TWI750165B - Liquid crystal alignment agent, liquid crystal alignment film and manufacturing method thereof, liquid crystal element, polymer and compound - Google Patents

Abstract

（式（1）中，R¹ 為含有可具有取代基的環丁烷環結構的四價有機基，R² 為二價有機基；X¹ 及X² 分別獨立地為羥基或碳數1～40的一價有機基；其中，X¹ 及X² 的至少任一者為具有反應性基的一價有機基。）The present invention provides a liquid crystal that can obtain a liquid crystal element having good heat resistance and exhibiting good liquid crystal alignment and afterimage characteristics even if no special treatment is performed after light irradiation to the film when the photo-alignment method is applied. Orientation agent. The polymer (P) which has a partial structure represented by Formula (1) is contained in a liquid crystal aligning agent.

(In formula (1), R ¹ is a tetravalent organic group containing an optionally substituted cyclobutane ring structure, R ² is a divalent organic group; X ¹ and X ² are each independently a hydroxyl group or a carbon number of 1- The monovalent organic group of 40; wherein, ^{at least any one of X 1} and X ² is a monovalent organic group having a reactive group.)

Description

Liquid crystal aligning agent, liquid crystal aligning film, its manufacturing method, liquid crystal element, polymer, and compound

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, a method for producing the same, a liquid crystal element, a polymer, and a compound.

Liquid crystal elements are widely used in televisions, mobile devices, various monitors, and the like. In addition, in a liquid crystal element, a liquid crystal aligning film has been used in order to control the orientation of liquid crystal molecules in a liquid crystal cell. Conventionally, as methods of obtaining an organic film having a liquid crystal alignment control force, a method of rubbing an organic film, a method of obliquely vapor-depositing silicon oxide, a method of forming a monomolecular film having a long-chain alkyl group, a method of A method of irradiating a photosensitive organic film with light (photo-alignment method), and the like.

The photo-alignment method can impart uniform liquid crystal orientation to a photosensitive organic film while suppressing the generation of static electricity and dust, and can also achieve precise control of the liquid crystal orientation direction. Therefore, various researches have been advanced in recent years (for example, refer to the patent document). 1). Patent Document 1 discloses that a liquid crystal aligning agent containing a polyimide precursor having a cyclobutane ring structure in the main chain or a polyimide is applied on a substrate and calcined, and the obtained After the film is irradiated with polarized radiation, an organic solvent with a boiling point of 110°C to 180°C is brought into contact with the film, and further contacted with water or a water-soluble organic solvent with a boiling point of 50°C to 105°C, followed by heat treatment at 150°C or higher, thereby obtaining Liquid crystal alignment film. In addition, it is disclosed that in the case of imparting alignment ability to the film by performing cleaning treatment and heat treatment of such a film and using a photo-alignment method, in-plane switching (In-Plane Switching, IPS) driving method or fringe field. In the liquid crystal display element of the Fringe Field Switching (FFS) driving method, the afterimage caused by the AC driving that occurs is suppressed.

[Prior Art Document] [Patent Document] [Patent Document 1] International Publication No. 2014/084362

[Problems to be Solved by Invention]

However, in the method described in Patent Document 1, since steps of washing and heating the film are required, the number of steps increases, and the cost or complexity may be increased when manufacturing a liquid crystal element. In addition, in recent years, large-screen and high-definition liquid crystal televisions have become the mainstay, and the popularization of small display terminals such as smartphones (smartphones) and tablet personal computers (PCs) has been promoted, and the high definition of liquid crystal panels has been promoted. The requirements and cost reduction requirements are further increased. Therefore, it has become more important than ever to develop a technique for producing a liquid crystal element having various properties related to the display quality of the liquid crystal element, such as liquid crystal orientation and afterimage characteristics, as inexpensively as possible.

Currently, liquid crystal elements can be applied to a wide range of devices or applications ranging from large-screen LCD TVs to small display devices such as smart phones and tablet PCs. In addition, with the multi-purpose use of liquid crystal elements, it is assumed that they are used in a more severe high-temperature environment by being placed or installed in places where high temperatures may occur, such as in a car or outdoors, or by being driven for a long time compared with the past. Therefore, high reliability with respect to heat resistance is required as a liquid crystal element. However, when a liquid crystal aligning film is produced by a photo-alignment treatment using a liquid crystal aligning agent containing a polyimide-based polymer having a cyclobutane ring structure in the main chain, there is a concern that it may be caused by When the obtained liquid crystal element is exposed to light for a long time in a high temperature environment, a decomposed product is easily generated, and the reliability of the heat resistance deteriorates.

The present invention has been made in view of the above-mentioned circumstances, and one of its objects is to provide a film having good heat resistance and exhibiting good heat resistance even if no special treatment is performed after the film is irradiated with light when a photo-alignment method is applied. The liquid crystal aligning agent of the liquid crystal element of a liquid crystal aligning property and an afterimage characteristic.

[Technical means to solve the problem]

The inventors of the present invention have actively studied to achieve the above-mentioned problems of the prior art, and as a result, have found that the problems can be solved by using a polymer having a specific partial structure in an alignment film material, and have completed the present invention. Specifically, the following means are provided.

（式（1）中，R¹ 為含有可具有取代基的環丁烷環結構的四價有機基，R² 為二價有機基；X¹ 及X² 分別獨立地為羥基或碳數1～40的一價有機基；其中，X¹ 及X² 的至少任一者為具有反應性基的一價有機基）。<1> A liquid crystal aligning agent containing a polymer (P) having a partial structure represented by the following formula (1);

(In formula (1), R ¹ is a tetravalent organic group containing an optionally substituted cyclobutane ring structure, R ² is a divalent organic group; X ¹ and X ² are each independently a hydroxyl group or a carbon number of 1- The monovalent organic group of 40; wherein, ^{at least any one of X 1} and X ² is a monovalent organic group having a reactive group).

<2> The manufacturing method of a liquid crystal aligning film which forms a coating film using the liquid crystal aligning agent of the said <1>, irradiates this coating film with light, and provides a liquid crystal aligning ability.

<3> A liquid crystal aligning film formed using the liquid crystal aligning agent of said <1>.

<4> A liquid crystal element including the liquid crystal aligning film according to the above <3>.

<5> A polymer having a partial structure represented by the formula (1).

<6> A compound or a salt thereof represented by the following formula (1-1) or the following formula (1-2);

[hua 2]

(In formula (1-1) and formula (1-2), X ¹¹ and X ¹² are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms; wherein, at least any one of ^{X 11} and X ¹² is a monovalent organic group with a reactive group; R ^{3 is} independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a monovalent aliphatic group with 1 to 10 carbon atoms that may have a substituent; X is One selected from the group consisting of a hydroxyl group, a chlorine atom, a bromine atom, and a structure represented by each of the following formulae (4-1) to (4-6))

[hua 3]

(In formulas (4-1) to (4-6), "*" represents a bond).

[Effect of invention]

According to the liquid crystal aligning agent of this indication, even if it does not perform special processes, such as washing|cleaning of a film and heating, after irradiation of a radiation, the liquid crystal element which shows high heat resistance and favorable liquid crystal aligning property and an afterimage characteristic can be obtained. That is, when the alignment ability is imparted to the film by the photo-alignment method, it is possible to obtain a liquid crystal element having high heat resistance, few afterimages, and favorable liquid crystal alignment properties with as few steps as possible.

In order to make the above-mentioned features and advantages of the present invention more obvious and easy to understand, the following embodiments are given and described in detail with the accompanying drawings as follows.

Hereinafter, the components to be prepared in the liquid crystal aligning agent of the present disclosure and other components arbitrarily prepared as necessary will be described.

"Polymer (P)"

The liquid crystal aligning agent of this disclosure contains the polymer (P) which has the partial structure represented by the said formula (1). In the above formula (1), R ¹ is a tetravalent group derived from a tetracarboxylic acid derivative having a cyclobutane ring structure, and is preferably a partial structure represented by the following formula (r-1). That is, the polymer (P) preferably has at least one of a partial structure represented by the following formula (1-A) and a partial structure represented by the following formula (1-B).

[hua 4]

(In formula (r-1), R ^{3 is} each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a monovalent aliphatic group having 1 to 10 carbon atoms which may have a substituent)

[hua 5]

(In the formula (1-A) and formula (1-B), R ( 1) is R ^2, X and ¹ X ² are the meanings of the Formula ^2, X and X ^{2 are} the same meaning as ¹ .R ³ The same as ^{R 3} in the formula (r-1))

In the formula (r-1), ^{the optionally substituted monovalent aliphatic group having 1 to 10 carbon atoms in R 3} is preferably an alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkyl group, an alkoxy group, a Fluoroalkoxy, or "-COOR ²⁰ " (wherein, R ²⁰ is an alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkyl group, an alkoxy group, or a fluorine-containing alkoxy group). In addition, the four R ³ in the formula may be the same or different from each other.

R ² is a divalent group derived from a diamine compound, and examples thereof include a divalent group obtained by removing two primary amino groups from a conventionally known diamine compound.

Examples of the monovalent organic group having 1 to 40 carbon atoms in X ¹ and X ² include a monovalent hydrocarbon group having 1 to 40 carbon atoms, and the methylene group of the hydrocarbon group is -O-, -S-, -CO-. , -COO-, -COS-, -NR ³ -, -CO-NR ³ -, -Si(R ³ ) ₂ - (wherein R ³ is a hydrogen atom or a monovalent hydrocarbon group with 1 to 12 carbon atoms), - At least one of the hydrogen atoms bonded to the carbon atoms of the monovalent group A, monovalent hydrocarbon group or monovalent group A substituted by N=N-, -SO _{2 -, etc. is substituted by a halogen atom (fluorine atom, chlorine atom,} bromine atom, iodine atom, etc.), hydroxyl, alkoxy, nitro, amino, mercapto, nitroso, alkylsilyl, alkoxysilyl, silanol, sulfinic, phosphino, carboxyl, A monovalent group substituted with a cyano group, a sulfo group, an acyl group, etc., a monovalent group having a heterocyclic ring, and the like. However, ^{at least any one of X 1} and X ² is a monovalent organic group having a reactive group.

Here, a "hydrocarbon group" in this specification means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group including only a chain structure and not including a cyclic structure in the main chain. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. Among them, it is not necessary to include only the alicyclic hydrocarbon structure, and those having a chain structure in a part thereof are also included. The "aromatic hydrocarbon group" refers to a hydrocarbon group including an aromatic ring structure as a ring structure. However, it is not necessary to include only an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be included in a part thereof. "Aliphatic group" means a chain hydrocarbon group and an alicyclic hydrocarbon group.

