JP2016035500A - Liquid crystal alignment agent, manufacturing method of liquid crystal alignment agent, liquid crystal alignment film, manufacturing method of liquid crystal alignment film, liquid crystal display device, phase difference film, and manufacturing method of phase difference film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal alignment agent that can provide a liquid crystal display device preventing the occurrence of display unevenness around a sealing agent and provide a liquid crystal alignment film having a good surface unevenness property.SOLUTION: A liquid crystal alignment agent contains a compound (P) having a partial structure represented by the following formula (1), wherein Ris a monovalent organic group and "*" represents a bonding hand.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal aligning agent, a method for producing a liquid crystal aligning agent, a liquid crystal alignment film, a method for producing a liquid crystal aligning film, a liquid crystal display element, a retardation film, and a method for producing a retardation film.

  Conventionally, as a liquid crystal display element, various drive systems having different electrode structures, properties of liquid crystal molecules to be used, manufacturing processes, and the like have been developed. For example, a TN (Twisted Nematic) type and an STN (Super Twisted Nematic) type have been developed. Various liquid crystal display elements such as VA (Vertical Alignment), IPS (In-Plane Switching), and FFS (fringe field switching) are known. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. As a material for the liquid crystal alignment film, polyamic acid or polyimide is generally used from the viewpoints of various properties such as heat resistance, mechanical strength, and affinity with liquid crystal.

  In recent years, various liquid crystal aligning agents have been proposed in order to further improve the performance of the liquid crystal aligning film as the liquid crystal display element becomes highly fine (see, for example, Patent Document 1 and Patent Document 2). Patent Document 1 discloses a liquid crystal aligning agent containing a polyamic acid or a derivative thereof using a monoamine having a hydroxyl group as a polymer terminator. Patent Document 2 contains, as a polymer component of the liquid crystal aligning agent, a polyamic acid and a polyamic acid ester in which at least a part of the terminal amino group is terminal-modified so as to have a specific structure including an amide bond. Is disclosed.

  In addition, various optical materials are used for liquid crystal display elements. Above all, retardation films eliminate the object of viewing color dependency and the viewing angle dependency that the display color and contrast ratio change depending on the visual direction. It is used for the purpose. As such retardation films, those having a liquid crystal alignment film formed on the surface of a substrate such as a TAC film and a liquid crystal layer formed by curing a polymerizable liquid crystal on the surface of the liquid crystal alignment film are known. ing. In recent years, a liquid crystal alignment film in a retardation film has been produced by using a photo-alignment method that imparts liquid crystal alignment ability by irradiating a radiation-sensitive organic thin film formed on the substrate surface with polarized or non-polarized radiation. Various liquid crystal aligning agents for retardation films for producing a liquid crystal aligning film by such a method have been proposed (for example, see Patent Document 3).

JP 2013-010889 A International Publication No. 2011/115077 JP 2012-37868 A

  A liquid crystal display is manufactured by disposing a pair of substrates on which a liquid crystal alignment film is formed facing each other and disposing a liquid crystal between the pair of facing substrates. In this case, the pair of substrates is sealed with an epoxy resin or the like. It is pasted using an agent. Here, in touch panel type display panels represented by smartphones and tablet PCs, attempts have been made to narrow the frame in order to make the movable area of the touch panel wider and to make the liquid crystal panel more compact. In addition, display unevenness may be visually recognized around the sealant as the liquid crystal panel is narrowed, which is not satisfactory in terms of display quality. In order to increase the definition of the liquid crystal display, a liquid crystal display element in which display unevenness around the sealant is hardly visible (bezel unevenness resistance is high) is required.

  Moreover, when the surface unevenness | corrugation property of the coating film formed using the liquid crystal aligning agent is not favorable, we are anxious about the reliability of a liquid crystal aligning film or a liquid crystal display element falling. With the recent diversification of liquid crystal display elements, the liquid crystal display elements are expected to be used in more severe situations, and it is desirable to further improve the reliability of the liquid crystal display elements.

  An object of the present invention is to provide a liquid crystal aligning agent from which a liquid crystal display element with little occurrence of display unevenness around a sealing agent is obtained and from which a liquid crystal aligning film having excellent surface unevenness can be obtained.

  The present inventor diligently studied to achieve the above-described problems of the prior art, and found that the above problems can be solved by including a compound having a specific structure in the liquid crystal aligning agent. Specifically, the following liquid crystal aligning agent, liquid crystal aligning agent manufacturing method, liquid crystal aligning film, liquid crystal aligning film manufacturing method, liquid crystal display element, retardation film, and retardation film manufacturing method are provided.

  In one aspect, the present invention provides a liquid crystal aligning agent containing a compound (P) having a partial structure represented by the following formula (1).

（式（１）中、Ｒ^１は１価の有機基である。「＊」は結合手を表す。）

(In Formula (1), R ¹ is a monovalent organic group. “*” Represents a bond.)

  In another aspect, the present invention is represented by the above formula (1) through a reaction step of reacting a compound having a carbonyl group with a primary amine compound represented by the following formula (a). A method for producing a liquid crystal aligning agent containing the compound (P) having a partial structure is provided.

（式（ａ）中、Ｒ^１は１価の有機基である。）

(In formula (a), R ¹ is a monovalent organic group.)

  In another aspect, a liquid crystal alignment film formed using the liquid crystal alignment agent is provided. Moreover, a liquid crystal display element provided with the said liquid crystal aligning film and a phase difference film provided with the said liquid crystal aligning film are provided. Furthermore, in another aspect, the step of coating the liquid crystal aligning agent on a substrate to form a coating film, the step of irradiating the coating film with light, and the polymerization on the coating film after the light irradiation And a step of applying and curing a liquid crystal.

  By including the compound (P) having the partial structure represented by the above formula (1) as one component of the liquid crystal aligning agent, a liquid crystal display element with little occurrence of display unevenness around the sealing agent can be obtained. Moreover, according to the liquid crystal aligning agent containing a compound (P), the coating film with favorable surface unevenness | corrugation can be formed, Therefore, a liquid crystal display element with favorable reliability can be obtained.

The schematic block diagram of a FFS type liquid crystal cell. The plane schematic diagram of the top electrode used for manufacture of the liquid crystal display element by rubbing process. (A) is a top view of a top electrode, (b) is the elements on larger scale of a top electrode. The figure which shows the drive electrode of 4 systems. The plane schematic diagram of the top electrode used for manufacture of the liquid crystal display element by a photo-alignment process. (A) is a top view of a top electrode, (b) is the elements on larger scale of a top electrode.

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

（式（１）中、Ｒ^１は１価の有機基である。「＊」は結合手を表す。） <Compound (P)>
The liquid crystal aligning agent of this embodiment contains the compound (P) which has a partial structure represented by following formula (1).

(In Formula (1), R ¹ is a monovalent organic group. “*” Represents a bond.)

The compound (P) may constitute at least a part of the polymer component of the liquid crystal aligning agent, or may be a relatively low-molecular compound constituting other than the polymer component. Preferably, compound (P) is in the form of a polymer.
When the compound (P) is a polymer, the main skeleton is not particularly limited, but specific examples include, for example, polyamic acid, polyimide, polyamic acid ester, polysiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative. Main skeletons such as poly (styrene-phenylmaleimide) derivatives and poly (meth) acrylates. Among these, it is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyester, and poly (meth) acrylate from the viewpoint of heat resistance, mechanical strength, affinity with liquid crystal, and the like. It is preferably an at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide. In addition, the compound (P) used for preparation of a liquid crystal aligning agent may be only 1 type, and is good also as a 2 or more types of blend type | system | group. (Meth) acrylate is meant to include acrylate and methacrylate.

Examples of the monovalent organic group for R ¹ include a monovalent hydrocarbon group and a methylene group of a hydrocarbon group represented by —O—, —S—, —CO—, —COO—, —COS—, —NR ³ —. , —CO—NR ³ —, —Si (R ³ ) ₂ — (wherein R ³ is a monovalent hydrocarbon group having 1 to 12 carbon atoms), —N═N—, —SO ₂ — and the like. At least one hydrogen atom bonded to the carbon atom of the monovalent group and the hydrocarbon group is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxyl group, And monovalent groups substituted with a cyano group, a formyl group, and the like, and monovalent groups having a heterocyclic ring. R ¹ is preferably bonded to the nitrogen atom in the formula (1) with a hydrocarbon group, and more preferably bonded with a chain hydrocarbon group or an alicyclic hydrocarbon group.

  Here, in the present specification, the “hydrocarbon group” means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The “chain hydrocarbon group” means a linear hydrocarbon group and a branched hydrocarbon group that are composed only of a chain structure without including a cyclic structure in the main chain. However, it may be saturated or unsaturated. The “alicyclic hydrocarbon group” means a hydrocarbon group that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. However, it is not necessary to be comprised only by the structure of an alicyclic hydrocarbon, The thing which has a chain structure in the part is also included. “Aromatic hydrocarbon group” means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure.

（式（ａ）中、Ｒ^１は上記式（１）と同義である。） Compound (P) can be synthesized by appropriately combining organic chemistry methods. As an example, there is a method of synthesizing by a step of reacting a compound having a carbonyl group (hereinafter also referred to as “carbonyl group-containing compound”) with a primary amine compound represented by the following formula (a). Can be mentioned.

(In formula (a), R ¹ has the same meaning as in formula (1) above.)

(Primary amine compound)
As the primary amine compound (hereinafter also referred to as “primary amine compound (A)” or “compound (A)”) to be reacted with the carbonyl group-containing compound, a primary amine having a functional functional group is preferably used. be able to. Here, the “functional functional group” is a functional group capable of imparting a polymer with a function related to basic characteristics required for a liquid crystal aligning agent, a liquid crystal alignment film, or a liquid crystal display element. , Functional groups capable of imparting functions such as liquid crystal orientation (including photo-alignment) and coatability. By using a primary amine compound having a functional functional group, it can be said that a desired function can be imparted to the compound by using a Schiff base as a platform (platform) for introducing the functional functional group. As a primary amine which has a functional functional group, the compound etc. which are represented, for example by following formula (3) are mentioned.

（式（３）中、Ａ^１は機能性官能基であり、Ｒ^１ａは単結合又は２価の炭化水素基である。）

(In Formula (3), A ¹ is a functional functional group, and R ^1a is a single bond or a divalent hydrocarbon group.)

In the above formula (3), as the functional group of A ^1, for example, reliability can impart groups (reliability group), a liquid crystal alignment properties capable imparting group (orientation group), can impart coatability Examples of such groups (applicable groups).
The divalent hydrocarbon group for R ^1a includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof include divalent chain hydrocarbon groups such as methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, nonanediyl group, and decandiyl group. These may be linear or branched. The divalent alicyclic hydrocarbon group of ^{R 1,} a cyclohexylene _{group, -Rc- (CH 2) n -} ( provided that, Rc cyclohexylene radical, n is an integer of 1 to 5. As the divalent aromatic hydrocarbon group, for example, a phenylene group, a biphenylene group, —Ph— (CH ₂ ) _n — (where Ph is a phenylene group, and n is an integer of 1 to 5) Etc.). R ^1a is preferably a divalent chain hydrocarbon group or alicyclic hydrocarbon group from the viewpoint of increasing the reactivity with the carbonyl group, and is preferably an alkanediyl group having 1 to 10 carbon atoms. More preferably, it is a C1-C5 alkanediyl group.

(Primary amine compound having a reliable group)
As an example of the compound represented by the above formula (3), a primary amine compound having a reliability group as the functional functional group (A ¹ ) (hereinafter also referred to as “amine compound (am-1)”) may be mentioned. It is done. Examples of the reliable group as the functional functional group (A ¹ ) include a group having a nitrogen-containing heterocyclic ring, a group having a tertiary amine structure, and a group capable of expressing radical scavenging ability.

Nitrogen-containing heterocycle having a reliability group is, for example, pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, purine, quinoline, isoquinoline, naphthyridine, quinoxaline, phthalazine, triazine, thiazole, A heterocyclic ring having a double bond-containing ring structure such as isothiazole, benzothiazole, 5,6,7,8-tetrahydroquinoline (hereinafter also referred to as “aromatic nitrogen-containing heterocycle” for convenience);
Heterocycles having no double bond-containing ring structure such as piperidine, piperazine, pyrrolidine, hexamethyleneimine, decahydroquinoline (hereinafter also referred to as “non-aromatic nitrogen-containing heterocycle” for the sake of convenience), and the like. It is done. These rings may have a substituent. Specific examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methyl group, an ethyl group, a propyl group and the like. An alkyl group; an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group and a tolyl group;
Among these, the nitrogen-containing heterocyclic ring possessed by the reliability group is preferably a non-aromatic heterocyclic ring, and more preferably piperidine or piperazine.

