this to 150 ° C. and then gradually cooling to room temperature.
<Evaluation of liquid crystal cell>
The residual image characteristics, the voltage holding ratio and the contrast were evaluated in the same manner as in Example 1 using the liquid crystal cell manufactured above. The results are shown in Table 3 below.

Comparative Example 2
A liquid crystal aligning agent was prepared in the same manner as in Example 9 except that the type and amount of the polymer used were changed as shown in Table 3 below, and a liquid crystal cell was manufactured and evaluated. The results are shown in Table 3 below.

[Example 10]
<Preparation of Liquid Crystal Alignment Agent>
To 20 parts by mass of (PPA-10) polymerized in the above polymerization example 11 and 80 parts by mass of (PPA-9) polymerized in polymerization example 10 as polymer components, NMP and butyl cellosolve (BC) as an organic solvent are added, It was set as the solution whose solvent composition is NMP: BC = 50: 50 (mass ratio) and solid content concentration 4.0 mass%. The solution was filtered using a filter with a pore size of 1 μm to prepare a liquid crystal aligning agent (G-10).
<Manufacture of VA type liquid crystal cell>
The liquid crystal aligning agent (G-10) prepared above was apply | coated by the spinner on each electrode surface of this pair of glass substrate using a pair of glass substrate which has the transparent electrode which consists of ITO films on one side. Next, after prebaking for 1 minute on a hot plate at 80 ° C., post-baking was performed for 10 minutes on a hot plate at 230 ° C. to form a coating having a film thickness of about 0.08 μm. Subsequently, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer edge of the surface of one of the substrates having the liquid crystal alignment film, and then the two substrates are arranged opposite to each other via a gap. The outer edges were brought into contact with each other and pressed to cure the adhesive. Then, nematic liquid crystal (manufactured by Merck, MLC-6608) was filled between a pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell. Two liquid crystal cells were prepared.
<Evaluation of afterimage characteristics (image sticking characteristics)>
Two liquid crystal cells manufactured above were placed under an environment of 25 ° C. and 1 atm, and a synthetic voltage of 3.5 V AC and 5 V DC was applied for 2 hours to one of them (the other one is a reference). Immediately after that, a voltage of 4 V AC was applied. The time until it became impossible to visually confirm the difference in light transmittance with the reference from when the application of a voltage of 4 V AC was started was measured. If the time is less than 50 seconds, "good (優良)", if it is 50 seconds or more and less than 100 seconds, the afterimage characteristic "good (○)", if it is 100 seconds or more and less than 150 seconds The characteristics “good (Δ)” and the afterimage characteristics when exceeding 150 seconds were evaluated as “defect (x)”. As a result, it was an evaluation of "good" in this example.
<Evaluation of voltage holding ratio>
After applying a voltage of 5 V for 60 microseconds and applying a span of 167 milliseconds to the two liquid crystal cells manufactured above, the voltage retention was measured 167 milliseconds after the release of the application. When the voltage holding ratio is 99.0% or more as “good (○)”, 98.0% or more and less than 99.0% as “OK (Δ)”, and less than 98.0% as “defect (×)” The voltage holding ratio was determined to be "good". In addition, as a measuring apparatus of a voltage holding ratio, the model name "VHR-1" made from Toyo-Technica Co., Ltd. was used.
<Evaluation of reliability>
With respect to the liquid crystal display element, the rate of change in voltage holding ratio (ΔVHR) after 200 hours of stress application was measured while the backlight was on. The voltage holding ratio was measured by applying a voltage of 1 V to the liquid crystal display element with an application time of 60 microseconds and a span of 1670 milliseconds, and then measuring the voltage holding ratio 1670 milliseconds after the release of the application. The measuring apparatus used VHR-1 manufactured by Toyo Corporation. The rate of change ΔVHR (%) was determined by the following formula (ex-1).
ΔVHR = ((VHRBF−VHRAF) ÷ VHRBF) × 100 (ex-1)
(In the formula (ex-1), VHRBF is a voltage holding ratio before applying a stress, and VHRAF is a voltage holding ratio after applying a stress.)
The evaluation of reliability is “good A (◎)” when the change rate ΔVHR is less than 1.0%, “good B (○)” when the change rate ΔVHR is 1.0% or more and less than 2.0%. The case of 2.0% or more and less than 3.0% was regarded as “OK (Δ)”, and the case of 3.0% or more as “Defective (×)”. As a result, in the liquid crystal display element of this example, ΔVHR = 1.5%, and the reliability was “good B”.

Comparative Example 3
A liquid crystal aligning agent was prepared in the same manner as in Example 10 except that the type and amount of the polymer used were changed as shown in Table 4 below, and a liquid crystal cell was manufactured and evaluated. The results are shown in Table 4 below.

  From the above results, a liquid crystal display device excellent in residual image characteristics and voltage retention and excellent in contrast by containing the polymer [P] having a partial structure represented by the above formula (1) in a liquid crystal aligning agent It became clear that you could get Moreover, the liquid crystal display element manufactured using the liquid crystal aligning agent containing polymer [P] was favorable also about reliability.

Claims (4)

The liquid crystal aligning agent which is at least 1 type chosen from the group which consists of a polyamic acid, a polyamic acid ester, a polyimide, and a polyamide, and contains polymer [P] which has the partial structure represented by following formula (1).

(In formula (1), R ¹ and R ⁵ are each independently an alkanediyl group, and R ² and R ⁴ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or R ⁰ is a divalent organic group having a cyclic structure (except when R ⁰ is bonded to —NR ² — and —NR ⁴ — via a carbonyl group). ) The liquid crystal aligning agent of Claim 1 to which R < ⁰ > in the said Formula (1) is ^couple | bonded with -NR < ² >-and -NR < ⁴ >-by cyclic structure.   The liquid crystal aligning film formed using the liquid crystal aligning agent of Claim 1 or 2.   The liquid crystal element which comprises the liquid crystal aligning film of Claim 3.