The reactive group possessed by at least one of X ¹ and X ² is preferably between the reactive groups and/or with the maleimide compound in the presence of at least one of heat, light, acid, base and free radical. A base that forms a covalent bond. The reactive group is preferably a group that reacts with at least one of heat and light. Specific examples of the reactive group include structures represented by the following formulae (5-1) to (5-10), (meth)acryloyloxy groups, styryl groups, and vinylphenyl groups, for example. , a (meth)acrylamido group, a vinyloxy group (CH ₂ =CH-O-), a group represented by each of the following formulae (p-1) and (p-2), and the like. A vinylphenyl group and a vinyloxy group are an example of the structure represented by following formula (5-1).

[hua 6]

(In formulas (5-1) to (5-10), R ⁴¹ is a divalent aliphatic group having 1 to 6 carbon ^{atoms which may have a substituent, and R 5 is} each independently a hydrogen atom or may have a substituent A monovalent aliphatic group with 1 to 6 carbon atoms. Among them, ^{any two aliphatic groups in R 41} and R ⁵ can be bonded to each other to form a ring structure. Formula (5-1), formula (5-9) A plurality of R ^{5 in} can be the same or different from each other. "*" indicates a bonding bond)

[hua 7]

(In formula (p-1), X ⁵ is an oxygen atom or -NH-. "*" represents a bond)

In the formula (5-1), the ^{divalent aliphatic group having 1 to 6 carbon atoms in R 41} is preferably an alkanediyl group or an alkenediyl group. As ^{a substituent which R 41} may have, a halogen atom, an alkoxy group, etc. are mentioned, for example. The monovalent aliphatic group having 1 to 6 carbon atoms in ^{R 5 is preferably an alkyl group or an alkenyl group.}

In the above formulae (5-2) to (5-10), the divalent aliphatic group having 1 to 6 carbon atoms ^{in R 41 is preferably an alkanediyl group.} Regarding ^{the substituent which R 41} may have, the description of the above formula (5-1) can be applied. The monovalent aliphatic group having 1 to 6 carbon atoms in ^{R 5 is preferably an alkyl group.} From the viewpoint of reactivity, R ⁵ in formula (5-5) is particularly preferably a hydrogen atom or a methyl group.

The reactive group is preferably selected from the above-mentioned formula (5-1) from the viewpoint of obtaining a liquid crystal element having more excellent liquid crystal alignment properties, alternating current (AC) afterimage characteristics, and heat resistance. - At least one of the structures represented by the respective formulas (5-10) and the group consisting of (meth)acryloyloxy groups, more preferably selected from the above-mentioned formulas (5-1) and (5-2) ), at least one of the structures represented by formulas (5-4) to (5-6) and the group consisting of (meth)acryloyloxy groups. In addition, in this specification, "(meth)acrylic group" means an acrylic group and a methacrylic group.

The exemplified reactive group may be directly bonded to the carbonyl group in the formula (1), or may be bonded via a divalent linking group. Examples of the divalent linking group include an oxygen atom, an alkanediyl group having 1 to 20 carbon atoms, and a divalent group having -O-, -CO-, -COO-, etc. between the carbon-carbon bonds of the alkanediyl group. price base etc.

At least one of X ¹ and X ² is preferably selected from the group consisting of a structure represented by each of the following formulae (2-1) to (2-10) and a (meth)acryloyloxy group One, more preferably selected from the structures represented by the following formula (2-1), formula (2-2), formula (2-4) to formula (2-6), and (meth)acryloyloxy one of the groups formed. ^{In addition, regarding the description of R 4} and R ⁵ in the following formulas (2-1) to (2-10), ^{R 41 in} the above formulas (5-1) to (5-10) can be applied, respectively. and the description of ^{R 5.}

[hua 8]

(In formulas (2-1) to (2-10), R ⁴ is a divalent aliphatic group having 1 to 6 carbon ^{atoms which may have a substituent, and R 5 is} each independently a hydrogen atom or may have a substituent A monovalent aliphatic group with 1 to 6 carbon atoms. Among them, ^{any two aliphatic groups in R 4} and R ⁵ can be bonded to each other to form a ring structure. Formula (2-1), formula (2-9) A plurality of R ^{5 in} can be the same or different from each other. "*" indicates a bonding bond)

[Synthesis of polymer (P)]

The method for synthesizing the polymer (P) is not particularly limited, and a preferable method includes a compound (hereinafter, also referred to as a compound represented by each of the formula (1-1) and the formula (1-2) containing the A method of reacting a tetracarboxylic acid derivative which is at least one of "specific acid derivatives") with a diamine compound.

In addition, in this specification, "tetracarboxylic acid derivative" includes tetracarboxylic dianhydride obtained by dehydration condensation of four carboxyl groups of tetracarboxylic acid, and at least one of the four carboxyl groups of tetracarboxylic acid obtained by "- COX ³ ″ (wherein, X ³ is a halogen atom or a monovalent organic group having 1 to 40 carbon atoms) substituted compounds. Specifically, in addition to the tetracarboxylic dianhydride, for example, one or two of the four carboxyl groups in the tetracarboxylic acid are esterified and the remainder is a carboxyl group, and the four carboxyl groups in the tetracarboxylic acid are mentioned. A compound in which one or both of them are esterified and a leaving group (for example, a halogen atom, a structure represented by each of the above formulas (4-1) to (4-6), etc.) is introduced into the remaining carboxyl group. or its salt, etc.

Regarding the above-mentioned formula (1-1) and formula (1-2), the description of the above-mentioned formula (r-1) can be applied to the preferred example of ^{R 3 .} At least any one of X ¹¹ and X ¹² is preferably selected from the group consisting of the structure and (meth)acryloyloxy group represented by each of the above formulae (2-1) to (2-10) A sort of. In addition, when X ¹¹ and X ¹² are groups that do not have a reactive group, X ¹¹ and X ^{12 are} preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

X is preferably a hydroxyl group or a chlorine atom. Further, when X is a hydroxyl group, the specific acid dianhydride is a tetracarboxylic acid diester, and when X is a chlorine atom or a bromine atom, the specific acid dianhydride is a tetracarboxylic acid diester dihalide.

[Tetracarboxylic acid derivatives]

(Specific Acid Derivatives)

The specific acid derivative can be obtained, for example, by the following method. A method of reacting an anhydride with a compound having a reactive group (hereinafter, also referred to as "reactive group-containing compound (E)"); [2] reacting tetracarboxylic dianhydride containing a specific tetracarboxylic dianhydride with a A method of reacting with a compound (E) having a radical group to obtain a tetracarboxylic acid diester, and then reacting with a compound having the above-mentioned leaving group (for example, a halogenating agent).

･Specified tetracarboxylic dianhydride

The specific tetracarboxylic dianhydride is not particularly limited as long as it has a cyclobutane ring structure, and is specifically represented by the following formula (4).

[Chemical 9]

(In formula (4), A ¹ is a tetravalent organic group having a cyclobutane ring structure)

In the formula (4), A ¹ is preferably a structure represented by the formula (r-1). Specific examples of the specific tetracarboxylic dianhydride include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1-methyl-1,2,3,4-cyclobutanetetracarboxylate Acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3-trimethyl-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1-ethyl-1,2,3,4-cyclobutane Alkanetetracarboxylic dianhydride, 1,3-diethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1-ethyl-3-methyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, a compound represented by each of the following formulae (T-1-1) to (T-1-16), and the like.

[Chemical 10]

The specific tetracarboxylic dianhydride is preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid among these The dianhydride is particularly preferably 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride. Moreover, as a specific tetracarboxylic dianhydride, it can use individually by 1 type or in combination of 2 or more types.

･Reactive group-containing compound (E)

The reactive group-containing compound (E) is not particularly limited as long as it has a reactive group and a functional group that reacts with an acid dianhydride group, but is preferably a compound represented by the following formula (3-1).

[Chemical 11]

(In formula (3-1), A ² is a reactive group, and R ¹¹ is a single bond or a (k+1)-valent hydrocarbon group. k is an integer of 1 to 3)

In the formula (3-1), as ^{the (k+1)-valent hydrocarbon group for R 11} , a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group can be mentioned. k is preferably 1, and as ^{a specific example of R 11} in this case, the divalent chain hydrocarbon group includes, for example, a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, and a heptyl group. Diyl, octanediyl, nonanediyl, decanediyl, etc. may be linear or branched. Moreover, as a divalent alicyclic hydrocarbon group of ^{R 11 , a cyclohexylene group, -R c} -(CH ₂ ) _n - (wherein R ^c is a cyclohexylene group, and n is an integer of 1 to 5), etc., can be mentioned, For example, the divalent aromatic hydrocarbon group includes a phenylene group, a biphenylene group, and -Ph-(CH ₂ ) _n - (wherein Ph is a phenylene group, and n is an integer of 1 to 5).

A ² can be applied to the description of the reactive group of the formula (1) and the description of the preferred specific example.

Specific examples of the compound represented by the formula (3-1) include compounds represented by the following formulae (3-1-1) to (3-1-16), for example. In addition, the reactive group-containing compound (E) may be used alone or in combination of two or more.

[Chemical 12]

･Reaction of tetracarboxylic dianhydride with reactive group-containing compound (E)

The reaction of the tetracarboxylic dianhydride and the reactive group-containing compound (E) can be carried out in an organic solvent if necessary. The organic solvent to be used is not particularly limited as long as it is inactive with respect to the tetracarboxylic dianhydride and the reactive group-containing compound (E). Examples thereof include ketones such as acetone and methyl ethyl ketone; hexane, Hydrocarbons such as heptane and toluene; halogen hydrocarbons such as chloroform and 1,2-dichloroethane; ethers such as tetrahydrofuran, diethyl ether, and 1,4-dioxane; nitrile compounds such as acetonitrile and propionitrile, and the like. Moreover, these organic solvents can be used individually by 1 type or in combination of 2 or more types.

The use ratio of the reactive group-containing compound (E) is usually 2 mol to 100 mol, preferably 2 mol to 40 mol, relative to 1 mol of tetracarboxylic dianhydride. The reaction temperature at this time can be appropriately set according to the type of the reactive group-containing compound (E) to be used, but it is preferably -20°C to 150°C, and more preferably 0°C to 100°C. The reaction time is preferably 0.1 to 24 hours, and more preferably 0.5 to 12 hours. In addition, after the reaction, reprecipitation may be performed if necessary. Then, by washing and drying the obtained precipitate as necessary, the target compound (tetracarboxylic acid diester) can be obtained.

In the above-mentioned method [2], when the tetracarboxylic acid diester obtained by the above-mentioned reaction is reacted with an appropriate halogenating agent such as thionine chloride, it is preferably carried out in an organic solvent. Regarding conditions such as an organic solvent, a reaction temperature, and a reaction time, the description of the reaction conditions of the tetracarboxylic dianhydride and the reactive group-containing compound (E) can be applied.