When the amine compound (am-1) is a primary amine compound having a nitrogen-containing heterocyclic ring, from the viewpoint of suppressing the sublimation of the amine compound (am-1) and increasing the reactivity with the carbonyl group, (1) The number of carbon atoms in the remaining partial structure excluding the primary amino group is 11 or more, (2) the total number of atoms in the remaining partial structure excluding the primary amino group is 12 or more, and (3 It is preferable that at least one of the conditions that the molecular weight of the remaining partial structure excluding the primary amino group is 150 or more is satisfied.
Here, in the above (1), the carbon number of the remaining partial structure excluding the primary amino group is more preferably 11 to 40, and further preferably 11 to 30. In the above (2), the number of atoms of the remaining partial structure excluding the primary amino group is more preferably 12 to 42. In the above (3), the molecular weight of the remaining partial structure excluding the primary amino group is more preferably 150 to 1000, and further preferably 150 to 500.
The primary amine compound having a nitrogen-containing heterocycle preferably satisfies at least one of the conditions (1) to (3), but suppresses sublimation of the amine compound (am-1). From the viewpoint, it is more preferable that all the conditions (1) to (3) are satisfied.

（式（Ａ−１）中、Ａ^２は水素原子又は炭素数１〜２０の１価の炭化水素基であり、Ａ^３は２価の窒素含有複素環基であり、Ａ^４は単結合又は２価の芳香族炭化水素環基であり、Ｒ^１ｂは単結合、２価の鎖状炭化水素基又は２価の脂環式炭化水素基である。ただし、Ａ^２及びＡ^４の少なくともいずれかは芳香族炭化水素環を有する。） Preferable specific examples of the primary amine compound having a nitrogen-containing heterocyclic ring or a tertiary amine structure include compounds represented by the following formula (A-1).

(In Formula (A-1), A ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, A ³ is a divalent nitrogen-containing heterocyclic group, and A ⁴ is a single bond or A divalent aromatic hydrocarbon ring group, and R ^1b is a single bond, a divalent chain hydrocarbon group or a divalent alicyclic hydrocarbon group, provided that at least one of A ² and A ⁴ Has an aromatic hydrocarbon ring.)

In formula (A-1), examples of the monovalent hydrocarbon group represented by A ² include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, octyl, nonyl, and decanyl; cyclohexyl Groups, alicyclic hydrocarbon groups such as methylcyclohexyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, and biphenyl group. When A ⁴ is a single bond, A ² is preferably an aromatic hydrocarbon group, more preferably a phenyl group.
Divalent nitrogen-containing heterocyclic group of A ³ is a group obtained by removing two hydrogen atoms bonded to atoms constituting a ring nitrogen-containing heterocycle. The nitrogen-containing heterocycle is preferably the non-aromatic nitrogen-containing heterocycle, and more preferably piperidine or piperazine.
Examples of the divalent aromatic hydrocarbon ring group represented by A ⁴ include a phenylene group and a biphenylene group, and a 1,4-phenylene group is more preferable.

Preferable specific examples when the amine compound (am-1) is a nitrogen-containing heterocyclic ring or a primary amine compound having a tertiary amine structure include, for example, the following formulas (A-1-1) to (A-1- And compounds represented by each of 21).

  Among the above, from the viewpoint of reactivity with the carbonyl group, among the above formulas (A-1-2) to (A-1-6), formula (A-1-8), and formula (A-1-9) ), Formula (A-1-11), Formula (A-1-12), Formula (A-1-14), Formula (A-1-15), Formula (A-1-17), Formula (A) It is preferable to use a compound represented by each of -1-18), formula (A-1-20), and formula (A-1-21). In addition, the said compound can be used individually by 1 type or in combination of 2 or more types.

When the amine compound (am-1) has a group capable of expressing radical scavenging ability as the functional functional group (A ¹ ), for example, the group includes a group having a hindered amine structure, a group having a hindered phenol structure, Examples thereof include a group having a catechol structure and a hydroquinone structure. Specific examples thereof include, for example, a group represented by the following formula (b-2) as a group having a hindered amine structure; and a group having a hindered phenol structure, for example, represented by the following formula (b-3). A group having a catechol structure, for example, a group represented by the following formula (b-4); a group having a hydroquinone structure, for example, a group represented by the following formula (b-5), Each can be mentioned.

（式（ｂ−２）中、Ｒ^４は水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜１３のアラルキル基、１，３−ジオキソブチル基又は１，４−ジオキソブチル基である。ただし、Ｒ^４は、Ｒ^４が有する水素原子の１つを取り除いた２価の基として分子鎖の一部を形成していてもよい。Ｒ^５〜Ｒ^８は、それぞれ独立に炭素数１〜６のアルキル基、炭素数６〜１２のアリール基又は炭素数７〜１３のアラルキル基である。Ｘ^１は単結合、酸素原子、カルボニル基、＊＊−（ＣＨ_２）_ｎ−Ｏ−（ｎは１〜４の整数）又は＊＊−ＣＯＮＨ−であり、Ｘ^２〜Ｘ^５は、それぞれ独立に単結合、カルボニル基、＊＊−ＣＨ_２−ＣＯ−又は＊＊−ＣＨ_２−ＣＨ（ＯＨ）−である。但し、＊＊は、ピペリジン環と結合する結合手を示す。＊は結合手を示す。）

(In formula (b-2), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, a 1,3-dioxobutyl group, or 1 , 4-dioxobutyl group, provided that R ⁴ may form part of a molecular chain as a divalent group in which one of the hydrogen atoms of R ⁴ is removed, R ^{5 to} R ⁸ being Are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms, X ¹ is a single bond, an oxygen atom, a carbonyl group, **-(CH _{2) n} -O- (n is an integer from 1 to 4) or ** - is ^CONH-, X 2 to X ⁵ each independently represent a single bond, a carbonyl group, ** _- CH 2 -CO- or * _{* -CH 2 -CH (OH) -} . it is where ** is bound to piperidine ring A bond that. * Represents a bond.)

（式（ｂ−３）中、Ｒ^９は炭素数４〜１６の炭化水素基、又は当該炭化水素基の炭素−炭素結合間に「−Ｏ−」及び「−Ｓ−」のうちの少なくともいずれかを含む基である。Ｒ^１０は水素原子又は炭素数１〜１６の炭化水素基であり、ａは０〜３の整数である。ａが２又は３の場合、複数のＲ^１０は互いに同じでも異なっていてもよい。＊は結合手を示す。）

(In Formula (b-3), R ⁹ is a hydrocarbon group having 4 to 16 carbon atoms, or at least one of “—O—” and “—S—” between carbon-carbon bonds of the hydrocarbon group. R ¹⁰ is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms, and a is an integer of 0 to 3. When a is 2 or 3, a plurality of R ¹⁰ are the same as each other However, they may be different. * Indicates a bond.)

（式（ｂ−４）中、Ｒ^２０は水素原子又は炭素数１〜１６の炭化水素基であり、ａは０〜３の整数である。ａが２又は３の場合、複数のＲ^１１は互いに同じでも異なっていてもよい。＊は結合手を示す。）
（式（ｂ−５）中、Ｒ^３０は水素原子又は炭素数１〜１６の炭化水素基であり、ａは０〜３の整数である。ａが２又は３の場合、複数のＲ^１１は互いに同じでも異なっていてもよい。＊は結合手を示す。）

(In the formula (b-4), R ²⁰ is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms, and a is an integer of 0 to 3. When a is 2 or 3, a plurality of R ¹¹ are (They may be the same or different from each other. * Indicates a bond.)
(In the formula (b-5), R ³⁰ is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms, and a is an integer of 0 to 3. When a is 2 or 3, a plurality of R ¹¹ are (They may be the same or different from each other. * Indicates a bond.)

Regarding R ^{4 in the} above formula (b-2), examples of the alkyl group having 1 to 20 carbon atoms include the same groups as those exemplified for the group “—C _c H _{2c + 1} ” in the above formula (D-1). .
Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, fluorophenyl group, chlorophenyl group, propylphenyl group, butylphenyl group, 3-chloro-4-methylphenyl group, 4-pyridinyl group, and 2-phenyl-4. -Quinolinyl group, 2- (4'-t-butylphenyl) -4-quinolinyl group, 2- (2'-thiophenyl) -4-quinolinyl group and the like;
Examples of the aralkyl group having 7 to 13 carbon atoms include a benzyl group and a phenethyl group.
Examples of the alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 12 carbon atoms, and the aralkyl group having 7 to 13 carbon atoms of R ^{5 to} R ⁸ include groups having a corresponding carbon number among the examples of R ⁴ described above. It is done.

Examples of the group represented by “—X ² —R ⁵ ”, “—X ³ —R ⁶ ”, “—X ⁴ —R ⁷ ”, and “—X ⁵ —R ⁸ ” in the above formula (b-2) For example, methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, benzoyl group, 4-formylbenzoyl group, 2-hydroxy-2-phenylethyl group, 2-oxo-2- (3,4, And 5-trimethoxyphenyl) ethyl group. Incidentally, ^"- X 2 -R ^{5", "-} X 3 -R ^{6", "-} X 4 -R ^7" and ^"-X 5 -R ^8" may be different even in respectively the same .

Regarding R ^{9 in the} above formula (b-3), examples of the hydrocarbon group having 4 to 16 carbon atoms include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specifically, as the aliphatic hydrocarbon group, for example, a group having 4 to 16 carbon atoms among the groups exemplified in the group “—C _c H _{2c + 1} ” of the above formula (D-1); an alicyclic hydrocarbon group For example, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an isobornyl group, etc., an adamantyl group, a tricyclodecanyl group, etc .; As an aromatic hydrocarbon group, for example, a phenyl group, a fluorophenyl group, a benzyl group, a phenethyl group, etc .; Each can be mentioned. R ⁹ is a monovalent group including at least one of “—O—” and “—S—” between the carbon-carbon bonds of the hydrocarbon groups having 4 to 16 carbon atoms exemplified above. It may be a group of
Preferable specific examples of R ⁹ include, for example, t-butyl group, 1-methylpentadecyl, 1-ethylpentadecyl, octylthiomethyl group, decylthiomethyl group, dodecylthiomethyl group, tetradecylthiomethyl group and the like. It is done.

In the above formulas (b-3) to (b-5), the hydrocarbon group having 1 to 16 carbon atoms of R ¹⁰ , R ²⁰ and R ³⁰ includes a methyl group, an ethyl group, a propyl group, etc. groups exemplified in the description of R ⁹ and the like.
The bonding position of R ¹⁰ , R ²⁰ and R ³⁰ is not particularly limited, and may be any of ortho, meta and para positions with respect to the phenolic hydroxyl group. Preferable specific examples of R ¹⁰ , R ²⁰ and R ³⁰ include, for example, methyl group, ethyl group, t-butyl group, 1-methylpentadecyl, 1-ethylpentadecyl and the like.

Preferable specific examples when the amine compound (am-1) is a primary amine compound having a group capable of expressing radical scavenging ability include, for example, the following formulas (A-2-1) to (A-2-7): ) And the like.

  In addition, the compounds represented by the above formulas (A-2-1) to (A-2-4) have a nitrogen-containing heterocyclic ring, and are referred to as “primary amine compounds having a nitrogen-containing heterocyclic ring”. Also applies. The compounds having a group capable of expressing the radical scavenging ability can be used singly or in combination of two or more.

(Amine compound having an orientation group)
An example of the compound represented by the above formula (3) is an amine compound having an orientation group as the functional functional group (A ¹ ) (hereinafter also referred to as “amine compound (am-2)”). Examples of the orientation group as the functional functional group (A ¹ ) include a group having a linear structure, a group having a mesogen skeleton, a group having a bulky structure, and a photoalignment group.

（式中、ｊは１〜２０の整数であり、ｈは０〜１０の整数であり、ｉは１〜１０の整数である。） Specific examples of the group having a linear structure, the group having a mesogenic skeleton, and the group having a bulky structure include the same groups as those exemplified in the orientation group that may be introduced into the side chain of the polyamic acid. .
Specific examples of the primary amine compound having a linear structure, a mesogenic skeleton or a bulky structure among the amine compounds (am-2) include, for example, n-butylamine, n-pentylamine, n-hexylamine, laurylamine, Examples thereof include long-chain aliphatic amines having 4 to 20 carbon atoms such as stearylamine, and compounds represented by the following formulas (A-3-1) to (A-3-9).

(In the formula, j is an integer of 1 to 20, h is an integer of 0 to 10, and i is an integer of 1 to 10.)

（式（ｐ）中、Ｘ^３は、硫黄原子、酸素原子又は−ＮＨ−である。「＊」はそれぞれ結合手を示す。但し、２つの「＊」のうち少なくとも一方は芳香環に結合している。） As the photoalignment group, a group exhibiting photoalignment by photoisomerization, photodimerization, photolysis, or the like can be employed. Specifically, for example, an azo-containing group containing an azo compound or a derivative thereof as a basic skeleton, a cinnamic acid-containing group having a cinnamic acid structure containing a cinnamic acid or a derivative thereof as a basic skeleton, a chalcone or a derivative thereof as a basic skeleton Containing chalcone-containing group, benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, a polyimide-containing structure containing polyimide or a derivative thereof as a basic skeleton, the following formula (P)

(In formula (p), X ³ is a sulfur atom, an oxygen atom or —NH—. “*” Represents a bond, respectively, provided that at least one of two “*” is bonded to an aromatic ring. ing.)

An ester group-containing structure containing a partial structure represented by the above as a basic skeleton, and the like.
The two “*” in the formula (p) are preferably bonded to an aromatic ring from the viewpoint of photoreactivity. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring.
The photoalignable group as the functional functional group A ¹ is preferably a cinnamic acid-containing group, a group having a cyclobutane ring, or an azo-containing group from the viewpoint of good photoalignment.

（式（ｂ−５）及び式（ｂ−６）中、Ｒ^１１及びＲ^１４は、それぞれ独立に水素原子、フッ素原子、炭素数１〜２０のアルキル基又は炭素数１〜２０のフルオロアルキル基である。Ｘ^１１、Ｘ^１２及びＸ^１３は、それぞれ独立に単結合、酸素原子、硫黄原子、＊−ＣＯＯ−又は＊−ＯＣＯ−（ただし、「＊」を付した結合手がそれぞれＲ^１１、Ｒ^１２又はＲ^１４と結合する。）である。Ｒ^１２及びＲ^１５は、それぞれ独立に１，４−フェニレン基又は１，４−シクロヘキシレン基である。Ｘ^１４は単結合、炭素数１〜３のアルカンジイル基、酸素原子、硫黄原子又は−ＮＨ−である。Ｘ^１５は単結合、酸素原子、＊−ＣＯＯ−又は＊−ＯＣＯ−（ただし、「＊」を付した結合手がベンゼン環と結合する。）である。Ｒ^１６は２価の芳香族基、２価の脂環式基又は２価の複素環基である。Ｒ^１３及びＲ^１８は、それぞれ独立にフッ素原子、シアノ基又はメチル基である。ａ、ｂ及びｄはそれぞれ独立に０〜３の整数であり、ｃ及びｇはそれぞれ独立に０〜４の整数である。） Specific examples of the cinnamic acid-containing group include a group represented by the following formula (b-5) and a group represented by the following formula (b-6).

(In Formula (b-5) and Formula (b-6), R ¹¹ and R ¹⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 20 carbon atoms. X ¹¹ , X ¹² and X ¹³ are each independently a single bond, an oxygen atom, a sulfur atom, * —COO— or * —OCO— (wherein the bond with “*” is R ¹¹ , bind to R ¹² or ^{R 14.)} a is ^{.R 12} and ^{R 15} are each independently a 1,4-phenylene group or a 1,4-cyclohexylene group ^{.X 14} is a single bond, 1 to carbon atoms 3 is an alkanediyl group, an oxygen atom, a sulfur atom or —NH—, wherein X ¹⁵ is a single bond, an oxygen atom, * —COO— or * —OCO— (where the bond marked with “*” is a benzene ring binds to.) in which ^{.R 16} is divalent Kozokumoto, a divalent alicyclic group or a divalent heterocyclic group .R ¹³ and R ¹⁸ are each independently a fluorine atom, a cyano group or a methyl group .a, b and d are each independently And c and g are each independently an integer of 0 to 4.)

（式中、ｐは１〜１０の整数である。Ｒ^１１及びＲ^１４は上記式（ｂ−５）及び式（ｂ−６）中のＲ^１１及びＲ^１４と同義である。） Preferable specific examples of the primary amine compound having a photoalignment group among the amine compounds (am-2) are represented by, for example, the following formulas (A-3-10) to (A-3-23). And the like.

(Wherein, p is an integer of 1 to ^{.R 11} and ^{R 14} have the same meanings as ^{R 11} and ^{R 14} in the formula (b-5) and formula (b-6).)

  Specific examples of the group having a cyclobutane ring include, for example, a group containing cyclobutanetetracarboxylic acid or a derivative thereof as a basic skeleton, and specific examples of the azo-containing group include, for example, azobenzene or a derivative thereof as a basic skeleton. Examples thereof include azobenzene-containing groups contained as: In addition, a compound (am-2) can be used individually by 1 type or in combination of 2 or more types.

(Amine compound having a coatable group)
As an example of the compound represented by the formula (3), an amine compound having a coatable group as the functional functional group (A ¹ ) (hereinafter also referred to as “amine compound (am-3)”) can be given. The coatable group preferably has a polar group, and specific examples thereof include a group having a hydroxyl group and a group having an ether bond.
When the amine compound (am-3) has a hydroxyl group, the number of hydroxyl groups contained in one molecule is not particularly limited, but is preferably 2 or more in view of a high effect of improving coating properties. It is preferable that it is a piece. Moreover, as group which has an ether bond, the group etc. which contain -O- between the carbon-carbon bonds of a C2-C10 alkyl group are mentioned, for example.

（式中、Ｒ^２２は水素原子又はメチル基である。）
なお、アミン化合物（ａｍ−３）は１種を単独で又は２種以上を組み合わせて使用することができる。また、化合物（Ａ）は、上記の１種を単独で又は２種以上を組み合わせて使用することができる。 Specific examples of the amine compound (am-3) include, for example, compounds represented by the following formulas (A-4-1) to (A-4-6) as primary amine compounds having a hydroxyl group; Examples of the primary amine compound having an ether bond include diethylene glycol amine, polyethylene glycol amine, and polypropylene glycol amine.

(In the formula, R ²² is a hydrogen atom or a methyl group.)
In addition, an amine compound (am-3) can be used individually by 1 type or in combination of 2 or more types. Moreover, a compound (A) can use said 1 type individually or in combination of 2 or more types.

(Carbonyl group-containing compound)
The carbonyl group-containing compound to be subjected to the reaction with the primary amine compound (A) can be appropriately selected according to the method for synthesizing the compound (P). As a synthesis method of the compound (P), for example, [1] a method of obtaining a compound (P) by using a polymer as a carbonyl group-containing compound and reacting the polymer with a primary amine compound (A); [2] The monomer (X) having the specific partial structure is synthesized by reacting the carbonyl group-containing compound with the primary amine compound (A), and then a raw material composition containing the monomer (X) is prepared. And a method of obtaining the compound (P) by polymerization used.

In the case of Method [1] The polymer as the carbonyl group-containing compound used in Method [1] (hereinafter also referred to as “carbonyl group-containing polymer (Q)”) is the kind of the target compound (P). It can be selected as appropriate according to the conditions. Preferably, it is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyester and poly (meth) acrylate, more preferably selected from the group consisting of polyamic acid, polyamic acid ester and polyimide. At least one polymer.

  The polyamic acid as the carbonyl group-containing polymer (Q) can be obtained, for example, by reacting a tetracarboxylic dianhydride and a diamine.

(Tetracarboxylic dianhydride)
Examples of tetracarboxylic dianhydrides used for the synthesis of polyamic acid include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. it can. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic 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- No 1,2-dicarboxylic acid Product, 3,5,6-tricarboxy-2-carboxymethylnorbornane-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 Oxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2 ] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), 1 , 3-Propylene glycol bis (am Hydrotrimellitate) etc .;

  Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like; respectively, and tetracarboxylic dianhydrides described in JP 2010-97188 A can be used. In addition, as tetracarboxylic dianhydride used for the synthesis | combination of a polyamic acid, these 1 type can be used individually or in combination of 2 or more types.

As tetracarboxylic dianhydride used for the synthesis of polyamic acid, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3 in that liquid crystal orientation and solubility in a solvent can be improved. , 5-Tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3- Dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 3-oxa Bicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3 Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [ 5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, cyclopentane It is preferable to include at least one compound selected from the group consisting of tetracarboxylic dianhydride and pyromellitic dianhydride. The amount of these preferred compounds used (the total amount when two or more are used) is preferably 5 mol% or more based on the total amount of tetracarboxylic dianhydride used for the synthesis of polyamic acid. It is more preferable to set it as 10 mol% or more, and it is more preferable to set it as 20 mol% or more.

(Diamine)
Examples of the diamine used for the synthesis of the polyamic acid include aliphatic diamine, alicyclic diamine, aromatic diamine, and diaminoorganosiloxane. Specific examples of these include aliphatic diamines such as m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and 1,3-bis (aminomethyl) cyclohexane. ;
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine) and the like;

（式（Ｄ−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。） Examples of aromatic diamines include dodecanoxydiaminobenzene, tetradecanoxydiaminobenzene, pentadecanoxydiaminobenzene, hexadecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, and cholesteryloxydiaminobenzene. Cholestanyl diaminobenzoate, cholesteryl diaminobenzoate, lanostannyl diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 1,1-bis (4 -((Aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((amino Phenoxy Methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, N- (2,4-diaminophenyl) -4 -(4-Heptylcyclohexyl) benzamide, the following formula (D-1)

(In Formula (D-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, provided that a and b are not 0 at the same time.)

Oriented 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, 1,7-bis (4-aminophenoxy) heptane, bis [2- (4-aminophenyl) ethyl] hexanedioic acid, N, N-bis (4-aminophenyl) methylamine, 1,5 -Diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4 ' -Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) Luolene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) Bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole N-phenyl-3,6-diaminocarbazole, N, N′-bis (4-aminophenyl) -benzi Other diamines such as N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid , Etc .;
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; and the diamines described in JP-A 2010-97188 can be used.

Examples of the divalent group represented by “—X ^I — (R ^I —X ^II ) _n —” in the formula (D-1) include an alkanediyl group having 1 to 3 carbon atoms, * —O—, * —COO— or * —O—C ₂ H ₄ —O— (however, a bond marked with “*” is bonded to a diaminophenyl group) is preferred. Examples of the group “—C _c H _{2c + 1} ” include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, and a tetradecyl group. Group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like, and these are preferably linear. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to other groups.

なお、ポリアミック酸の合成に使用するジアミンとしては、これらの化合物の１種を単独で又は２種以上を適宜選択して使用することができる。 Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-3).

In addition, as diamine used for the synthesis | combination of a polyamic acid, 1 type of these compounds can be used individually or in combination of 2 or more types as appropriate.

（式（Ｄ−２）中、Ｒ^３１及びＲ^３２は、それぞれ独立に単結合、炭素数１〜２０の２価の炭化水素基、又は炭素数１〜２０の２価の炭化水素基の炭素−炭素結合間に−Ｏ−若しくは−ＣＯ−を有する２価の基である。）
で表される化合物等が挙げられる。
カルボニル基含有重合体（Ｑ）を合成する場合、カルボニル基含有ジアミンの配合割合は、ポリアミック酸の合成に使用する全ジアミンに対して、１０モル％以上とすることが好ましく、１０〜９０モル％とすることがより好ましい。 When synthesizing a polyamic acid, a diamine having a carbonyl group (hereinafter also referred to as “carbonyl group-containing diamine”) is used as at least a part of the diamine used in the reaction, whereby a polyamic as a carbonyl group-containing polymer (Q) is obtained. Acids can be synthesized. Specific examples of the carbonyl group-containing diamine include, for example, the following formula (D-2)

(In the formula (D-2), R ³¹ and R ³² are each independently a single bond, a carbon atom of a divalent hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom of a divalent hydrocarbon group having 1 to 20 carbon atoms. -A divalent group having -O- or -CO- between carbon bonds.
The compound etc. which are represented by these are mentioned.
When synthesizing the carbonyl group-containing polymer (Q), the blending ratio of the carbonyl group-containing diamine is preferably 10 mol% or more, and preferably 10 to 90 mol% with respect to the total diamine used for the synthesis of the polyamic acid. More preferably.

  When applied to a liquid crystal aligning agent for a TN type, STN type or vertical alignment type liquid crystal display element, a group (orientation group) capable of imparting liquid crystal alignment ability to the coating film is introduced into the side chain of the polyamic acid. Also good. Examples of the orientation group introduced into the side chain of the polyamic acid include a group having a linear structure, a group having a mesogenic skeleton, and a group having a bulky structure. An alkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, a group having a polycyclic structure, and the like. The polyamic acid having an orientation group can be obtained, for example, by polymerization containing an orientation group-containing diamine in the monomer composition. When using orientation group containing diamine, it is preferable that the compounding quantity shall be 3 mol% or more with respect to all the diamine used for a synthesis | combination, and it is more preferable to set it as 5-70 mol%.