･Other acid derivatives

When synthesizing the polymer (P), as the tetracarboxylic acid derivative, only a specific acid derivative may be used, or a specific acid derivative and a tetracarboxylic acid derivative different from the specific acid derivative (hereinafter, also referred to as the specific acid derivative) may be used in combination. "other acid derivatives"). Examples of other acid derivatives include tetracarboxylic acid diesters having no reactive group, tetracarboxylic acid diester dihalides having no reactive group, and tetracarboxylic dianhydrides having no cyclobutane ring structure. (Hereinafter, also referred to as "other tetracarboxylic dianhydride"), a reaction product with a reactive group-containing compound (E), a tetracarboxylic dianhydride, and the like.

The other tetracarboxylic dianhydride is not particularly limited. As a specific example, aliphatic tetracarboxylic dianhydride, for example, ethylenediaminetetraacetic acid dianhydride, etc. can be mentioned;

Alicyclic tetracarboxylic dianhydrides include, for example, 2,3,5-tricarboxycyclopentylacetic 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, 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexane Alkene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicycle [3.3.0] Octane-2:4,6:8-dianhydride, cyclohexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, etc.; for example, aromatic tetracarboxylic dianhydrides include: Phenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, p-phenylene bis(trimellitic acid monoester anhydride), ethylene glycol bis(dehydrated trimellitic acid anhydride) acid ester), 1,3-propanediol bis (anhydrotrimellitic acid ester), etc.; other than these, the tetracarboxylic dianhydride described in Unexamined-Japanese-Patent No. 2010-97188 can be used. In addition, when synthesizing the polymer (P), other tetracarboxylic dianhydrides may be used alone or in combination of two or more.

When synthesizing the polymer (P), from the viewpoint of sufficiently obtaining the effects of the present disclosure, the use ratio of the specific acid derivative is preferably set to 10 mol with respect to the total amount of the tetracarboxylic acid derivatives used in the synthesis %above. More preferably, it is 30 mol% or more, and still more preferably 50 mol% or more. Moreover, a specific acid derivative and other acid derivatives may be used individually by 1 type, respectively, and may be used in combination of 2 or more types.

[Diamine compound]

The diamine compound used for the synthesis of the polymer (P) is not particularly limited, and various diamine compounds can be used. Specific examples of the aliphatic diamines include m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, hexamethylenediamine, and the like; and alicyclic diamines include, for example, : 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), etc.;

Examples of aromatic diamines include dodecyloxydiaminobenzene, hexadecyloxydiaminobenzene, octadecyloxydiaminobenzene, cholestyloxydiaminobenzene, cholesteneoxydiaminobenzene Aminobenzene, cholestyl diaminobenzoate, cholestyl diaminobenzoate, lanostyl diaminobenzoate, 3,6-bis(4-aminobenzyloxy)cholesteryl Alkane, 3,6-bis(4-aminophenoxy)cholestane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 2, 5-Diamino-N,N-diallylaniline, the following formula (E-1)

[Chemical 13]

(In formula (E-1), X ^I and X ^II are each independently a single bond, -O-, -COO- or -OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, and R ^II is a single A bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1. However, a and b do not become 0 at the same time)

Side chain type diamines such as the indicated compounds:

p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl-4 '-Aminobenzoate, 4,4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 1,5-bis(4-aminophenoxy)pentane, bis[2-(4 -Aminophenyl)ethyl]hexanedioic acid, bis(4-aminophenyl)amine, N,N-bis(4-aminophenyl)methylamine, 2,6-diaminopyridine, 1,4 -Bis-(4-aminophenyl)-oxazine, N,N'-bis(4-aminophenyl)-benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy) ) phenyl] propane, 4,4'-(phenylenediisopropylidene)dianiline, 1,4-bis(4-aminophenoxy)benzene, 4-(4-aminophenoxycarbonyl) -1-(4-Aminophenyl)diphenylamine chain diamine;

For example, the diaminoorganosiloxane includes 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, and the like; other than these, those described in Japanese Patent Laid-Open No. 2010-97188 can be used. Diamine. In addition, the diamine compound used for the synthesis of the polymer (P) may have the above-mentioned group having a reactive group as a substituent.

The diamine compound used for the synthesis of the polymer (P) is preferably at least one containing p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenylethane among these. either. Furthermore, when synthesizing the polymer (P), the diamine compound may be used alone or in combination of two or more.

[Reaction of Tetracarboxylic Acid Derivative and Diamine Compound]

The reaction of the tetracarboxylic acid derivative and the diamine compound can be carried out by appropriately combining conventional methods of organic chemistry depending on the tetracarboxylic acid derivative to be used.

For example, when the tetracarboxylic acid derivative is a tetracarboxylic acid diester, a method of reacting the tetracarboxylic acid diester and the diamine compound preferably in an organic solvent in the presence of a suitable dehydration catalyst is available. As the dehydration catalyst used in the reaction, for example, halogenated 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine, carbonylimidazole, Cyclohexylcarbodiimide, phosphorus-based condensing agent, etc. The use ratio of these dehydration catalysts is preferably 2 mol to 3 mol, more preferably 2 mol to 2.5 mol, relative to 1 mol of the tetracarboxylic acid diester.

In addition, when the tetracarboxylic acid derivative is a tetracarboxylic acid diester dihalide, it is possible to use the tetracarboxylic acid diester dihalide and the diamine compound preferably in an organic solvent in the presence of a suitable base. method of reaction. Examples of the base used in the reaction include tertiary amines such as pyridine and triethylamine; and alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium, and potassium. The use ratio of the base is preferably 2 mol to 4 mol, more preferably 2 mol to 3 mol, relative to 1 mol of the diamine compound. In addition, the reaction of the tetracarboxylic acid diester dihalide and the diamine compound may be carried out in the presence of Lewis acid for the purpose of promoting the progress of the reaction. As Lewis acid, lithium halides, such as lithium chloride, etc. are mentioned, for example.

In the reaction between the tetracarboxylic acid derivative and the diamine compound, the ratio of the tetracarboxylic acid derivative and the diamine compound to be used in the reaction is preferably 1 equivalent of the amino group of the diamine compound, and the tetracarboxylic acid derivative has a The reaction-related group "—COX ⁴ (X ⁴ is a hydroxyl group or a leaving group)" is in a ratio of 0.2 to 2 equivalents. The reaction temperature is preferably -30°C to 150°C, and the reaction time is preferably 0.1 hour to 48 hours.

As an organic solvent used for a reaction, an aprotic polar solvent, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon etc. are mentioned, for example. Among these organic solvents, it is preferable to use at least one selected from the group consisting of aprotic polar solvents (organic solvents of the first group), or one or more organic solvents selected from the first group and selected from A mixture of one or more of the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the use ratio of the organic solvent of the second group is preferably 50 mass % or less, more preferably 40 mass %, relative to the total amount of the organic solvent of the first group and the organic solvent of the second group. Below, it is more preferable that it is 30 mass % or less.

Particularly preferred organic solvents preferably will be selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butylene One or more of the group consisting of lactone, tetramethylurea, hexamethylphosphoric triamine, m-cresol, xylenol, and halogenated phenols are used as a solvent, or these organic compounds are used within the range of the stated ratio. A mixture of one or more solvents and other organic solvents. It is preferable that the usage-amount (a) of an organic solvent is the amount which becomes 0.1 mass % - 50 mass % with respect to the total amount (a+b) of the monomer used for reaction with respect to the total amount (b) of the monomers used for reaction.

(terminal modifier)

When synthesizing the polymer (P), a moiety having the above formula (1) can be obtained as the polymer (P) by using a tetracarboxylic acid derivative, a diamine compound, and a terminal modifier having a functional group. A polymer with a structure and a functional group at the end of the polymer. In this case, when the polymer (Q) and the polymer (P) described later are contained in the liquid crystal aligning agent, the applicability of the liquid crystal aligning agent can be further improved, which is preferable from the point of view.

As a terminal modifier, a monoacid anhydride, a monocarbonyl chloride, a monoamine compound, a monoisocyanate compound etc. are mentioned, for example. As a functional group which a terminal modifier has, the said reactive group, a thiol group, a protected amino group, etc. are mentioned, for example.

Specific examples of such terminal modifiers include (meth)acryloyl chloride, 2-furancarboyl chloride, furfurylamine, 2-aminoethanethiol, 3-aminopropanethiol, N-(tertiary Butoxycarbonyl)-1,2-diaminoethane, N-(tert-butoxycarbonyl)-1,3-diaminopropane, etc. In addition, the terminal modifier may be used alone or in combination of two or more.

At the time of the above synthesis, the use ratio of the terminal modifier is preferably 20 mol parts or less, more preferably 0.001 mol parts to 10 mol parts, with respect to the total 100 mol parts of the diamine compounds used. share.

The polymer (P) is a reaction product of a tetracarboxylic acid derivative and a diamine compound containing at least one of the compounds represented by the formula (1-1) and the formula (1-2). The reaction product may be a polymer having only a structural unit derived from a tetracarboxylic acid derivative and a structural unit derived from a diamine compound, or may further have a structural unit derived from a tetracarboxylic acid derivative and a diamine derived structural unit. Other partial structures in which the building blocks of a compound differ. Examples of other partial structures include partial structures derived from the above-mentioned terminal modifier.

As mentioned above, the reaction solution which melt|dissolved the polymer (P) which is a polyamic acid ester can be obtained. The reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid ester contained in the reaction solution. The polyamic acid ester may have only the aramidic acid ester structure, or may be a partial ester product in which the aramidic acid structure and the aramidic acid ester structure coexist. In addition, the synthesis method of a polyamic acid ester is not limited to the above, For example, it can also be obtained by a method of reacting polyamic acid with an alcohol or a halogenated alkyl group having a reactive group.

The polymer (P) obtained in this way preferably has a solution viscosity of 20 mPa·s to 1,800 mPa·s when it is made into a solution with a concentration of 15% by mass, and more preferably has a solution viscosity of 50 mPa·s ~1,500 mPa·s solution viscosity. In addition, the solution viscosity (mPa·s) of the polymer (P) is determined by using an E-type rotational viscometer, and is determined for a good solvent (such as γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer (P). ) and the prepared polymer solution having a concentration of 15% by mass was measured at 25°C.

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer (P) measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 7 or less, and more preferably 5 or less. By being in such a molecular weight range, favorable orientation and stability of a liquid crystal element can be ensured.