When liquid crystal alignment ability is imparted to the coating film formed with the liquid crystal aligning agent by a photo-alignment method, the polyamic acid used for the synthesis of the polymer (P) may be a polymer having a photo-alignment structure. Specific examples of the photo-alignment structure include groups exemplified as the photo-alignment group that the amine compound (am-2) may have.
The polyamic acid having a photoalignment structure can be obtained, for example, by polymerization containing at least one of a tetracarboxylic dianhydride having a photoalignment structure and a diamine having a photoalignment structure in the monomer composition. In this case, from the viewpoint of photoreactivity, the proportion of the monomer having a photo-alignment structure is preferably 20 mol% or more with respect to the total amount of monomers used for polymer synthesis, and is 30 to 80 mol. % Is more preferable.

(Synthesis of polyamic acid)
The polyamic acid can be obtained by reacting the tetracarboxylic dianhydride and diamine as described above with a molecular weight modifier as necessary. The ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction is 0.2 to 2 for the tetracarboxylic dianhydride acid anhydride group to 1 equivalent of the amino group of the diamine. The ratio which becomes an equivalent is preferable, and the ratio which becomes 0.3-1.2 equivalent is more preferable.
Examples of the molecular weight modifier 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. Can be mentioned. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and diamine used.

  The polyamic acid synthesis reaction is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

  Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (first group organic solvent), or one or more selected from the first group of organic solvents And a mixture of at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second-group organic solvent). In the latter case, the proportion of the second group organic solvent used is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the first group organic solvent and the second group organic solvent. Or less, more preferably 30% by weight or less.

  Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol. And at least one selected from the group consisting of halogenated phenols is used as a solvent, or a mixture of one or more of these and another organic solvent is preferably used in the above range. The amount of organic solvent used (a) is such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution. Prefer

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used for the next step as it is, may be used for the next step after isolating the polyamic acid, or may be used for the next step after purifying the isolated polyamic acid. Good. These purification operations can be performed according to known methods.

[Polyamic acid ester]
Examples of the polyamic acid ester include [I] a method of reacting the polyamic acid obtained by the above synthesis reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester and a diamine, and [III] tetracarboxylic acid. It can be obtained by a method of reacting a diester dihalide and a diamine.

  Here, examples of the esterifying agent used in the method [I] include a hydroxyl group-containing compound, an acetal compound, a halide, and an epoxy group-containing compound. Specific examples thereof include hydroxyl group-containing compounds such as alcohols such as methanol, ethanol and propanol; phenols such as phenol and cresol; and acetal compounds such as N, N-dimethylformamide diethyl acetal, N, N-diethylformamide diethyl acetal and the like; halides such as methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like; epoxy group-containing Examples of the compound include propylene oxide.

The tetracarboxylic acid diester used in Method [II] can be obtained by ring-opening tetracarboxylic dianhydride using the above alcohols. The tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. In the case of obtaining a polyamic acid ester having a partial structure represented by the above formula (1), in methods [II] and [III], a carbonyl group-containing diamine is used as at least a part of the diamine used in the reaction. 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.
The reaction solution obtained by dissolving the polyamic acid ester may be used for the next step as it is, may be used for the next step after isolating the polyamic acid ester, or the isolated polyamic acid ester is purified. You may use for the next process. These purification operations can be performed according to known methods.

(Polyimide)
Polyimide can be obtained, for example, by dehydrating and ring-closing imidized polyamic acid synthesized as described above. When a polyimide is synthesized as a carbonyl group-containing polymer (Q), the diamine used for the synthesis is [i] an embodiment in which only a carbonyl group-containing diamine is used, and [ii] a carbonyl group-containing diamine and another diamine in combination. Or [iii] an embodiment using only other diamines. In the case of [i] and [ii], the “carbonyl group” possessed by the polyimide includes a carbonyl group derived from a carbonyl group-containing diamine and a carbonyl group having an imide ring structure, and in the case of [iii] above. The carbonyl group which an imide ring structure (imide group) has is included.

  The polyimide may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure possessed by the polyamic acid that is the precursor, and only a part of the amic acid structure may be dehydrated and cyclized. It may be a partially imidized product in which a ring structure coexists. From the viewpoint that the polyimide used for the reaction has sufficient reaction sites with the primary amine compound (A), the imidation ratio is preferably 5% or more, and preferably 10 to 99%. More preferably, it is more preferably 20 to 99%, and particularly preferably 40 to 99%. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.

  The polyamic acid is preferably dehydrated and closed by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating the solution as necessary. . Of these, the latter method is preferred.

  In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to a polyamic acid solution, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

(Reaction of carbonyl group-containing polymer (Q) with compound (A))
The reaction between the carbonyl group-containing polymer (Q) and the compound (A) is preferably carried out by mixing in an organic solvent. Examples of the organic solvent to be used include compounds exemplified as organic solvents that can be used for the synthesis of polyamic acid. The amount of the organic solvent used is preferably such that the total amount of the carbonyl group-containing polymer (Q) and the compound (A) is 0.1 to 50% by weight based on the total amount of the reaction solution.

When a polyimide is used as the carbonyl group-containing polymer (Q), the use ratio of the polyimide and the primary amine compound (A) is such that the amino group of the compound (A) is 0. A ratio of 001 to 2.0 molar equivalent is preferable, a ratio of 0.01 to 1.5 molar equivalent is more preferable, and a ratio of 0.05 to 1.0 molar equivalent is more preferable.
When polyamic acid or polyamic acid ester is used as the carbonyl group-containing polymer (Q), the amount of the primary amine compound (A) used in the reaction is 1 molar equivalent of the carbonyl group of the carbonyl group-containing diamine used in the polymerization reaction. The ratio with which the amino group of the compound (A) is 0.01 to 2.0 molar equivalents is preferable, and the ratio with 0.05 to 1.5 molar equivalents is more preferable.

  0-120 degreeC is preferable and, as for the reaction temperature in the said reaction, 10-100 degreeC is more preferable. The reaction time is preferably 0.1 to 12 hours, more preferably 0.5 to 6 hours. In addition, when mixing a carbonyl group containing polymer (Q) and a compound (A), in order to improve reactivity, you may mix while heating, or you may heat after mixing.

When preparing the liquid crystal aligning agent containing the compound (P) obtained by the method of said [1], the preparation method is not specifically limited. For example, after a carbonyl group-containing polymer (Q) and a primary amine compound (A) are reacted in advance to obtain a compound (P), a liquid crystal aligning agent is prepared using the obtained compound (P). Also good. Alternatively, a liquid crystal aligning agent containing the compound (P) is prepared by mixing the carbonyl group-containing polymer (Q) and the primary amine compound (A) in an organic solvent as a solvent when preparing the liquid crystal aligning agent. It may be prepared.
In the former case, the reaction solution containing the compound (P) may be used as it is for the preparation of the liquid crystal aligning agent, or after isolation of the compound (P), it may be used for the preparation of the liquid crystal aligning agent. The purified compound (P) may be purified and then used for preparing a liquid crystal aligning agent. These purification operations can be performed according to known methods.

（式（１−ｂ）中、Ａ^１及びＲ^１ａは上記式（３）と同義である。） In addition, the compound which has a functional functional group in a side chain can be obtained by using the compound represented by the said Formula (3) as a primary amine compound (A). Specifically, a compound having a partial structure represented by the following formula (1-b) can be obtained.

(In Formula (1-b), A ¹ and R ^1a have the same meanings as in Formula (3) above).

In the case of method [2] In the above method [2], the carbonyl group-containing compound used for the synthesis of the monomer (X) can be appropriately selected according to the main skeleton of the target compound (P). . For example, when a polyamic acid, polyamic acid ester or polyimide is obtained as the compound (P), a diamine having a carbonyl group is preferable from the viewpoint of easy synthesis of the compound.
The dehydration condensation reaction between the carbonyl group-containing compound and the primary amine compound (A) can be preferably carried out in an organic solvent, if necessary, in the presence of a catalyst. As an organic solvent used for reaction, the compound etc. which were illustrated as an organic solvent used for the synthesis | combination of a polyamic acid, for example are mentioned. The proportion of the carbonyl group-containing compound used for the synthesis reaction of the monomer (X) and the primary amine compound (A) is a carbonyl group with respect to 1 molar equivalent of the amino group of the primary amine compound (A). The ratio in which the carbonyl group of the containing compound is 0.2 to 2 molar equivalents is preferable, and the ratio in which 0.3 to 1.5 molar equivalents is more preferable. Various conditions such as reaction temperature and reaction time can be appropriately set according to the target compound.

The polymerization reaction using the raw material composition containing the monomer (X) can be performed by appropriately combining organic chemistry methods. For example, when the compound (P) is a polyamic acid, a polyamic acid ester or a polyimide, it can be carried out according to the synthesis method and reaction conditions described above.
In addition, regarding a polymer having a main skeleton other than polyamic acid, polyamic acid ester, and polyimide, a desired function can be imparted to the polymer by using a Schiff base for the introduction (platform) of a functional functional group. All of them have the same effect as possible. Therefore, the present invention can be similarly applied to a polymer having a main skeleton which is not described in Examples described later.

  When the compound (P) is a polymer, the solution viscosity and the weight average molecular weight (Mw) of the polymer can be appropriately selected according to the main skeleton. For example, in the case of polyamic acid, polyamic acid ester, and polyimide, the solution viscosity and weight average molecular weight (Mw) of the polymer are 20 to 1,800 mPa · s solution when the solution is 15% by weight. It is preferable to have a viscosity, and it is more preferable to have a solution viscosity of 50 to 1,500 mPa · s. The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. Moreover, the molecular weight distribution (Mw / Mn) represented by the ratio between Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.

<Other ingredients>
Although the liquid crystal aligning agent of this embodiment contains the above compounds (P), you may contain another component as needed. Examples of such other components include a polymer having no specific partial structure (hereinafter also referred to as “other polymer”), a compound having at least one epoxy group in the molecule (hereinafter referred to as “epoxy group-containing compound”). ), A functional silane compound, a metal chelate compound, a curing accelerator, a surfactant, and the like.

[Other polymers]
The above other polymers can be used for improving solution properties and electrical properties. The main skeleton of the other polymer is not particularly limited. Specifically, for example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, etc. as the main skeleton The polymer which has is mentioned.
When adding another polymer to a liquid crystal aligning agent, it is preferable that the mixture ratio shall be 50 weight part or less with respect to a total of 100 weight part of the polymer contained in a liquid crystal aligning agent, The amount is more preferably 40 parts by weight, and still more preferably 0.1 to 30 parts by weight.

[Epoxy group-containing compound]
The epoxy group-containing compound can be used to improve the adhesion and electrical properties with the substrate surface in the liquid crystal alignment film. Examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylylene diene Amine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diamy Diphenylmethane, N, N-diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane, N, N-diglycidyl - may be mentioned as being preferred and cyclohexylamine. In addition, as an example of the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used.
When these epoxy group-containing compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 40 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. More preferably, the content is ˜30 parts by weight.

[Functional silane compounds]
The functional silane compound can be used for the purpose of improving the printability of the liquid crystal aligning agent. Examples of such functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl -3,6- Methyl azananoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycid And xylpropyltrimethoxysilane.
When these functional silane compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 2 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. It is more preferable to set it to -0.2 weight part.

[Metal chelate compounds]
When the polymer component of the liquid crystal aligning agent has an epoxy structure, the metal chelate compound is a liquid crystal aligning agent (particularly a liquid crystal for a retardation film) for the purpose of ensuring the mechanical strength of the film formed by low-temperature treatment. Contained in the alignment agent). As the metal chelate compound, it is preferable to use an acetylacetone complex or acetoacetic acid complex of a metal selected from aluminum, titanium and zirconium. Specifically, for example, diisopropoxyethyl acetoacetate aluminum, tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetonate) Examples thereof include titanium, tri-n-butoxyethyl acetoacetate zirconium, and di-n-butoxybis (ethyl acetoacetate) zirconium. When the metal chelate compound is added, the use ratio thereof is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, with respect to a total of 100 parts of the components including the epoxy structure, More preferably, it is 1-30 weight part.

[Curing accelerator]
When the polymer component in the liquid crystal aligning agent has an epoxy structure, the curing accelerator is a liquid crystal in order to ensure the mechanical strength of the liquid crystal alignment film to be formed and the stability over time of the liquid crystal alignment. It is contained in an aligning agent (particularly, a liquid crystal aligning agent for a retardation film). As the curing accelerator, for example, a compound having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic anhydride group, or the like can be used. A compound having is preferred. Specific examples thereof include compounds having a phenol group such as cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol; compounds having a silanol group such as trimethylsilanol, triethylsilanol, 1 , 1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis (hydroxydimethylsilyl) benzene, triphenylsilanol, tri (p-tolyl) silanol, diphenylsilanediol, etc. be able to. When the curing accelerator is added, the use ratio thereof is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the total components including the epoxy structure, and further Preferably it is 1-30 weight part.

[Surfactant]
The surfactant can be contained in a liquid crystal aligning agent (particularly, a liquid crystal aligning agent for a retardation film) for the purpose of improving the applicability of the liquid crystal aligning agent to the substrate. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. be able to. The proportion of the surfactant used is preferably 10 parts by weight or less, and more preferably 1 part by weight or less with respect to 100 parts by weight of the total amount of the liquid crystal aligning agent.
In addition to the above, other components include compounds having at least one oxetanyl group in the molecule, antioxidants, and the like.

<Solvent>
The liquid crystal aligning agent of this embodiment is prepared as a liquid composition in which the compound (P) and other components used as necessary are preferably dispersed or dissolved in an appropriate solvent.

  Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, 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 methoxypropionate, ethyl ethoxypropionate, 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 acetate, diethylene glycol dimethyl ether, diethylene glycol Recall diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. be able to. These can be used individually by 1 type or in mixture of 2 or more types.

  The solid content concentration in the liquid crystal aligning agent (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc. It is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent is applied to the substrate surface as will be described later, and preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by weight, 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 weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive, and the viscosity of the liquid crystal aligning agent increases and the applicability decreases. There is a tendency.

  The particularly preferable solid content concentration range varies depending on the use of the liquid crystal aligning agent and the method used when the liquid crystal aligning agent is applied to the substrate. For example, when a liquid crystal aligning agent for a liquid crystal aligning film is applied to a substrate by a spinner method, the solid content concentration (the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) Is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s. Moreover, about the liquid crystal aligning agent for retardation films, the solid content density | concentration of a liquid crystal aligning agent is 0.2 to 10 weight% from a viewpoint which makes the applicability | paintability of a liquid crystal aligning agent, and the film thickness of the coating film formed moderate. It is preferable that it is the range of 3-10 weight%. The temperature at which the liquid crystal aligning agent is prepared is preferably 10 to 100 ° C, more preferably 20 to 80 ° C.

<Liquid crystal display element and retardation film>
A liquid crystal alignment film can be manufactured by using the liquid crystal aligning agent described above. Moreover, the liquid crystal aligning film formed using the liquid crystal aligning agent of this Embodiment can be applied preferably to the liquid crystal aligning film for liquid crystal display elements, and the liquid crystal aligning film for retardation films. The liquid crystal display element and the retardation film will be described below.

[Liquid crystal display element]
The liquid crystal display element of the present embodiment includes a liquid crystal alignment film formed using the above liquid crystal aligning agent. The operation mode of the liquid crystal display element is not particularly limited, and for example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB (Optically Compensated Bend) type. It can be applied to various driving methods. The liquid crystal display element can be manufactured, for example, by the following steps (I-1) to (I-3). In step (I-1), the substrate to be used varies depending on the desired operation mode. Steps (I-2) and (I-3) are common to each operation mode.

[Step (I-1): Formation of coating film]
First, a liquid crystal aligning agent is applied on the substrate, and then the coating surface is heated to form a coating film on the substrate.
(I-1A) When manufacturing a TN-type, STN-type, or VA-type liquid crystal display element, for example, first, a pair of two substrates provided with patterned transparent conductive films is formed, and each transparent conductive film is formed. On the surface, a liquid crystal aligning agent is preferably applied by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method, respectively. As the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, an 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. Can be used. In order to obtain a patterned transparent conductive film, for example, after forming a transparent conductive film without a pattern, a method of forming a pattern by photo-etching; a method of using a mask having a desired pattern when forming a transparent conductive film; And so on. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or a functional titanium compound is formed on the surface of the substrate surface on which the coating film is formed. It is also possible to perform a pretreatment to apply the above in advance.

  After applying the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. Then, a baking (post-baking) process is implemented for the purpose of removing a solvent completely and heat imidating the amic acid structure which exists in a polymer as needed. The firing temperature (post-bake temperature) at this time is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The thickness of the film thus formed is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

  (I-1B) When manufacturing an IPS type or FFS type liquid crystal display element, an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and an electrode are provided. A liquid crystal aligning agent is apply | coated to one surface of the counter substrate which is not formed, respectively, Then, each coating surface is heated, and a coating film is formed. Regarding the material used for the substrate and the transparent conductive film, the coating method, the heating conditions after coating, the patterning method for the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the coating film to be formed The same as (I-1A). As the metal film, for example, a film made of a metal such as chromium can be used.

  In both cases (I-1A) and (I-1B), a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film is formed by applying a liquid crystal aligning agent on the substrate and then removing the organic solvent. Is done. At this time, when the polymer contained in the liquid crystal aligning agent is a polyamic acid, a polyamic acid ester, or an imidized polymer having an imide ring structure and an amic acid structure, a coating film It is good also as a more imidized coating film by advancing the dehydration ring-closing reaction by further heating after formation.

[Step (I-2): Orientation treatment]
When manufacturing a TN type, STN type, IPS type, or FFS type liquid crystal display element, the process (alignment process) which provides liquid crystal aligning ability to the coating film formed at the said process (I-1) is implemented. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. As the alignment treatment, for example, a rubbing treatment that imparts liquid crystal alignment ability to the coating film by rubbing the coating film in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, cotton, etc., a coating film formed on the substrate And a photo-alignment treatment for imparting liquid crystal alignment ability to the coating film. On the other hand, when manufacturing a vertical alignment type liquid crystal display element, the coating film formed in the step (I-1) can be used as it is as a liquid crystal alignment film, but the coating film is subjected to an alignment treatment. Also good.

  The light irradiation in the photo-alignment treatment is (1) a method of irradiating the coating film after the post-baking process, (2) a method of irradiating the coating film after the pre-baking process and before the post-baking process, (3 ) It can be performed by a method of irradiating the coating film during heating of the coating film in at least one of the pre-bake process and the post-bake process.

The light applied to the coating film can be polarized or non-polarized radiation. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. When the radiation used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof. When non-polarized radiation is irradiated, the irradiation direction is an oblique direction.
As a light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. Ultraviolet rays in a preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter or a diffraction grating. The amount of light irradiation is preferably 100 to 50,000 J / m ² , more preferably 300 to 20,000 J / m ² . Moreover, you may perform light irradiation with respect to a coating film, heating a coating film, in order to improve the reactivity. The temperature at the time of heating is 30-250 degreeC normally, Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC.

  Note that the liquid crystal alignment film after the rubbing treatment is further subjected to a treatment for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film, or a surface of the liquid crystal alignment film. A resist film is formed on the part, and a rubbing process is performed in a direction different from the previous rubbing process, followed by a process of removing the resist film, so that the liquid crystal alignment film has different liquid crystal alignment capabilities for each region. . In this case, it is possible to improve the visibility characteristics of the obtained liquid crystal display element. A liquid crystal alignment film suitable for a VA liquid crystal display element can also be suitably used for a PSA (Polymer sustained alignment) type liquid crystal display element.

[Step (I-3): Construction of liquid crystal cell]
Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates disposed to face each other. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, two substrates are arranged opposite to each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell is manufactured by injecting and filling the liquid crystal into the cell gap partitioned by the step of sealing the injection hole. The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped at predetermined locations on the liquid crystal alignment film surface. After that, the other substrate is bonded so that the liquid crystal alignment films face each other and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell. . Regardless of which method is used, the liquid crystal cell manufactured as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase, and then slowly cooled to room temperature, thereby removing the flow alignment at the time of filling the liquid crystal. It is desirable to do.

  As the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenyl cyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals. Biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal, and the like can be used. Further, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck & Co., Inc.). A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.

  And a liquid crystal display element can be obtained by sticking a polarizing plate on the outer surface of a liquid crystal cell. As a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film itself in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films The polarizing plate which consists of can be mentioned.

[Phase difference film]
When producing a retardation film using the liquid crystal aligning agent of the present embodiment, it is possible to form a uniform liquid crystal aligning film while suppressing the generation of dust and static electricity during the process, radiation irradiation It is preferable to use a photo-alignment method in that a plurality of regions having different liquid crystal alignment directions can be arbitrarily formed on the substrate by using an appropriate photomask sometimes. Specifically, it can be produced through the following steps (II-1) to (II-3).

[Step (II-1): Formation of coating film by liquid crystal aligning agent]
First, a liquid crystal aligning agent is apply | coated on a board | substrate and a coating film is formed. As the substrate used here, a transparent substrate made of a synthetic resin such as triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, polymethyl methacrylate, polycarbonate, etc. is preferably exemplified. Can do. Of these, TAC is generally used as a protective layer for a polarizing film in a liquid crystal display device. In addition, polymethyl methacrylate can be preferably used as a substrate for a retardation film in that the hygroscopicity of the solvent is low, the optical properties are good, and the cost is low. In addition, for the substrate used for the application of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the coating film, a conventionally known pretreatment is performed on the surface of the substrate surface on which the coating film is formed. May be implemented.

  In many cases, the retardation film is used in combination with a polarizing film. At this time, it is necessary to attach the retardation film by precisely controlling the angle with respect to the polarization axis of the polarizing film in a specific direction so that the desired optical characteristics can be exhibited. Accordingly, by forming a liquid crystal alignment film having a liquid crystal alignment ability in a predetermined angle direction on a substrate such as a TAC film or polymethyl methacrylate, the angle of the retardation film is controlled on the polarizing film. The step of bonding can be omitted. Thereby, it can contribute to the improvement of productivity of a liquid crystal display element. In order to form a liquid crystal alignment film having a liquid crystal alignment ability in a predetermined angle direction, it is preferable to carry out by a photo-alignment method.

The liquid crystal aligning agent can be applied onto the substrate by an appropriate application method such as a roll coater method, a spinner method, a printing method, an ink jet method, a bar coater method, an extrusion die method, a direct gravure coater method, a chamber. Doctor coater method, offset gravure coater method, single roll kiss coater method, reverse kiss coater method using small diameter gravure roll, 3 reverse roll coater method, 4 reverse roll coater method, slot die method, air doctor coater method A positive rotation roll coater method, a blade coater method, a knife coater method, an impregnation coater method, an MB coater method, an MB reverse coater method, and the like can be employed.
After coating, the coated surface is heated (baked) to form a coating film. The heating temperature at this time is preferably 40 to 150 ° C, more preferably 80 to 140 ° C. The heating time is preferably 0.1 to 15 minutes, and more preferably 1 to 10 minutes. The film thickness of the coating film formed on the substrate is preferably 1 to 1,000 nm, more preferably 5 nm to 500 nm.

[Step (II-2): Light irradiation step]
Next, the coating film formed on the substrate as described above is irradiated with light to impart liquid crystal alignment ability to the coating film. Here, the description of the photo-alignment process in the step (I-2) can be applied to the description of the wavelength of light to be irradiated, the type of light, and the light source used. The dose of light is preferably in a 0.1~1,000mJ / cm ^2, more preferably to 1 to 500 mJ / cm ^2, and more preferably be 2~200mJ / cm ^2.

[Step (II-3): Formation of Liquid Crystal Layer]
Next, a polymerizable liquid crystal is applied and cured on the coating film after the light irradiation as described above. Thereby, the coating film (liquid crystal layer) containing a polymerizable liquid crystal is formed. The polymerizable liquid crystal used here is a liquid crystal compound or a liquid crystal composition that is polymerized by at least one treatment of heating and light irradiation. As such a polymerizable liquid crystal, a conventionally known one can be used. Specifically, for example, non-patent literature (“UV curable liquid crystal and its application”, liquid crystal, Vol. 3, No. 1 (1999)). , Pp 34-42). Further, cholesteric liquid crystal; discotic liquid crystal; twisted nematic alignment type liquid crystal to which a chiral agent is added may be used. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may further be a composition containing a known polymerization initiator, an appropriate solvent, and the like.
In order to apply the polymerizable liquid crystal as described above onto a coating film formed using a liquid crystal aligning agent, for example, an appropriate application method such as a bar coater method, a roll coater method, a spinner method, a printing method, an ink jet method or the like is used. Can be adopted.