By comparing the case of forming a film using a liquid crystal aligning agent containing a polymer (P) and the case of using a liquid crystal aligning agent containing only a polymer not having the partial structure represented by the formula (1) as a polymer component, There is an advantage that the generation of decomposition products caused by photo-alignment treatment can be suppressed. The reason for this is presumed that the cyclobutane ring in the main chain is decomposed by the reverse reaction of [2+2], and the molecular weight is reduced to give anisotropy to the film. Substantially generated decomposition products can be combined with components in the film, and the generation of decomposition products can be reduced. However, the content is only speculation, and does not limit the content of the present disclosure in any way.

"Other Ingredients"

＜Polymer (Q)＞

The liquid crystal aligning agent of the present disclosure may contain only the polymer (P) as a polymer component, or may contain the polymer (P) and at least one polymer selected from the group consisting of polyamic acid and polyimide (Q). It is presumed that when a coating film is formed on a substrate using a liquid crystal aligning agent containing a polymer (P) and a polymer (Q), the polymer (P) can be biased to exist in the outer layer of the coating film due to the difference in surface energy. , which can further improve the liquid crystal alignment and AC afterimage characteristics.

(polyamide)

The polyamic acid as the polymer (Q) can be obtained, for example, by reacting tetracarboxylic dianhydride with a diamine compound. As a tetracarboxylic dianhydride and a diamine compound used for a reaction, the tetracarboxylic dianhydride and a diamine compound etc. which were illustrated in the description of a polymer (P) are mentioned.

The use ratio of the tetracarboxylic dianhydride and the diamine compound to be used in the synthesis reaction of the polyamic acid is preferably a ratio of 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride with respect to 1 equivalent of the amino group of the diamine compound. , more preferably in a ratio of 0.3 to 1.2 equivalents. The synthesis reaction of polyamide is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours. When a polyamic acid is contained as the polymer (Q), the effect by the preparation of the polymer (P) can be obtained, and the printability can be further improved, which is preferable in this respect.

(polyimide)

The polyimide as the polymer (Q) can be obtained, for example, by dehydrating and ring-closing the polyimide synthesized as described above, followed by imidization. The polyimide may be a complete imide obtained by dehydrating and ring-closing all the amide structures of the polyamide that is a precursor thereof, or may be dehydrating and ring-closing only a part of the amide structure. On the other hand, a partial imide compound in which an amide acid structure and an amide ring structure coexist. The imidization rate of the polyimide used for preparation of the liquid crystal aligning agent is preferably 20% or more, more preferably 30% to 99%, still more preferably 40% to 99%. The imidization rate is expressed in percentage as the ratio of the number of imide ring structures to the sum of the number of imide acid structures and the number of imine ring structures in the polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamide acid is preferably a method of heating the polyamide acid, or by dissolving the polyamide acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating if necessary. method to carry out. Among the above, it is preferable to use the method described later.

In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to a polyamic acid solution, as the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used, for example. It is preferable that the usage-amount of a dehydrating agent shall be 0.01 mol - 20 mol with respect to 1 mol of the aramidic acid structure of a polyamic acid. As the dehydration ring-closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring-closure catalyst used is preferably 0.01 mol to 10 mol per 1 mol of the dehydrating agent to be used. As the organic solvent used for the dehydration ring-closure reaction, the organic solvent exemplified as the compound used for the reaction of the tetracarboxylic acid diester and the diamine is exemplified. The reaction temperature of the dehydration ring-closure reaction is preferably 0°C to 180°C, and the reaction time is preferably 1.0 hours to 120 hours. When a polyimide is contained as the polymer (Q), the effect by the preparation of the polymer (P) can be obtained, and the electrical properties can be further improved, which is preferable in this respect.

The polymer (Q) preferably has a solution viscosity of 20 mPa·s to 1,800 mPa·s when it is made into a solution with a concentration of 15% by mass, and more preferably has a solution viscosity of 50 mPa·s to 1,500 mPa·s solution viscosity. In addition, the solution viscosity (mPa·s) of the polymer (Q) was measured using an E-type rotational viscometer, and the value of the good solvent (such as γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer (Q) was determined. ) and the prepared polymer solution having a concentration of 15% by mass was measured at 25°C.

The weight average molecular weight (Mw) of the polymer (Q) in terms of polystyrene measured by GPC is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 7 or less, and more preferably 5 or less.

When the liquid crystal aligning agent of the present disclosure contains the polymer (Q), the content ratio of the polymer (P) is preferably 3 mass parts with respect to 100 parts by mass in total of the polymer (P) and the polymer (Q). part or more, more preferably 5 parts by mass to 95 parts by mass, still more preferably 10 parts by mass to 90 parts by mass, and particularly preferably 15 parts by mass to 85 parts by mass. Moreover, a polymer (P) and a polymer (Q) may each be used individually by 1 type, and may be used in combination of 2 or more types.

The liquid crystal aligning agent of this disclosure may contain components other than the polymer (Q) as other components. Examples of the other components include polymers other than the polymer (P) and the polymer (Q) (hereinafter, referred to as "other polymers"), and compounds having at least one epoxy group in the molecule (hereinafter, referred to as "other polymers"). "epoxy group-containing compound"), functional silane compound, photopolymerizable compound, antioxidant, metal complex compound, hardening accelerator, crosslinking agent, imidization accelerator, surfactant, filler , dispersant, photosensitizer, acid generator, alkali generator, free radical generator, etc. The liquid crystal aligning agent of the present disclosure preferably contains a polymer (P) and at least one selected from the group consisting of a functional silane compound, an acid generator, a base generator, and a radical generator.

(other polymers)

Other polymers can be used to improve solution properties or electrical properties. Examples of the other polymers include polyorganosiloxane, polyester, polyamide, cellulose derivatives, polyacetal, polystyrene derivatives, poly(styrene-phenylmaleide) imine) derivatives, poly(meth)acrylates, and the like. The compounding ratio of another polymer is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass with respect to 100 parts by mass in total of the polymers prepared in the liquid crystal aligning agent. the following.

(compounds containing epoxy groups)

The epoxy group-containing compound can be used to improve the adhesiveness or electrical properties of the liquid crystal aligning film to the surface of the substrate. As such an epoxy group-containing compound, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, N,N-diglycidyl - Benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, etc. In addition to this, as an example of the epoxy group-containing compound, the epoxy group-containing polyorganosiloxane described in International Publication No. WO 2009/096598 can be used. When adding an epoxy group-containing compound to a liquid crystal aligning agent, it is preferable that the said compounding ratio shall be 50 mass parts or less with respect to the total 100 mass parts of polymers contained in a liquid crystal aligning agent, More preferably It is set as 0.1 mass part - 30 mass parts.

(functional silane compound)

The functional silane compound can be used for the purpose of improving the printability of a liquid crystal aligning agent. Examples of such functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane Silane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, 10-trimethoxysilyl-1,4,7-triazadecyl Alkane, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- Glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. When adding a functional silane compound to a liquid crystal aligning agent, it is preferable that the said compounding ratio is 5 mass parts or less with respect to the total 100 mass parts of polymers, More preferably, it is 0.02-3 mass parts, More preferably It is 0.1 mass part - 2 mass parts.

(acid generator)

As an acid generator, it can select and use suitably from well-known compounds which generate|occur|produce an acid by heat or light. Specifically, as the thermal acid generator, for example, iodonium salts such as diphenyliodide triflate and bis(4-tert-butylphenyl)iodine trifluoromethanesulfonate, etc., can be mentioned. Examples of the generating agent include perium salts such as triphenyl perylene triflate; tetrahydrothiophenes such as 1-(4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate Onium salts; N-sulfonyloxyimide compounds such as N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide and the like. When adding an acid generator to a liquid crystal aligning agent, 50 mass parts or less are preferable with respect to the total 100 mass parts of polymers, and, as for the said compounding ratio, 0.1 mass part - 30 mass parts are more preferable.

(alkali generator)

As a base generator, it can select and use suitably from well-known compounds which generate|occur|produce a base by heat or light. Specifically, for example, imidazole-based thermal base generators; o-nitrobenzyl carbamate, α,α-dimethyl-3,5-dimethoxybenzyl carbamate, Oxyimino-based photobase generators, etc. When adding an alkali generator to a liquid crystal aligning agent, 50 mass parts or less are preferable with respect to the total 100 mass parts of polymers, and, as for the said compounding ratio, 0.1 mass part - 30 mass parts are more preferable.

(free radical generator)

As a radical generator, it can select and use suitably from well-known compounds which generate|occur|produce a radical by heat or light. Specifically, examples of the thermal radical generator include peroxides such as tert-butyl hydroperoxide and tert-butyl peroxyacetate; azobisisobutyronitrile (AIBN), 2,2'- Azo compounds such as azobis(isobutyronitrile); redox-based initiators, etc.; examples of photo-radical generators include acetophenone, 1-hydroxycyclohexyl phenyl ketone, fluorene, and triphenylamine , 3-methylacetophenone, 4,4'-dimethoxybenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone- 1,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, etc. When adding a radical generator to a liquid crystal aligning agent, 50 mass parts or less are preferable with respect to the total 100 mass parts of polymers, and, as for the said compounding ratio, 0.1-30 mass parts is more preferable.

＜Solvent＞

The liquid crystal aligning agent of the present disclosure is prepared as a liquid composition in which the polymer (P) and other components used as needed are preferably dispersed or dissolved in a suitable solvent.

As the organic solvent to be used, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, γ-butyrolactone, γ- -Butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, lactic acid Butyl ester, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, Ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisobutyl ketone Amyl ether, ethylene carbonate, propylene carbonate, etc. These can be used alone or in combination of two or more.

The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1 mass % ~10 mass % range. That is, as described later, a liquid crystal aligning agent is apply|coated to a board|substrate surface, and it is preferable to heat it, and form the coating film which is a liquid crystal aligning film or the coating film which becomes a liquid crystal aligning film. At this time, when solid content concentration is less than 1 mass %, the film thickness of a coating film becomes too small, and it becomes difficult to obtain a favorable liquid crystal aligning film. On the other hand, when the solid content concentration exceeds 10 mass %, the film thickness of the coating film becomes too large, and it becomes difficult to obtain a favorable liquid crystal aligning film, and the viscosity of the liquid crystal aligning agent increases and the applicability tends to decrease. .

The content ratio of the polymer (P) in the liquid crystal aligning agent of the present disclosure is preferably 3 parts by mass or more, and more preferably 5 parts by mass with respect to 100 parts by mass in total of the solid content (components other than the solvent) in the liquid crystal aligning agent More than that, more preferably 10 parts by mass or more.