Next, the coating film of the polymerizable liquid crystal formed as described above is subjected to one or more treatments selected from heating and light irradiation to cure the coating film to form a liquid crystal layer. It is preferable to perform these treatments in a superimposed manner because good alignment can be obtained.
The heating temperature of the coating film should be appropriately selected depending on the type of polymerizable liquid crystal used. For example, when using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40 to 80 ° C. The heating time is preferably 0.5 to 5 minutes.
As irradiation light, non-polarized ultraviolet rays having a wavelength in the range of 200 to 500 nm can be preferably used. The irradiation dose of light, preferably in the 50~10,000mJ / cm ^2, and more preferably a 100~5,000mJ / cm ^2.
The thickness of the liquid crystal layer to be formed is appropriately set depending on desired optical characteristics. For example, when manufacturing a half-wave plate for visible light having a wavelength of 540 nm, a thickness is selected such that the retardation of the formed retardation film is 240 to 300 nm. The thickness is selected such that the phase difference is 120 to 150 nm. The thickness of the liquid crystal layer from which the desired retardation is obtained varies depending on the optical characteristics of the polymerizable liquid crystal used. For example, when RMS03-013C manufactured by Merck is used, the thickness for manufacturing a quarter-wave plate is in the range of 0.6 to 1.5 μm.

  The retardation film obtained as described above can be preferably applied as a retardation film of a liquid crystal display element. The liquid crystal display element to which the retardation film manufactured using the liquid crystal aligning agent of the present embodiment is applied is not limited in its driving method, for example, TN type, STN type, IPS type, FFS type, VA type, etc. It can be applied to various methods. The retardation film is used by attaching the substrate-side surface of the retardation film to the outer surface of the polarizing plate disposed on the viewing side of the liquid crystal display element. Therefore, it is preferable that the retardation film substrate is made of TAC or an acrylic base, and the retardation film substrate also functions as a protective film for the polarizing film.

  Here, there is a roll-to-roll method as a method for producing a retardation film on an industrial scale. In this method, a film is unwound from a wound body of a long base film, a liquid crystal alignment film is formed on the unwound film, and a polymerizable liquid crystal is applied and cured on the liquid crystal alignment film. It is the method of performing the process and the process which laminates | stacks a protective film as needed in the continuous process, and collect | recovering the film after passing through these processes as a wound body. The retardation film formed using the liquid crystal aligning agent of this Embodiment has favorable adhesiveness with respect to a board | substrate, and even when this is stored as a wound body etc., a liquid crystal aligning film and a board | substrate are hard to peel. Therefore, it is possible to suppress a decrease in product yield when the retardation film is manufactured by the roll-to-roll method.

  The liquid crystal display element of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, cellular phones, smartphones, various types. It can be used for various display devices such as a monitor, a liquid crystal television, and an information display.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

In the following examples, the weight average molecular weight Mw of the polymer, the imidization rate, and the solution viscosity of the polymer solution were measured by the following methods. Hereinafter, the compound represented by Formula X may be simply referred to as “Compound X”.
[Weight average molecular weight Mw of polymer]
Mw is a polystyrene equivalent value measured by GPC under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Imidation rate of polymer]
A solution containing polyimide is poured into pure water, and the resulting precipitate is sufficiently dried at room temperature under reduced pressure, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR is measured at room temperature using tetramethylsilane as a reference substance. did. From the obtained ¹ H-NMR spectrum, the imidation ratio was determined using the following formula (EX-1).
Imidation ratio (%) = (1-A ¹ / A ² × α) × 100 (EX-1)
(In Formula (1), A ¹ is a peak area derived from protons of NH groups appearing near 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). 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 compounds>
[Synthesis Example 1-1; Synthesis of Compound (X-1)]
Compound (X-1) was synthesized according to the following scheme 1.

[Synthesis Example 1-2; Synthesis of Compound (X-2)]
Compound (X-2) was synthesized according to the following scheme 2.

[Synthesis Example 1-3; Synthesis of Compound (X-3)]
Compound (X-3) was synthesized according to the following scheme 3.

[Synthesis Example 1-4; Synthesis of Compound (A-3-16-1)]
Compound (A-3-16-1) was synthesized according to the following scheme 4.

<Synthesis of polymer>
[Synthesis Example 2-1; Synthesis of Polymer (PA-1)]
9.75 g of pyromellitic dianhydride as a tetracarboxylic dianhydride (93 mol parts relative to 100 mol parts of the total amount of diamines used in the synthesis) and 5.47 g of compound (X-2) as an amine compound (20 mol parts), and 14.77 g (80 mol parts) of bis [2- (4-aminophenyl) ethyl] hexanedioic acid were added to 85 g of N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL And dissolved in 85 g of a mixed solvent, and reacted at 30 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol, and then dried at 40 ° C. under reduced pressure for 15 hours to obtain 28.4 g of polyamic acid (hereinafter referred to as polymer (PA-1)). The obtained polymer (PA-1) was prepared to be 15% by weight with a solvent composition of NMP: GBL = 50: 50, and the viscosity of this solution was measured to be 541 mPa · s. Further, when this polymer solution was allowed to stand at 20 ° C. for 3 days, it did not gel and the storage stability was good.

[Synthesis Example 2-2 to Synthesis Example 2-4]
A polyamic acid was obtained in the same manner as in Synthesis Example 2-1, except that the types and amounts of tetracarboxylic dianhydride and amine compound used in the reaction were changed as shown in Table 1 below. When each of the polymer solutions obtained in Synthesis Example 2-2 to Synthesis Example 2-4 was allowed to stand at 20 ° C. for 3 days, none of them was gelled, and the storage stability was good.

The numerical values in Table 1 indicate, for tetracarboxylic dianhydrides, the usage ratio (mol%) relative to the total amount of tetracarboxylic dianhydrides used for the reaction, and for diamines, the total amount of diamine used for the reaction. The ratio of use (mol%) to the amount is shown.
Abbreviations of tetracarboxylic dianhydride and diamine in Table 1 are as follows.
(Tetracarboxylic dianhydride)
AN-1; 1,2,3,4-cyclobutanetetracarboxylic dianhydride AN-2; pyromellitic dianhydride AN-3; 2,3,5-tricarboxycyclopentylacetic dianhydride AN-4; 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione AN-5; 5- (2,5 -Dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione AN-6; bicyclo [3.3.0] Octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride (amine compound)
DA-1; Compound DA-2 represented by Formula (X-2); Compound DA-3 represented by Formula (X-3); 4,4′-diaminodiphenylmethane DA-4; -Bis (4-aminophenoxy) pentane DA-5; bis [2- (4-aminophenyl) ethyl] hexanedioic acid DA-6; 4,4'-diaminodiphenylamine DA-7; 3,5-diaminobenzoic acid DA-8; N- (2,4-diaminophenyl) -4- (4-heptylcyclohexyl) benzamide DA-9; 4- (tetradecoxy) benzene-1,3-diamine DA-10; 3,5- Cholestanyl diaminobenzoate MA-1; tris (hydroxymethyl) aminomethane The polymer (PA-2) is particularly suitable for a TN liquid crystal display device.

[Synthesis Example 2-5; Synthesis of Polymer (PI-1)]
21.48 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride (98 mol parts relative to 100 mol parts of the total amount of amine compounds used in the synthesis), and 3,4 as amine compounds 5.95 g (40 mol parts) of 5-diaminobenzoic acid and 22.56 g (60 mol parts) of bis [2- (4-aminophenyl) ethyl] hexanedioic acid were dissolved in 200 g of NMP and reacted at room temperature for 6 hours. Went. Next, 250 g of NMP was added, 15.2 g of pyridine and 19.6 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 100 ° C. for 5 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol, and then dried at 40 ° C. under reduced pressure for 15 hours to obtain polyimide (PI-1) having an imidation ratio of about 75%. The obtained polyimide (PI-1) was prepared so that it might become 15 weight% with NMP. When the viscosity of this solution was measured, it was 841 mPa · s. Moreover, when the obtained polymer solution was allowed to stand at 20 ° C. for 3 days, it did not gel and the storage stability was good.

[Synthesis Example 2-6; Synthesis of Polymer (PI-2)]
In the said synthesis example 2-5, the polyimide was obtained like the synthesis example 2-5 except having changed the kind and quantity of the tetracarboxylic dianhydride and amine compound which are used for reaction as the said Table 1. When the polyimide solution was allowed to stand at 20 ° C. for 3 days in the same manner as in Synthesis Example 2-5, it did not gel and the storage stability was good.

[Synthesis Example 2-7; Synthesis of Polymer (PES-1)]
Into a 1 L glass reaction vessel was added 87 g (0.5 mol) of dimethyl adipate, 445.7 g (0.7 mol) of the compound (X-1) obtained in Synthesis Example 1-1 as a diol compound, and 22 mg of potassium titanium oxalate. I took it. A transesterification reaction was carried out at 240 ° C. for 3 hours under a nitrogen atmosphere, and the produced methanol was removed from the reaction system to prepare a polyester having a low polymerization degree. Subsequently, the pressure was gradually reduced over 1 hour, and the temperature was raised to 0.4 mmHg and 280 ° C. Then, the polymer (PES-1) was obtained by performing a polycondensation reaction for 4 hours on these conditions.

<Preparation and evaluation of liquid crystal aligning agent>
[Example 1: rubbing alignment FFS type liquid crystal display element]
(1) Preparation of liquid crystal aligning agent As a polymer, the polymer (PI-1) obtained in Synthesis Example 2-5 and 4-amino-2,2,6,6-tetramethylpyridine (the above formula (A-2 -1)) in an amount of 30 mole parts relative to 100 mole parts of the imide group of the polymer (PI-1), γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP) ) And butyl cellosolve (BC) (GBL: NMP: BC = 40: 40: 20 (weight ratio)) to obtain a solution having a solid content concentration of 3.5% by weight. The liquid crystal aligning agent (R-1) was prepared by filtering this solution through a filter having a pore diameter of 0.2 μm.

(2) Evaluation of applicability The liquid crystal aligning agent (R-1) prepared above was applied on a glass substrate using a spinner, prebaked on a hot plate at 80 ° C. for 1 minute, and then the interior was filled with nitrogen. By heating (post-baking) in a substituted 200 ° C. oven for 1 hour, a coating film having an average film thickness of 1,000 mm was formed. This coating film was observed with a microscope having a magnification of 100 times and 10 times to examine the presence or absence of film thickness unevenness and pinholes. Evaluation is that the film thickness unevenness and the pinhole are not observed even when observed with a 100 × microscope, the coating property is “good”, and the 100 × microscope observes at least one of the film thickness unevenness and the pinhole. However, when both the film thickness unevenness and the pinhole were not observed with a 10 × microscope, the coating property was “OK”. At least one of the film thickness unevenness and the pinhole was clearly observed with a 10 × microscope. The case was evaluated as “bad” coating property. In this example, neither film thickness unevenness nor pinhole was observed even with a 100 × microscope, and the coating property was “good”.
(3) Evaluation of surface unevenness of coating film The coating film obtained above was observed with an atomic force microscope (AFM), and the center average roughness (Ra) was measured. In the evaluation, the surface roughness was “good” when Ra was less than 2.0 nm, “good” when it was 2.0 nm or more and less than 5.0 nm, and “bad” when it was 5.0 nm or more. In this example, Ra = 0.7 nm, and the surface unevenness was “good”.

(4) Evaluation of rubbing resistance The coating film obtained above was rubbed at a roll rotation speed of 1000 rpm, a stage moving speed of 20 cm / sec, and a hair foot indentation length of 0.4 mm by a rubbing machine having a roll wrapped with a cotton cloth. The treatment was performed 7 times. Foreign matter (a piece of coating film) due to rubbing scraping on the obtained substrate was observed with an optical microscope, and the number of foreign matters in a 500 μm × 500 μm region was measured. In the evaluation, the rubbing resistance was “good” when the number of foreign materials was 3 or less, and the rubbing resistance “good” when 4 or more and 7 or less, and the rubbing resistance “bad” when 8 or more. As a result, the rubbing resistance of this coating film was “good”.

(5) Manufacture of FFS type liquid crystal display element by rubbing process The FFS type liquid crystal display element 10 shown in FIG. 1 was produced. First, a glass substrate 11a having an electrode pair on one side of which a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and a top electrode 13 patterned in a comb shape are formed in this order, and an electrode The liquid crystal aligning agent (R-1) prepared in the above (1) is paired with the opposite glass substrate 11b not provided with the glass substrate 11a, and the surface of the glass substrate 11a having the transparent electrode and one surface of the opposite glass substrate 11b. The coating film was formed by coating using a spinner. Next, this coating film was pre-baked for 1 minute on a hot plate at 80 ° C., and then heated (post-baked) at 230 ° C. for 15 minutes in an oven in which the inside of the chamber was replaced with nitrogen, so that the average film thickness was 1,000 mm. A coating film was formed. A schematic plan view of the top electrode 13 used here is shown in FIG. 2A is a top view of the top electrode 13, and FIG. 2B is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2A. In this example, the line width d1 of the electrodes was 4 μm, and the distance d2 between the electrodes was 6 μm. Further, as the top electrode 13, four types of drive electrodes of electrode A, electrode B, electrode C, and electrode D were used. FIG. 3 shows the configuration of the drive electrode used. In this case, the bottom electrode 15 functions as a common electrode that acts on all of the four drive electrodes, and each of the four drive electrode regions serves as a pixel region.

  Subsequently, the surface of the coating film formed on the glass substrates 11 a and 11 b was rubbed with cotton to form the liquid crystal alignment film 12. In FIG.2 (b), the rubbing direction with respect to the coating film formed on the glass substrate 11a is shown by the arrow. Next, after applying the product name “XN-21-S” (manufactured by Mitsui Chemicals) as a sealant to the outer edge of the surface having the liquid crystal alignment film in one of the pair of substrates, Then, the substrates were bonded together via a spacer having a diameter of 3.5 μm so that the rubbing directions of the substrates 11a and 11b were antiparallel, and the sealant was cured. Next, liquid crystal MLC-6221 (manufactured by Merck & Co., Inc.) was injected between the pair of substrates through the liquid crystal injection port to form the liquid crystal layer 16. Furthermore, the liquid crystal display element 10 was produced by bonding a polarizing plate (not shown) on both outer surfaces of the substrates 11a and 11b so that the polarization directions of the two polarizing plates were orthogonal to each other.

(6) Evaluation of liquid crystal orientation For the FFS type liquid crystal display device manufactured as described above, the presence or absence of abnormal domains in the change in brightness when a voltage of 5 V is turned ON / OFF (applied / released) is observed with a microscope at a magnification of 50 times. did. In the evaluation, when the abnormal domain was not observed, the liquid crystal alignment was “good”, and when the abnormal domain was observed, the liquid crystal alignment was “bad”. In this liquid crystal display element, the liquid crystal orientation was “good”.
(7) Evaluation of voltage holding ratio For the FFS type liquid crystal display device manufactured as described above, a voltage of 5 V was applied at 23 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, and 167 milliseconds after the release of application. When the voltage holding ratio (VHR) of was measured, it was 99.3%. In addition, as a measuring apparatus, Toyo Technica Co., Ltd. make and VHR-1 were used.

(8) Heat resistance About the FFS type liquid crystal display element manufactured above, the voltage holding ratio was measured in the same manner as in the above (7), and the value was defined as the initial VHR (VHR _BF ). Next, the liquid crystal display element after the initial VHR measurement was left in an oven at 100 ° C. for 500 hours. Thereafter, the liquid crystal display element was left at room temperature and allowed to cool to room temperature, and then the voltage holding ratio (VHR _AF ) was measured in the same manner as described above. Further, the rate of change in voltage holding ratio (ΔVHR (%)) before and after application of thermal stress was determined by the following mathematical formula (EX-2).
ΔVHR = ((VHR _BF −VHR _AF ) ÷ VHR _BF ) × 100 (EX−2)
Evaluation of heat resistance is “good” when the rate of change ΔVHR is less than 4%, “good” when 4% or more and less than 5%, and “high” when 5% or more. Went as "bad". As a result, ΔVHR of the liquid crystal display element of this example was 1.2%, and the heat resistance was “good”.
(9) Light resistance About the FFS type liquid crystal display element manufactured above, the voltage holding ratio was measured in the same manner as in the above (7), and the value was defined as the initial VHR (VHR _BF ). Next, the liquid crystal display element after the initial VHR measurement was allowed to stand in an 80 ° C. oven under LED lamp irradiation for 200 hours, and then allowed to stand at room temperature and naturally cooled to room temperature. With respect to the liquid crystal cell after light irradiation, the voltage holding ratio was measured again by the same method as described above. This value was defined as a voltage holding ratio (VHR _AFBL ) after light irradiation. The decrease amount ΔVHR _BL (%) of the voltage holding ratio was obtained from the following formula (EX-3) and evaluated as light resistance.
ΔVHR _BL = ((VHR _BF −VHR _AFBL ) ÷ VHR _BF ) × 100 (EX-3)
When ΔVHR was less than 3%, light resistance was judged as “good”, when 3% or more and less than 5.0%, “good”, and when 5.0% or more, “bad”. . As a result, ΔVHR of the liquid crystal display element of this example was 0.9%, and the heat resistance was “good”.

(10) Uneven resistance around the sealant (bezel unevenness resistance)
The FFS type liquid crystal display device manufactured above was stored for 30 days under conditions of 25 ° C. and 50% RH, and then driven with an AC voltage of 5 V to observe the lighting state. The evaluation is “good” if the luminance difference (more black or more white) is not visually recognized around the sealant, but is “good” if the luminance difference disappears within 5 minutes after lighting. The case where the luminance difference disappeared within the super 20 minutes was judged “good”, and the case where the luminance difference was visually recognized even after 20 minutes passed was judged as “bad”. As a result, the luminance difference of the liquid crystal display element was not visually recognized, and was judged as “good”.

[Examples 2 to 8 and 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 and compound (A) were changed as shown in Table 2 below, and an FFS type liquid crystal was obtained by rubbing treatment. The display element was manufactured and various evaluations were performed. The evaluation results are shown in Tables 2 and 3 below. In Table 2, the numerical value of the compound (A) indicates the compounding ratio (mol part) of the compound (A) with respect to 100 mol part of the imide group of the polymer component in the liquid crystal aligning agent.

In Table 2, the abbreviations of the compound (A) are as follows.
A-1-23; a compound represented by the following formula (A-1-23)

As shown in Table 2 and Table 3, in Examples 1 to 8, the coating property of the liquid crystal aligning agent, the surface irregularity and rubbing resistance of the coating film, and the liquid crystal alignment property, voltage holding ratio, heat resistance, Both light resistance and bezel unevenness resistance were “good” or “good” results, and various characteristics were balanced. In contrast, in Comparative Example 1, the surface unevenness, voltage holding ratio, heat resistance, light resistance, and bezel unevenness resistance were all inferior to those of the examples.
The reason why the surface irregularity is “good” or “good” in the examples using the liquid crystal aligning agent containing the compound having the partial structure represented by the above formula (1) is not clear. The reason is presumed that the compound (A) that forms a Schiff base with the polymer loses the crystallinity of the polymer, increases the solubility, and improves the coating property. Thereby, it is estimated that the unevenness | corrugation of the surface was suppressed as a result of hardening while the coating film was leveled.

[Example 9: Photo-alignment FFS type liquid crystal display element]
(1) Preparation of liquid crystal aligning agent As a polymer, the polymer (PI-1) obtained in Synthesis Example 2-5 and the compound represented by the above formula (A-3-16-1) are polymerized (PI- 1) An amount of 50 mole parts with respect to 100 mole parts of imide groups is a mixed solvent (GBL: NMP: γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC)). BC = 40: 40: 20 (weight ratio)) to obtain a solution having a solid concentration of 3.5% by weight. A liquid crystal aligning agent (R-9) was prepared by filtering this solution through a filter having a pore diameter of 0.2 μm.

(2) Evaluation of surface irregularity of coating film After applying liquid crystal aligning agent (R-9) prepared above on a glass substrate using a spinner and prebaking for 1 minute on an 80 ° C. hot plate, A coating film having an average film thickness of 1,000 mm was formed by heating (post-baking) for 1 hour in an oven at 200 ° C. in which the inside of the chamber was replaced with nitrogen. The surface irregularity of this coating film was evaluated in the same manner as in Example 1 (3). As a result, the surface roughness was “good”.
(3) Evaluation of orientation The coating film obtained above was irradiated with polarized ultraviolet rays 300 J / m ² containing a 313 nm emission line from the normal direction of the substrate using an Hg-Xe lamp and a Grand Taylor prism. Treated. The refractive index anisotropy (nm) of this glass substrate with an alignment film was measured using a liquid crystal alignment film inspection apparatus (RayScan) manufactured by MORITEX. The evaluation was “good” when 0.020 nm or more, “good” when less than 0.020 nm and less than 0.010 nm, and “bad” when less than 0.010 nm. As a result, this substrate was 0.035 nm and was “good”.

(4) Manufacture of FFS type liquid crystal display element by photo-alignment method First, the liquid crystal aligning agent prepared by said (1) on each surface of a pair of glass substrate 11a, 11b similar to (5) of the said Example 1, respectively. (R-9) was applied using a spinner to form a coating film. Next, this coating film was pre-baked for 1 minute on a hot plate at 80 ° C., and then heated (post-baked) at 230 ° C. for 15 minutes in an oven in which the inside of the chamber was replaced with nitrogen, so that the average film thickness was 1,000 mm. A coating film was formed. A schematic plan view of the top electrode 13 used here is shown in FIG. 4A is a top view of the top electrode 13, and FIG. 4B is an enlarged view of a portion C1 surrounded by a broken line in FIG. 4A. In this example, a substrate having a top electrode having a line width d1 of electrodes of 4 μm and a distance d2 between the electrodes of 6 μm was used. As the top electrode 13, four drive electrodes of electrode A, electrode B, electrode C, and electrode D were used as in Example 1 (see FIG. 3).
Next, each surface of these coating films is irradiated with polarized ultraviolet rays 300 J / m ² including a 313 nm emission line from the substrate normal direction using an Hg-Xe lamp and a Grand Taylor prism, respectively, to form a liquid crystal alignment film. A pair of substrates was obtained. At this time, the irradiation direction of the polarized ultraviolet ray is from the normal direction of the substrate, and the polarization plane direction is set so that the direction of the line segment in which the polarization plane of the polarized ultraviolet ray is projected onto the substrate is the direction of the double-headed arrow in FIG. The light irradiation process was performed.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface having one liquid crystal alignment film of the above substrates by screen printing, and then the liquid crystal alignment film surfaces of a pair of substrates Were placed so that the planes of polarization of polarized ultraviolet rays projected onto the substrate were parallel and pressure bonded, and the adhesive was heat cured at 150 ° C. for 1 hour. Next, liquid crystal “MLC-6221” manufactured by Merck Co., Ltd. was filled into the substrate gap from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, this was heated to 150 ° C. and then gradually cooled to room temperature.
Next, an FFS type liquid crystal display element was manufactured by laminating polarizing plates on both outer surfaces of the substrate. At this time, one of the polarizing plates is stuck so that the polarization direction thereof is parallel to the direction of projection of the polarization plane of the polarized ultraviolet light of the liquid crystal alignment film onto the substrate surface, and the other one has the polarization direction first. The polarizing plate was stuck so as to be orthogonal to the polarization direction of the polarizing plate.

(5) Evaluation of liquid crystal orientation About the photo-alignment FFS type liquid crystal display element manufactured above, liquid crystal orientation was evaluated like (6) of the said Example 1. FIG. As a result, this liquid crystal display element had “good” liquid crystal alignment.
(6) Evaluation of voltage holding ratio About the photo-alignment type FFS liquid crystal display element manufactured above, voltage holding ratio (VHR) was measured similarly to (7) of the said Example 1, and voltage holding ratio was evaluated. As a result, VHR was 99.3%.
(7) Heat resistance The voltage holding ratios (VHR _BF and VHR _AF ) are measured in the same manner as (8) in Example 1 above, and the heat resistance of the liquid crystal display element is determined by the rate of change of the voltage holding ratio before and after application of thermal stress. Evaluated. As a result, ΔVHR was 2.4%, and the heat resistance was judged as “good”.

(8) Light _{resistance The} voltage holding ratios (VHR _BF and VHR _AFBL ) are measured in the same manner as (9) in Example 1 above, and the light resistance of the liquid crystal display element is changed by the change in the voltage holding ratio before and after _{application of} light stress. evaluated. As a result, ΔVHR was 2.5%, and light resistance was judged as “good”.
(9) Unevenness around sealant (bezel unevenness resistance)
The bezel unevenness resistance was evaluated in the same manner as in Example 10 (10). As a result, the luminance difference of the liquid crystal display element was not visually recognized, and the bezel unevenness resistance was determined to be “good”.

[Example 10: VA liquid crystal display element]
(1) Preparation of liquid crystal aligning agent As a polymer, the polymer (PA-3) obtained in Synthesis Example 2-3 was mixed with NMP and butyl cellosolve (BC) (NMP: BC = 50: 50 (weight ratio)). ) To obtain a solution having a solid content concentration of 6.0% by weight. A liquid crystal aligning agent (R-10) was prepared by filtering this solution through a filter having a pore diameter of 0.2 μm.