《Liquid crystal aligning film and liquid crystal element》

The liquid crystal aligning film of this disclosure is formed using the liquid crystal aligning agent prepared as described above. Moreover, the liquid crystal element of this indication is equipped with the liquid crystal aligning film formed using the liquid crystal aligning agent demonstrated above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited. For example, it can be applied to a twisted nematic (TN) type, a super twisted nematic (STN) type, and a vertical alignment (Vertical Alignment, VA) type. (including Vertical Alignment-Multi-domain Vertical Alignment (VA-MVA) type, Vertical Alignment-Patterned Vertical Alignment (VA-PVA) type, etc.), coplanar switching (In-Plane Switching, IPS) type, fringe field switching (fringe field switching, FFS) type, Optically Compensated Bend (Optically Compensated Bend, OCB) type and other modes. A liquid crystal element can be manufactured by a method including the following steps 1 to 3, for example. Step 1 uses different substrates depending on the desired mode of operation. Steps 2 and 3 are common to all operation modes.

(Step 1: Formation of coating film)

First, a liquid crystal aligning agent is apply|coated on a board|substrate, Preferably, a coating surface is heated, and a coating film is formed on a board|substrate. As the substrate, for example, glass such as float glass and soda glass can be used; polyethylene terephthalate, polybutylene terephthalate, polyether terephthalate, and polycarbonate can be used , Poly(alicyclic olefin) and other plastic transparent substrates. As the transparent conductive film provided on one surface of the substrate, a Nessa (NESA) film (registered trademark of PPG, USA) _{containing tin oxide (SnO 2 ), a film containing indium oxide-tin oxide (In 2} O ₃ -SnO ₂ ) can be used The indium tin oxide (Indium Tin Oxide, ITO) film and so on. In the case of manufacturing a TN type, STN type or VA type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, when manufacturing an IPS type or FFS type liquid crystal element, a substrate provided with electrodes including a comb-shaped transparent conductive film or a metal film patterned and a counter substrate provided with no electrodes are used. As the metal film, for example, a film containing a metal such as chromium can be used. The coating of the liquid crystal aligning agent on the substrate is preferably performed on the electrode formation surface by a lithographic method, a spin coating method, a roll coater method, or an inkjet printing method.

After applying the liquid crystal aligning agent, it is preferable to perform preheating (prebaking) for the purpose of preventing sagging of the applied liquid crystal aligning agent. The pre-baking temperature is preferably 30° C. to 200° C., and the pre-baking time is preferably 0.25 minutes to 10 minutes. Then, the solvent is completely removed, and if necessary, a calcination (post-baking) step is performed for the purpose of thermal imidization of the amide acid structure present in the polymer. The roasting temperature (post-baking temperature) at this time is preferably 80° C. to 300° C., and the post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the film formed in this manner is preferably 0.001 μm to 1 μm. After apply|coating a liquid crystal aligning agent on a board|substrate, an organic solvent is removed, and a liquid crystal aligning film or the coating film which becomes a liquid crystal aligning film is formed.

(Step 2: Orientation Processing)

When producing a TN type, STN type, IPS type, or FFS type liquid crystal element, the coating film formed in the above-mentioned step 1 is subjected to a treatment (orientation treatment) for imparting liquid crystal alignment ability. Thereby, the orientation ability of a liquid crystal molecule is given to a coating film, and it becomes a liquid crystal aligning film. Examples of the alignment treatment include: a rubbing treatment in which a liquid crystal alignment ability is imparted to the coating film by rubbing the coating film in a fixed direction with a roll on which a cloth containing fibers such as nylon, rayon, and cotton is wound; The photo-alignment process etc. which perform light irradiation on the coating film on a board|substrate and give a liquid crystal alignment ability to a coating film. In particular, the polymer (P) has a high photosensitivity and can express anisotropy in a coating film even with a small exposure amount, so that the photo-alignment method can be preferably applied. On the other hand, in the case of producing a vertical alignment type liquid crystal element, the coating film formed in the above-mentioned step 1 may be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment treatment.

The light irradiation in the photo-alignment treatment can be performed by the following methods: a method of irradiating the coating film after the post-baking step; a method of irradiating the coating film after the pre-baking step and before the post-baking step; In at least any one of a baking process and a post-baking process, the method etc. which irradiate a coating film during the heating process of a coating film. In the photo-alignment treatment, as radiation to irradiate the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. Ultraviolet rays containing light having a wavelength of 200 nm to 400 nm are preferable. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. In addition, when the radiation used is linearly polarized light or partially polarized light, the substrate surface may be irradiated from a vertical direction, a substrate surface may be irradiated from an oblique direction, or a combination of these may be performed. In the case of irradiating non-polarized radiation, the direction of irradiation 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 and the like can be used. The irradiation dose of radiation is preferably 400 J/m ² to 50,000 J/m ² , and more preferably 1,000 J/m ² to 20,000 J/m ² . In order to improve the reactivity, light irradiation to the coating film may be performed while heating the coating film.

After light irradiation for orientation ability imparting, for example, water, an organic solvent (for example, methanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.), or a The mixture is used to clean the surface of the substrate, or to heat the substrate. When a coating film is formed using the liquid crystal aligning agent of the present disclosure, even if such a cleaning treatment or heat treatment is not performed, a liquid crystal element having good display performance can be obtained, and cost reduction can be achieved, which is preferable in this respect .

(Step 3: Construction of Liquid Crystal Cell)

A liquid crystal cell is manufactured by preparing two board|substrates in which the liquid crystal aligning film was formed as mentioned above, and arrange|positioning a liquid crystal between the two board|substrates arrange|positioned facing each other. When manufacturing a liquid crystal cell, for example, the following method can be mentioned: (1) The two substrates are arranged to face each other through a gap (spacer) so that the liquid crystal aligning films face each other, and the peripheral parts of the two substrates are adhered using a sealant. The method of sealing the injection hole after injecting and filling the liquid crystal on the surface of the substrate and the cell gap divided by the sealant; (2) Coating the sealant on a predetermined part of one of the substrates forming the liquid crystal alignment film, and then aligning the liquid crystal After dripping liquid crystals at a predetermined number of places on the film surface, another substrate is attached with the liquid crystal aligning film facing each other, and the liquid crystal is spread over the entire surface of the substrate (One Drop Fill, ODF). ) way) etc. It is desirable to further heat the produced liquid crystal cell to a temperature at which the liquid crystal to be used takes an isotropic phase, and then to cool slowly to room temperature, thereby removing the flow alignment at the time of liquid crystal filling.

As the sealing agent, for example, epoxy resin containing a curing agent and alumina balls as spacers can be used. As the spacer, a photospacer, a bead spacer, or the like can be used. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azoxy liquid crystals can be used. Liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane Liquid crystal, cubane liquid crystal, etc. Moreover, you may add and use, for example, a cholesteric liquid crystal, a chiral agent, a ferroelectric liquid crystal, etc. to these liquid crystals.

Next, a polarizing plate is bonded to the outer surface of a liquid crystal cell as needed, and a liquid crystal element is produced. Examples of the polarizing plate include a polarizing plate formed by sandwiching a polarizing film called an "H film" with a cellulose acetate protective film, or a polarizing plate including an H film itself, which is a polarizing plate made of a polymer A film formed by absorbing iodine while extending and orienting vinyl alcohol.

The liquid crystal element of the present disclosure can be effectively applied to various applications, such as watches, portable game machines, word processors, note type personal computers, and car navigation systems. navigation system), camcorder (camcorder), personal digital assistant (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart phone, various monitors, LCD TV, information display (information display) and other various Display devices, or dimming films, etc. Moreover, the liquid crystal element formed using the liquid crystal aligning agent of this disclosure can also be applied to a retardation film.

[Example]

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

In the following examples, the molecular weight of the polymer was measured by the following method.

[Molecular weight of polymer]

The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were measured by gel permeation chromatography (GPC) under the following conditions, and the molecular weight distribution (Mw/Mn) was determined.

Measuring device: manufactured by Tosoh Co., Ltd., HLC-8020

Column: manufactured by Tosoh Corporation, used by connecting TSK guardcolumn α, TSK gel α-M, and TSK gel α-2500 in series

Developing solvent: A solution in which 9.4 g of lithium bromide monohydrate and 1.7 g of phosphoric acid were dissolved in 3 L of dimethylformamide

Temperature: 35℃

Flow rate: 1.0 mL/min

The structures and abbreviations of the main compounds used in the following examples are as follows.

(Tetracarboxylic dianhydride) TA-1: 1,2,3,4-butanetetracarboxylic dianhydride TA-2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride TA-3: (1R,2R,3S,4S)-1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride TA-4: trans-1,2,3,4-ring Pentanetetracarboxylic dianhydride TA-5: 2,3,5-tricarboxycyclopentylacetic dianhydride TA-6: Pyromellitic dianhydride

[Chemical 14]

(Diamine) DA-1: p-phenylenediamine DA-2: 4,4'-diaminodiphenylmethane DA-3: 4,4'-ethylenediphenylamine DA-4: 2,2'-dimethyl Alkyl-4,4'-diaminobiphenyl DA-5: N-(tert-butoxycarbonyl)-2,5-diaminobenzylamine DA-6: 4-amino-N-(4-aminophenyl) )-N-(tert-butoxycarbonyl)benzamide DA-7: 4,4'-diaminodiphenylamine DA-8: 4,4'-diamino-N4,N4'-bis(4 -Aminophenyl)-N4,N4'-dimethylbiphenyl DA-9: N-2-(4-aminophenylethyl)-N-methylamine DA-10: 6,6'-(呱oxazine-1,4-diyl)-bis(pyridin-3-amine) DA-11: 1,4-phenoxy-bis(4-aminobenzoate) DA-12: 4-aminophenyl -3-(4-Aminophenyl)-2-methacrylate

[Chemical 15]

(Terminal modifier) EC-1: Methacryloyl chloride EC-2: 2-furancarboyl chloride EC-3: furfurylamine EC-4: 2-aminoethanethiol EC-5: N-(tert-butyl) oxycarbonyl)-1,2-diaminoethane

[Chemical 16]

(Imidation accelerator) I-1: 3-(2-hydroxyphenyl)-N-(pyridin-3-ylmethyl)propionamide I-2: N-α-(9-fluorenylmethyl) Oxycarbonyl)-N-(tert-butoxycarbonyl)-L-histidine (functional silane compound) S-1: 3-glycidyloxypropylmethyldiethoxysilane (epoxy-containing compound) CL-1: N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane CL-2: N,N,N',N'-tetrakis(2 -Hydroxyethyl)ethylenediamine (dehydration catalyst) DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine chloride (Solvent) NMP: N-methyl-2-pyrrolidone γBL: γ-butyrolactone BC: Butyl cellosolve

[Example 1a]

22.42 g (100 mmol) of TA-3, 100 mL of tetrahydrofuran, and 0.79 g (10.0 mmol) of pyridine were placed in a 200 mL three-necked flask equipped with a nitrogen gas introduction tube, a reflux cooling tube, and a thermometer, and the reaction was carried out under nitrogen flow. Stir to suspend it. To this suspension was added 15.14 g (210 mmol) of β-methallyl alcohol, followed by stirring at room temperature for 2 hours. Furthermore, it was made to react at 60 degreeC for 8 hours, and the colorless and transparent solution was obtained. The reaction solution was concentrated under reduced pressure at 60° C., and further vacuum-dried to obtain a mixture of a compound represented by the following formula (DE-1a) and a compound represented by the following formula (DE-1b) (hereinafter, Called DE-1a/b) 36.84 g.