(2) Evaluation of continuous printability About liquid crystal aligning agent (R-10) prepared above, the printability (continuous printability) at the time of printing on a board | substrate continuously for a long time was evaluated. Evaluation was performed as follows. First, for each of the prepared liquid crystal alignment agents, using a liquid crystal alignment film printer (Nissha Printing Co., Ltd., Angstromer type “S40L-532”), the dropping amount of the liquid crystal alignment agent on the anilox roll is determined. It apply | coated on the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film | membrane on the conditions of 20 drops (about 0.2g). The application to the substrate was performed 20 times using a new substrate at 1 minute intervals.
Subsequently, the liquid crystal aligning agent was dispensed on the anilox roll at one minute intervals (one way), and each time the operation of bringing the anilox roll into contact with the printing plate (hereinafter referred to as idle operation) was performed 10 times in total ( Do not print on glass substrate). This idling operation is not performed in the actual manufacturing process of the liquid crystal display element, but is an operation performed to intentionally perform the printing of the liquid crystal aligning agent under severe conditions.
After 10 times of idling, this printing was performed using a glass substrate. In this printing, after idle operation, 5 substrates are loaded at 30 second intervals, and each substrate after applying the liquid crystal aligning agent is heated (prebaked) at 80 ° C. for 1 minute to remove the solvent, and then 200 ° C. Was heated (post-baked) for 10 minutes to form a coating film having a thickness of about 80 nm. The continuous printability was evaluated by observing this coating film with a microscope having a magnification of 20 times. The evaluation is “good” when polyimide deposition is not observed from the first printing after the blank operation, while polyimide deposition is observed at the first printing after the blank operation, while the printing is performed five times. The case where no precipitation of polyimide was observed was judged as “Yes”, and the case where the precipitation of polyimide was observed even after repeating this printing five times was regarded as “bad”. In addition, it has been experimentally known that with a liquid crystal aligning agent having good printability, the deposition of polyimide is improved (disappeared) while the substrate is continuously charged. In this example, no precipitation of polyimide was observed from the first time, and the printability was judged as “good”.

(3) Evaluation of surface irregularity of coating film Liquid crystal aligning agent (R-10) on the transparent electrode surface of the glass substrate with a transparent electrode made of ITO film by the same printing method as the evaluation of continuous printability in (2) above. Was applied. The surface irregularity of this coating film was evaluated in the same manner as in Example 1 (3). As a result, the surface roughness was “good”.

(4) Manufacture of liquid crystal display element The liquid crystal aligning agent (R-10) was apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film | membrane by the printing method similar to evaluation of the continuous printability of said (2). . The formation of the liquid crystal alignment film was repeated to obtain a pair (two) of substrates having the liquid crystal alignment film. Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to either one of the outer edges of the pair of substrates having the liquid crystal alignment film, and then superposed so that the liquid crystal alignment film surfaces face each other. And then the adhesive was cured. Next, a liquid crystal cell was manufactured by filling a nematic liquid crystal (MLC, MLC-6608) between a pair of substrates from a liquid crystal injection port and then sealing the liquid crystal injection port with an acrylic photo-curing adhesive. This was repeated to produce another pair of liquid crystal cells.

(5) Evaluation of afterimage characteristics (evaluation of pretilt angle stability)]
The liquid crystal cells produced above are described in “T. J. Scheffer et. Al., J. Appl. Phys. Vol 48, p1783 (1977)” and “F. Nakano, et. Al., JPN. J. Appl. Phys. Vol.19, p2013 (1980) "and measured by a rotating crystal method using He-Ne laser light. The measurement was performed with respect to a pretilt angle (initial pretilt angle θini) before voltage application to the liquid crystal cell, and a pretilt angle after driving for 13 hours at AC 9 V at room temperature (pretilt angle θac after driving). Further, the pretilt angle change rate β [%] was calculated by the following mathematical formula (EX-4). When the pretilt angle change rate β was less than 5%, it was evaluated as “good”, and when it was 5% or more, “bad”, the pretilt angle change rate of this liquid crystal cell was 2.9%. It was judged as “good”.
Pretilt angle change rate β [%] = (θac−θini) / θini × 100 (EX-4)

(6) Evaluation of voltage holding ratio About the liquid crystal cell manufactured above, voltage holding ratio (VHR) was measured similarly to (7) of the said Example 1, and voltage holding ratio was evaluated. As a result, VHR was 99.0%.
(7) Heat resistance For the liquid crystal cell produced above, the voltage holding ratios (VHR _BF and VHR _AF ) were measured in the same manner as in (8) of Example 1 above, and the change in voltage holding ratio before and after applying thermal stress. The heat resistance of the liquid crystal display element was evaluated based on the rate. As a result, ΔVHR was 2.9%, and the heat resistance was judged as “good”.

(8) Light resistance For the liquid crystal cell produced above, the voltage holding ratios (VHR _BF and VHR _AFBL ) were measured in the same manner as in (9) of Example 1 above, and the change in voltage holding ratio before and after the _{application of} light stress. Thus, the light resistance of the liquid crystal display element was evaluated. As a result, ΔVHR was 2.0%, and light resistance was judged as “good”.
(9) Unevenness around sealant (bezel unevenness resistance)
About the liquid crystal cell manufactured above, bezel unevenness resistance was evaluated in the same manner as (10) of Example 1 above. As a result, the luminance difference of the liquid crystal display element was not visually recognized, and the bezel unevenness resistance was determined to be “good”.

[Examples 11 to 13, Comparative Example 2 and Comparative Example 3]
A liquid crystal aligning agent was prepared in the same manner as in Example 10 except that the types and amounts of the polymer and the compound (A) were changed as shown in Table 4 below, and a VA type liquid crystal cell was produced and subjected to various evaluations. It was. The evaluation results are shown in Tables 4 and 5 below. In Table 4, the numerical value of the compound (A) indicates the compounding amount (mol part) of the compound (A) with respect to 100 mol part of the imide group of the polymer component in the liquid crystal aligning agent.

In Table 4, the abbreviations of the compound (A) are as follows.
A-3-6-1; a compound represented by the above formula (A-3-6), wherein h = 1 and j = 3; A-3-6-2; the above formula (A-3-6) And a compound represented by h = 0 and j = 7

  As shown in Tables 4 and 5, even in the case of the VA type liquid crystal cell, in the examples, all evaluations were “good” or “good”, and various characteristics were balanced. On the other hand, in the comparative example, it was judged as “bad” by a plurality of evaluations, and the result was inferior to that of the example.

[Example 14: retardation film]
(1) Preparation of Liquid Crystal Alignment Agent The polymer (PI-1) obtained in Synthesis Example 2-5 and the compound (A-3-16-1) obtained in Synthesis Example 1-4 were polymerized (PI- 1) A mixed solvent (PGMEA) composed of propylene glycol monomethyl ether acetate (PGMEA), N-methyl-2-pyrrolidone (NMP) and butyl acetate (BTLAC) with respect to 100 mole parts of imide groups. : NMP: BTLAC = 30: 30: 40 (weight ratio)) to obtain a solution having a solid content concentration of 4.5% by weight. A liquid crystal aligning agent (R-14) was prepared by filtering this solution through a filter having a pore diameter of 0.2 μm.

(2) Production of retardation film The liquid crystal aligning agent (R-14) prepared above is applied to one side of a TAC film as a substrate with a bar coater, and baked in an oven at 120 ° C for 2 minutes to form a film. A coating film having a thickness of 100 nm was formed. Next, the surface of the coating film was irradiated perpendicularly from the substrate normal line with polarized ultraviolet rays of 10 mJ / cm ² containing an emission line of 313 nm using a Hg—Xe lamp and a Grand Taylor prism. Next, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck & Co., Inc.) was filtered through a filter having a pore size of 0.2 μm, and this polymerizable liquid crystal was applied onto the coated film after light irradiation by a bar coater. A coating film was formed. After baking for 1 minute in an oven adjusted to a temperature of 50 ° C., an unpolarized ultraviolet ray containing 365 nm emission line was irradiated at 1,000 mJ / cm ² from a direction perpendicular to the coating surface using an Hg-Xe lamp. A retardation film was produced by curing a polymerizable liquid crystal to form a liquid crystal layer.

(3) Evaluation of liquid crystal orientation About the retardation film manufactured by said (2), liquid crystal orientation is observed by observing the presence or absence of an abnormal domain by visual observation under crossed Nicols and a polarizing microscope (magnification 2.5 times). evaluated. The evaluation was that the alignment was good visually and the abnormal domain was not observed with a polarizing microscope, the liquid crystal orientation was “good”, and the abnormal domain was not observed with the polarizing microscope, but the abnormal domain was observed with a polarizing microscope. The case where the liquid crystal orientation was “possible”, and the case where an abnormal domain was observed visually and with a polarizing microscope was regarded as “Poor”. As a result, this retardation film was evaluated as “good” for liquid crystal alignment.

(4) Adhesiveness Using the retardation film produced in the above (2), the adhesiveness of the coating film formed with the liquid crystal aligning agent to the substrate was evaluated. First, using an equally spaced spacer with a guide, a cutter knife was used to cut from the surface on the liquid crystal layer side of the retardation film to form 10 × 10 lattice patterns within a range of 1 cm × 1 cm. The depth of each cut was made to reach the middle of the substrate thickness from the surface of the liquid crystal layer. Next, after attaching a cellophane tape so as to cover the entire surface of the lattice pattern, the cellophane tape was peeled off. The notches in the lattice pattern after peeling were observed visually under crossed Nicols to evaluate the adhesion. The evaluation was that the adhesion was “good” when no peeling was observed at the portion along the cut line and at the intersection of the lattice pattern, and the number of lattices where peeling was observed in the above portion was the number of the entire lattice pattern. On the other hand, when the amount is less than 15%, the adhesion is “possible”, and when the number of lattices where peeling is observed in the above portion is 15% or more with respect to the total number of lattice patterns, the adhesion is “bad”. went. As a result, this retardation film had good adhesion.

  DESCRIPTION OF SYMBOLS 10 ... Liquid crystal display element, 11a, 11b ... Glass substrate, 12 ... Liquid crystal aligning film, 13 ... Top electrode, 14 ... Insulating layer, 15 ... Bottom electrode, 16 ... Liquid crystal layer

Claims (15)

The liquid crystal aligning agent containing the compound (P) which has a partial structure represented by following formula (1).

(In Formula (1), R ¹ is a monovalent organic group. “*” Represents a bond.)   The liquid crystal aligning agent according to claim 1, wherein the compound (P) is a polymer. The partial structure, a compound having a carbonyl group, a structure formed by the reaction of a primary amine compound having a R ^1, a liquid crystal aligning agent according to claim 1 or 2. Contains a compound (P) having a partial structure represented by the following formula (1) through a reaction step of reacting a compound having a carbonyl group with a primary amine compound represented by the following formula (a). The manufacturing method of the liquid crystal aligning agent which manufactures the liquid crystal aligning agent to do.

(In formula (a), R ¹ is a monovalent organic group.)

(In Formula (1), R ¹ is a monovalent organic group. “*” Represents a bond.)   The method for producing a liquid crystal aligning agent according to claim 4, wherein the compound (P) is a polymer.   The method for producing a liquid crystal aligning agent according to claim 5, wherein the compound having a carbonyl group is at least one polymer selected from the group consisting of polyamic acid, polyimide, and polyamic acid ester.   The method for producing a liquid crystal aligning agent according to claim 6, wherein the compound having a carbonyl group is polyimide. The reaction step is a step of synthesizing the monomer (X) as a compound having a partial structure represented by the above formula (1) by reacting the compound having the carbonyl group with the primary amine compound. Yes,
The manufacturing method of the liquid crystal aligning agent of Claim 5 which further includes the process of obtaining the said compound (P) by superposition | polymerization using the raw material composition containing the said monomer (X).   The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-3, or the liquid crystal aligning agent manufactured by the manufacturing method as described in any one of Claims 4-8.   The liquid crystal aligning agent as described in any one of Claims 1-3 or the liquid crystal aligning agent manufactured by the manufacturing method as described in any one of Claims 4-8 is apply | coated to a board | substrate, and a coating film is formed. A liquid crystal alignment film obtained by irradiating the coating film with light.   After apply | coating the liquid crystal aligning agent as described in any one of Claims 1-3, or the liquid crystal aligning agent manufactured by the manufacturing method as described in any one of Claims 4-8 to a board | substrate, a rubbing process is carried out. Obtained liquid crystal alignment film.   The liquid crystal aligning agent as described in any one of Claims 1-3 or the liquid crystal aligning agent manufactured by the manufacturing method as described in any one of Claims 4-8 is apply | coated on a board | substrate, and a coating film is formed. A method for producing a liquid crystal alignment film, comprising: a step of applying a light to the coating film to impart liquid crystal alignment ability.   A liquid crystal display element provided with the liquid crystal aligning film as described in any one of Claims 9-11.   A retardation film comprising the liquid crystal alignment film according to claim 9.   The liquid crystal aligning agent as described in any one of Claims 1-3 or the liquid crystal aligning agent manufactured by the manufacturing method as described in any one of Claims 4-8 is apply | coated on a board | substrate, and a coating film is formed. And a step of irradiating the coating film with light, and a step of applying and curing a polymerizable liquid crystal on the coating film after the light irradiation.

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