[Chemical 17]

[Example 2a]

18.42 g (50.0 mmol) of DE-1a/b and 100 mL of toluene were put into a 100 mL eggplant-shaped flask equipped with a nitrogen gas introduction tube and a reflux cooling tube, and the mixture was stirred at 80° C. for 30 minutes. Then, the mixture was cooled to room temperature while stirring, and further stirred at room temperature for 30 minutes. The obtained suspension was filtered and washed twice with 5 mL of toluene. The obtained solid was vacuum-dried at 60°C to obtain 15.47 g (42.0 mmol, 84% yield) of DE-1a as a white powder.

[Example 3a]

14.74 g (40.0 mmol) of DE-1a, 80 mL of heptane, and 0.032 g (0.40 mmol) of pyridine were put into a 500 mL three-necked flask equipped with a nitrogen gas introduction tube, a reflux cooling tube, and a thermometer, and the flask was placed under a nitrogen stream. and stirred at 75°C. 14.28 g (120 mmol) of sulfite chloride was slowly added dropwise over 20 minutes, and bubbling accompanying the progress of the reaction was confirmed. After the dropwise addition, the reaction was carried out at 75°C for 2 hours to obtain a colorless and transparent solution. The reaction solution was concentrated under reduced pressure at 60°C, and excess thionite chloride was distilled off. To the obtained liquid, 80 mL of heptane was added, the mixture was stirred at room temperature, and the precipitated insoluble components were removed by filtration. The filtrate was concentrated under reduced pressure at 60°C, and further dried under vacuum at 60°C for 4 hours to obtain 15.89 g (39.2 mmol, 15.89 g (39.2 mmol) of the compound represented by the following formula (DC-1a) as a colorless transparent liquid. rate of 98%).

[Chemical 18]

[Example 4a]

Except having changed 15.14 g (210 mmol) of β-methallyl alcohol to 20.60 g (210 mmol) of furfuryl alcohol, the following formula (DE-2a) was obtained in the same manner as in Example 1a. 42.04 g of a mixture of the compound represented by the following formula (DE-2b) (hereinafter referred to as DE-2a/b).

[Chemical 19]

[Example 5a]

9.81 g (50 mmol) of TA-2, 50 mL of tetrahydrofuran, and 0.40 g (5.0 mmol) of pyridine were placed in a 100 mL three-necked flask equipped with a nitrogen gas introduction tube, a reflux cooling tube, and a thermometer, and the reaction was carried out under nitrogen flow. Stir to suspend it. To this suspension was added 13.66 g (105 mmol) of 2-hydroxyethyl methacrylate, and the mixture was stirred at room temperature for 2 hours. Furthermore, it was made to react at 40 degreeC for 24 hours, and the colorless and transparent solution was obtained. The reaction solution was concentrated under reduced pressure at 40°C, and further vacuum-dried to obtain a mixture of a compound represented by the following formula (DE-3a) and a compound represented by the following formula (DE-3b) (hereinafter, Known as DE-3a/b) 22.82 g.

[hua 20]

[Example 6a]

The following formula (DE-4a) was obtained in the same manner as in Example 1a, except that 15.14 g (210 mmol) of β-methallyl alcohol was changed to 11.77 g (210 mmol) of propargyl alcohol. 33.63 g of a mixture of the represented compound and the compound represented by the following formula (DE-4b) (hereinafter referred to as DE-4a/b).

[Chemical 21]

[Example 7a]

Except having changed 15.14 g (210 mmol) of β-methallyl alcohol to 15.56 g (210 mmol) of hydroxyacetone, the following formula (DE-5a) was obtained in the same manner as in Example 1a. 37.23 g of a mixture of the compound and the compound represented by the following formula (DE-5b) (hereinafter referred to as DE-5a/b).

[Chemical 22]

[Example 8a]

The following formula (DE- 21.61 g of a mixture of the compound represented by 6a) and the compound represented by the following formula (DE-6b) (hereinafter referred to as DE-6a/b).

[Chemical 23]

[Synthesis Example 9]

9.81 g (50 mmol) of 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride, 50 mL of tetrahydrofuran, 0.40 g (5.0 mmol) of pyridine was suspended by stirring under nitrogen flow. To this suspension, 6.4 g (200 mmol) of methanol was added, and the mixture was stirred at room temperature for 24 hours to obtain a colorless and transparent solution. The reaction solution was concentrated under reduced pressure at 60°C, and further vacuum-dried to obtain a mixture of a compound represented by the following formula (DE-7a) and a compound represented by the following formula (DE-7b) (hereinafter, Known as DE-7a/b) 14.41 g.

[Chemical 24]

[Synthesis Example 10]

The compound represented by the following formula (DE-8a) was synthesized according to the method described in Example 4 of International Publication No. WO 2010/092989. In addition, a compound represented by the following formula (DC-8a) was synthesized according to the method described in Example 47 of International Publication No. WO 2010/092989.

[Chemical 25]

[Synthesis Example 11]

1.63 g (11.0 mmol) of 3,4-dihydrocoumarin and 1.08 g (10.0 mmol) of 3-(amino) were placed in a 50 mL eggplant-shaped flask equipped with a nitrogen gas introduction tube, a reflux cooling tube, and a thermometer. methyl)pyridine, 10 mL of tetrahydrofuran, heated to reflux at 80°C for 3 hours under nitrogen flow. To this reaction solution, 40 ml of heptane was added to precipitate a product, which was then filtered. The obtained solid was washed with heptane and dried under reduced pressure to obtain 2.51 g (9.8 mmol) of 3-(2-hydroxyphenyl)-N-(pyridin-3-ylmethyl)propionamide.

[Chemical 26]

[Synthesis Example 12]

N-(tert-butoxycarbonyl)-2,5-diaminobenzylamine was synthesized according to the method described in Synthesis Example 7 of International Publication No. 2011/115118.

[Example 1]

3.54 g (9.6 mmol) of DE-1a/b, 1.08 g (10.0 mmol) of DA-1, 31.0 g of NMP, 0.51 g (5.0 mmol) of DE-1a/b, 31.0 g of NMP, and 0.51 g (5.0 mmol) were placed in a 50 mL three-necked flask equipped with a nitrogen gas inlet tube and a thermometer. ) of triethylamine, cooled to about 10 °C, and 8.30 g (30.0 mmol) of DMT-MM as a triazine-based dehydration condensing agent was added, and reacted for 24 hours at room temperature under nitrogen flow. The obtained polymerization solution was diluted with NMP, and was poured into methanol gradually while stirring, and was made to coagulate. The precipitated solid was recovered, washed with stirring twice in methanol, and vacuum-dried at 60° C. to obtain a white powder of polyamic acid ester (PAE-1). The polymer had a number average molecular weight Mn of 11,000 and a molecular weight distribution Mw/Mn of 3.0.

[Example 2]

Except having changed DE-1a/b to DE-1a 3.54 g (9.6 mmol), it carried out similarly to Example 1, and obtained polyamic acid ester (PAE-2). The polymer had a number average molecular weight Mn of 12,000 and a molecular weight distribution Mw/Mn of 4.1.

[Example 3]

Polycarbamic acid ester (PAE) was obtained in the same manner as in Example 1, except that DE-1a/b was changed to 2.83 g (7.68 mmol) of DE-1a and 0.553 g (1.92 mmol) of DE-7a/b. -3). The polymer had a number average molecular weight Mn of 21,000 and a molecular weight distribution Mw/Mn of 3.5.

[Example 4]

1.03 g (9.5 mmol) of DA-1, 0.106 g (0.50 mmol) of DA-3, and 20.0 g of NMP were put into a 50 mL three-necked flask equipped with a nitrogen gas introduction tube and a thermometer, and prepared by cooling to about 10°C Diamine solution. To the solution was added an acyl chloride solution prepared by preliminarily dissolving 3.89 g (9.6 mmol) of DC-1a in 1.90 g (21.6 mmol) of pyridine and 20.0 g of γBL, and reacted at room temperature for 4 hours under a nitrogen stream. To this polymerization solution, 0.209 g (2.0 mmol) of EC-1 was added, and the reaction was further carried out for 4 hours. The obtained polymerization solution was diluted with γBL, poured into deionized water gradually while stirring, and solidified. The precipitated solid was recovered, and washed twice with stirring in isopropanol, and vacuum-dried at 60° C. to obtain a white powder of polycarbamic acid ester (PAE-4). The polymer had a number average molecular weight Mn of 8,000 and a molecular weight distribution Mw/Mn of 2.1.

[Example 5]

0.973 g (9.0 mmol) of DA-1, 0.327 g (1.0 mmol) of DA-6, and 20.0 g of NMP were put into a 50 mL three-necked flask equipped with a nitrogen gas inlet tube and a thermometer, cooled to about 10° C. to prepare Diamine solution. To the solution was added an acyl chloride solution prepared by preliminarily dissolving 3.89 g (9.6 mmol) of DC-1a in 1.90 g (21.6 mmol) of pyridine and 20.0 g of γBL, and reacted at room temperature for 4 hours under a nitrogen stream. To this polymerization solution, 0.261 g (2.0 mmol) of EC-2 was added, and the reaction was further carried out for 4 hours. The obtained polymerization solution was diluted with γBL, poured into deionized water gradually while stirring, and solidified. The precipitated solid was recovered, and washed twice with stirring in isopropanol, and vacuum-dried at 60° C. to obtain a white powder of polycarbamic acid ester (PAE-5). The polymer had a number average molecular weight Mn of 25,000 and a molecular weight distribution Mw/Mn of 4.5.

[Example 6]

4.04 g (9.6 mmol) of DE-2a/b, 0.995 g (9.2 mmol) of DA-1, and 0.078 g (0.8 mmol) of EC-3 were placed in a 50 mL three-necked flask equipped with a nitrogen gas inlet tube and a thermometer. , 31.0 g of NMP, 0.51 g (5.0 mmol) of triethylamine, cooled to about 10 °C and added 8.30 g (30.0 mmol) of DMT-MM, reacted at room temperature for 24 hours under nitrogen flow. The obtained polymerization solution was diluted with NMP, and was poured into methanol gradually while stirring, and was made to coagulate. The precipitated solid was recovered, washed with stirring twice in methanol, and vacuum-dried at 60° C. to obtain a white powder of polyamic acid ester (PAE-6). The polymer had a number average molecular weight Mn of 15,000 and a molecular weight distribution Mw/Mn of 3.2.

[Example 7]

2.19 g (4.8 mmol) of DE-3a/b, 1.38 g (4.8 mmol) of DE-8a, and 1.08 g (10.0 mmol) of DA-1 were placed in a 50 mL three-necked flask equipped with a nitrogen gas inlet tube and a thermometer. , 31.0 g of NMP, 0.51 g (5.0 mmol) of triethylamine, cooled to about 10 °C and added 8.30 g (30.0 mmol) of DMT-MM, reacted at room temperature for 24 hours under nitrogen flow. The obtained polymerization solution was diluted with NMP, and was poured into methanol gradually while stirring, and was made to coagulate. The precipitated solid was recovered, washed with stirring twice in methanol, and vacuum-dried at 60° C. to obtain a white powder of polyamic acid ester (PAE-7). The polymer had a number average molecular weight Mn of 18,000 and a molecular weight distribution Mw/Mn of 1.8.

[Example 8]

3.23 g (9.6 mmol) of DE-4a/b, 0.995 g (9.2 mmol) of DA-1, and 0.062 g (0.8 mmol) of EC-4 were placed in a 50 mL three-necked flask equipped with a nitrogen gas inlet tube and a thermometer. , 31.0 g of NMP, 0.51 g (5.0 mmol) of triethylamine, cooled to about 10 °C and added 8.30 g (30.0 mmol) of DMT-MM, reacted at room temperature for 24 hours under nitrogen flow. The obtained polymerization solution was diluted with NMP, and was poured into methanol gradually while stirring, and was made to coagulate. The precipitated solid was recovered, washed with stirring twice in methanol, and vacuum-dried at 60° C. to obtain a white powder of polyamic acid ester (PAE-8). The polymer had a number average molecular weight Mn of 12,000 and a molecular weight distribution Mw/Mn of 3.3.

[Example 9]

3.57 g (9.6 mmol) of DE-5a/b, 0.796 g (7.36 mmol) of DA-1, and 0.437 g (1.84 mmol) of DA-5 were placed in a 50 mL three-necked flask equipped with a nitrogen gas inlet tube and a thermometer. , 0.128 g (0.80 mmol) of EC-5, 31.0 g of NMP, 0.51 g (5.0 mmol) of triethylamine, cooled to about 10 °C and added 8.30 g (30.0 mmol) of DMT-MM, under nitrogen The reaction was carried out at room temperature for 24 hours. The obtained polymerization solution was diluted with NMP, and was poured into methanol gradually while stirring, and was made to coagulate. The precipitated solid was recovered, washed with stirring twice in methanol, and vacuum-dried at 60° C. to obtain a white powder of polyamic acid ester (PAE-9). The polymer had a number average molecular weight Mn of 12,000 and a molecular weight distribution Mw/Mn of 3.5.

[Example 10]

2.08 g (4.8 mmol) of DE-6a/b, 1.38 g (4.8 mmol) of DE-8a, and 0.796 g (7.36 mmol) of DA-1 were placed in a 50 mL three-necked flask equipped with a nitrogen gas inlet tube and a thermometer. , 0.437 g (1.84 mmol) of DA-5, 0.128 g (0.80 mmol) of EC-5, 31.0 g of NMP, 0.51 g (5.0 mmol) of triethylamine, cooled to about 10°C and added 8.30 g (30.0 mmol) of DMT-MM under nitrogen flow at room temperature for 24 h. The obtained polymerization solution was diluted with NMP, and was poured into methanol gradually while stirring, and was made to coagulate. The precipitated solid was recovered, washed with stirring twice in methanol, and vacuum-dried at 60° C. to obtain a white powder of polycarbamic acid ester (PAE-10). The polymer had a number average molecular weight Mn of 20,000 and a molecular weight distribution Mw/Mn of 3.0.

[Synthesis Example 13]

1.08 g (10.0 mmol) of DA-1 and 16.0 g of NMP were put into a 50 mL three-necked flask equipped with a nitrogen gas introduction tube and a thermometer, and cooled to about 10° C. to prepare a diamine solution. To the solution was added an acyl chloride solution prepared by preliminarily dissolving 3.12 g (9.6 mmol) of DC-8a in 1.90 g (21.6 mmol) of pyridine and 16.0 g of γBL, and reacted at room temperature for 4 hours under a nitrogen stream. The obtained polymerization solution was diluted with γBL, poured into deionized water gradually while stirring, and solidified. The precipitated solid was recovered, and washed twice with stirring in isopropanol, and vacuum-dried at 60° C. to obtain a white powder of polyurethane (PAE-11). The polymer had a number average molecular weight Mn of 19,000 and a molecular weight distribution Mw/Mn of 1.5.

[Synthesis Example 14]

100 mol parts of TA-3 as tetracarboxylic dianhydride and 100 mol parts of DA-1 as diamine were dissolved in NMP, and reacted at room temperature for 6 hours to obtain a polymer containing 20 mass %. A solution of amino acid (PAA-1).

[Synthesis Example 15]

100 mol parts of TA-2 as tetracarboxylic dianhydride and 100 mol parts of DA-4 as diamine were dissolved in NMP and reacted at room temperature for 6 hours to obtain a polymer containing 20 mass %. Amino acid (PAA-2) solution.

[Synthesis Example 16]

100 mol parts of TA-1 as tetracarboxylic dianhydride and 100 mol parts of DA-7 as diamine were dissolved in NMP and reacted at room temperature for 6 hours to obtain a polymer containing 20 mass %. Amino acid (PAA-3) solution.

[Synthesis Example 17]

100 mol parts of TA-4 as tetracarboxylic dianhydride, 80 mol parts of DA-2 as diamines, and 20 mol parts of DA-8 were dissolved in NMP and carried out at room temperature for 6 hours The reaction was carried out to obtain a solution containing 20% by mass of polyamic acid (PAA-4).

The kind and compounding ratio of the compound used for the synthesis|combination of a polymer are shown in following Table 1. In addition, in following Table 1, "molar ratio" shows the usage ratio (molar ratio) of each compound used for synthesis (The same is true in following Table 3).

[Table 1]

[Example 11: Photo-alignment FFS-type liquid crystal display element]

(1) Preparation of liquid crystal aligning agent

The polymer (PAE-1) obtained in Example 1 as a polymer was dissolved in γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP) and In a mixed solvent (GBL:NMP:BC=80:10:10 (mass ratio)) of butyl cellosolve (BC), a solution having a solid content concentration of 4.0 mass % was prepared. A liquid crystal aligning agent (R-1) was prepared by filtering this solution with the screening program of 0.2 micrometers of pore diameters.

(2) Evaluation of coatability

The liquid crystal aligning agent (R-1) prepared above was coated on a glass substrate using a spin coater, pre-baked for 1 minute on a hot plate at 80°C, and then used in an oven at 230°C that replaced the inside of the warehouse with nitrogen. Heating (post-baking) was performed for 30 minutes to form a coating film with an average film thickness of 0.1 μm. The coating film was observed with a microscope with a magnification of 100 times and 10 times, and the presence or absence of film thickness unevenness and pinholes was investigated. Regarding the evaluation, the coating property was evaluated as “good” when both the film thickness unevenness and pinholes were not observed even when observed with a 100-fold microscope, and the film thickness unevenness and pinholes were observed with a 100-fold microscope. When at least one of the film thickness unevenness and pinholes were not observed under a 10x microscope, the coating property was evaluated as "ok", and at least one of the film thickness unevenness and pinholes was clearly observed under a 10x microscope. The case of the case was evaluated as "poor" in applicability. In the present Example, neither the unevenness of the film thickness nor the pinholes were observed under a microscope of 100 times, and the coating property was "good".

(3) Measurement of the imidization rate of the polymer component in the coating film

Regarding the coating film obtained in the above (2), the absorbance α1 in the vicinity of 1360 cm-1 (absorption due to the CN stretching vibration of the imide group) in the FT-IR measurement and the absorbance α1 in the vicinity of 1500 cm-1 The absorbance α2 of absorption (absorption derived from the C=C stretching vibration of the aromatic ring) was used to calculate the imidization rate (%) by the following formula (4).

Imidization rate (%)={(α1 _{230 ℃} /α2 _{230 ℃} )/(α1 _{300 ℃} /α2 _{300 ℃} )}´100…(4)

(In the formula (4), α1 _{230 °C} and α2 _{230 °C} are the measurement results of the coating film obtained in the above (2), and α1 _{300 °C} and α2 _{300 °C} are the values of 300°C using nitrogen gas replacement in the chamber. The measurement results of the coating film after being heated in an oven for 90 minutes. Among them, the imidization rate of the coating film heated at 300°C was 100%)

As a result, the imidization rate of the coating film was 30%.

(4) Adhesion

The adhesiveness of the coating film formed with the liquid crystal aligning agent and a board|substrate was evaluated using the coating film manufactured by the said (2). First, the coating film was cut with a dicing knife using equally spaced spacers with guides to form 10×10 lattice patterns within a range of 1 cm×1 cm. The depth of each cut is formed so as to reach the middle of the coating film. Next, after the cellophane tape was adhered so as to cover the entire surface of the lattice pattern, the cellophane tape was peeled off. The cut part of the lattice pattern after peeling was observed by visual observation under the crossed Nicols, and the adhesiveness was evaluated. The evaluation was performed as follows: the part along the notch line and the intersection part of the lattice pattern was not observed to be peeled, and the adhesion was evaluated as "⊚", and the number of lattice eyes in which peeling was observed in the part was relative to the entire lattice pattern. Adhesion "0" was evaluated when the number of objects was less than 15%, adhesion between 15% and more and less than 20% was evaluated as adhesion "△", and 20% or more was evaluated as "´". As a result, the adhesiveness of this coating film was "△".

(5) Manufacture of liquid crystal display element by photo-alignment method

Using a spin coater, the liquid crystal aligning agent (R-1) prepared as described above was applied to a glass substrate in which a flat electrode, an insulating layer and a comb-shaped electrode were sequentially laminated on one side so that the film thickness was 0.1 μm, and Each surface of the opposing glass substrate on which the electrode was not provided was dried with a hot plate at 80° C. for 1 minute, and dried with a clean oven at 200° C. for 1 hour to form a coating film. The coating film surface was irradiated with 500 mJ/cm 2 of polarized ultraviolet rays containing bright lines of 254 nm from the substrate normal direction using a Hg-Xe lamp to form a liquid crystal aligning film. Next, with respect to the pair of substrates subjected to the above-mentioned light irradiation treatment, an epoxy resin adhesive containing alumina balls having a diameter of 5.5 μm was screen-printed and applied to the surface on which the liquid crystal aligning film was to be formed, leaving a liquid crystal injection port. Then, the substrates were superimposed and crimped so that the projection direction of the polarization axis at the time of light irradiation to the substrate surface became antiparallel, and the adhesive was thermally cured at 150° C. for 1 hour. Next, after filling a nematic liquid crystal (Merck & Co. make, MLC-7028) between the pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, after heating to 150 degreeC, it cooled to room temperature gradually. Next, a polarizing plate was bonded to both outer surfaces of the substrate to produce a liquid crystal display element of a lateral electric field (FFS) method.

(6) Evaluation of liquid crystal orientation

The liquid crystal display element manufactured in the above (5) was observed with a microscope at a magnification of 50 times for the presence or absence of abnormal regions of light and dark changes when a voltage of 5V was turned ON and OFF (applied and released). Regarding the evaluation, the case where no abnormal region was observed was evaluated as "good" liquid crystal orientation, and the case where abnormal region was observed was evaluated as "poor" in liquid crystal alignment. As a result, it evaluated as "good" in this Example.

(7) Contrast evaluation after driving stress (evaluation of AC afterimage characteristics)

An FFS-type liquid crystal cell was produced by performing the same operation as the above (5) except that the polarizing plate was not bonded to the outer both surfaces of the substrate. This FFS-type liquid crystal cell was driven with an AC voltage of 10 V for 30 hours, and then the minimum relative value represented by the following formula (2) was measured using a device in which a polarizing element and an analyzer were arranged between the light source and the light quantity detector. Transmittance (%).

Minimum relative transmittance (%)=(β-B0)/(B100-B0)×100…(2)

(In Equation (2), B0 is the light transmittance under the crossed Nicols using the blank. B100 is the light transmittance under the parallel Nicols using the blank. β is the crossed Nicols, the The liquid crystal display element is sandwiched between the polarizing element and the analyzer to achieve the minimum amount of light transmission)

The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element, and in the FFS type liquid crystal display element, the lower the black level in the dark state, the better the contrast. The minimum relative transmittance of less than 1.0% was evaluated as the AC afterimage characteristic "◎", the case of 1.0% or more and less than 1.5% was evaluated as "○", the case of 1.5% or more and less than 2.0% was evaluated as "△", and the 2.0% or more rated it as "´". As a result, it was evaluated as "△" in this Example.

(8) Observation of tiny bright spots (heat-resistant reliability test)

The evaluation of the minute bright spot was performed by performing the same operation as the above (5) except that the polarizing plate was not bonded to the outer sides of the substrate, in a constant temperature bath at 100°C. After internal storage for 21 days, the presence or absence of minute bright spots in the liquid crystal cell was observed with a microscope. Furthermore, when the decomposed product generated by light irradiation for photo-alignment treatment remained in the film, it was found that by exposing the liquid crystal display element in a high temperature environment for a long time, the decomposed product oozes out to the surface of the film, and gradually disappears in the liquid crystal. Crystallization was observed as tiny bright spots. In addition, the observation area was 680 μm × 680 μm, and observation was performed at a microscope magnification of 100 times. Regarding the evaluation, the case where no microscopic bright spot was observed was evaluated as "0", the case where the number of observed microscopic bright spots was 1 or 2 was evaluated as "△", and the number of observed microscopic bright spots was 3 or more and A case of 5 points or less was rated as "´", and a case of 6 points or more was observed as "´´". As a result, it was evaluated as "0" in this Example.

[Example 12 to Example 22, Comparative Example 1 to Comparative Example 3]

In the said Example 11, except having changed the kind and compounding ratio of the polymer and additive contained in the liquid crystal aligning agent as shown in the following Table 2, the liquid crystal aligning agent was prepared in the same manner as in Example 11, and FFS was produced. Various evaluations were performed using a type liquid crystal display element or a liquid crystal cell. The evaluation results are shown in Table 2 below. In addition, the compounding ratio of polymer 1 and polymer 2 in the liquid crystal aligning agent in Table 2 is represented by mass parts in terms of solid content, and the compounding ratio of additive 1 and additive 2 is represented by the solid content of polymer 1 and polymer 2. The total mass is expressed in parts by mass when it is set to 100 parts by mass.

[Table 2]

In Example 11 - Example 22, the coating property and adhesiveness of a liquid crystal aligning agent, and the liquid crystal aligning property of a liquid crystal display element, AC afterimage characteristic, and heat resistance were balanced. In particular, in Examples 14 to 18, Example 20, and Example 21, the above-mentioned properties were all "good", "⊚" or "0", and the balance of various properties was excellent. In addition, in Example 19 and Example 22, the AC afterimage characteristics were evaluated as "0", and the results were slightly poor, but the coating properties, liquid crystal alignment properties, and heat resistance were the same as the other Examples. good results. On the other hand, Comparative Examples 1 to 3 are inferior to Examples in a plurality of evaluation items.

Moreover, when Example 12 - Example 22 were compared with the comparative example 1, the high imidization rate was shown in the Example, and the AC afterimage characteristic became favorable. It is considered that the reason for this is that the interaction with the liquid crystal may be improved by the increase in the imidization rate, and the liquid crystal orientation may be improved.

Moreover, from the result of the comparative example 1, it turns out that the photodecomposability is low in polyamic acid, and the liquid-crystal orientation becomes unsatisfactory by the exposure amount of the equivalent polarized ultraviolet-ray.

Furthermore, from Example 14 to Example 18, Example 20 to Example 22, and the comparison with Comparative Example 3, it is considered that in the liquid crystal aligning agent containing the terminal-modified polyamic acid ester and polyamic acid, the source The fine unevenness|corrugation from the phase separation of a polyamic acid ester and a polyamic acid is suppressed, and coating property becomes favorable.

From the results of the above Examples 11 to 22 and Comparative Examples 1 to 3, according to the liquid crystal aligning agent containing a polyamic acid ester having a reactive group in a side chain, even if it is not carried out after the photo-alignment treatment It is also good in heat resistance (especially long-term heat resistance) in the cleaning treatment for rinsing the decomposition products in the film. In Examples 14 to 18, it was taught that the long-term heat resistance is particularly excellent, and the diffusion and/or crystallization of the photodegradation product, which is a causative substance of minute bright spots, is suppressed.

[Synthesis Example 18 to Synthesis Example 22]

Except having changed the kind and amount of the tetracarboxylic dianhydride and the diamine compound as shown in Table 3, it carried out similarly to Synthesis Example 14, and obtained the solution containing polyamic acid (PAA-5-PAA-9).

[Example 23]

1.08 g (10.0 mmol) of DA-1 and 20.0 g of NMP were put into a 50 mL three-necked flask equipped with a nitrogen gas introduction tube and a thermometer, and cooled to about 10° C. to prepare a diamine solution. To the solution was added an acyl chloride solution prepared by preliminarily dissolving 3.89 g (9.6 mmol) of DC-1a in 1.90 g (21.6 mmol) of pyridine and 20.0 g of γBL, and reacted at room temperature for 4 hours under a nitrogen stream. The obtained polymerization solution was diluted with γBL, poured into deionized water gradually while stirring, and solidified. The precipitated solid was recovered, and washed twice with stirring in isopropanol, and vacuum-dried at 60° C. to obtain a white powder of polyurethane (PAE-12). The polymer had a number average molecular weight Mn of 20,000 and a molecular weight distribution Mw/Mn of 3.20.

[Example 24 to Example 27]

Polyamides (PAE-13 to PAE-16) were obtained in the same manner as in Example 23, except that the types and amounts of the tetracarboxylic acid derivatives and the diamine compounds were changed as shown in Table 3 below. The polymer (PAE-13) had a number average molecular weight Mn of 22,000 and a molecular weight distribution Mw/Mn of 3.90, and the polymer (PAE-14) had a number average molecular weight Mn of 30,000 and a molecular weight distribution Mw/Mn of 4.10. The polymer (PAE-15) had a number average molecular weight Mn of 11,000 and a molecular weight distribution Mw/Mn of 3.00, and the polymer (PAE-16) had a number average molecular weight Mn of 10,000 and a molecular weight distribution Mw/Mn of 2.90.

[Example 28]

With reference to the method described in Synthesis Example 4 of International Publication No. WO 2015/152174, the following method was used to synthesize a polyamic acid ester-polyamic acid copolymer (PAE-17).

3.50 g (9.5 mmol) of DE-1a and 55.4 g of NMP were added to a 100 mL three-necked flask equipped with a nitrogen gas introduction tube and a thermometer, and were dissolved by stirring. Next, 2.11 g (20.9 mmol) of triethylamine and 2.05 g (19.0 mmol) of DA-1 were added and dissolved by stirring. The solution was cooled to about 10°C, and 7.28 g (19.0 mmol) of diphenyl (2,3-dihydro-2-thio-3-benzoxazolyl)phosphonate was added, followed by 11.9 g of NMP under nitrogen flow at room temperature for 12 hours. Then, 0.95 g (3.80 mmol) of diphenyl phosphate and 2.00 g (8.93 mmol) of TA-3 were added, and 11.9 g of NMP was further added, and the mixture was reacted at room temperature for 12 hours under nitrogen flow. While stirring, the obtained polymerization solution was gradually poured into methanol (600 g) and solidified. The precipitated solid was recovered, and after stirring and washing in methanol was repeated twice, vacuum drying was performed at 60° C. to obtain a powder of a polyamic acid ester-polyamic acid copolymer (PAE-17). The polymer had a number average molecular weight Mn of 20,000 and a molecular weight distribution Mw/Mn of 3.50.

[table 3]

[Example 29 to Example 41]

In the said Example 11, except having changed the kinds of polymers and additives contained in the liquid crystal aligning agent as shown in the following Table 4, a liquid crystal aligning agent was prepared in the same manner as in Example 11, and an FFS type liquid crystal display was produced. Various evaluations were performed on the element or the liquid crystal cell. The evaluation results are shown in Table 4 below.

[Table 4]

In Examples 29 to 41, the coating properties and adhesive properties of the liquid crystal aligning agent, and the liquid crystal alignment properties in the liquid crystal display element, AC afterimage characteristics, and heat resistance were all “good”, “⊚”, or “○”. ” and achieved a balance of various properties. Among them, the liquid crystal alignment properties and AC afterimage characteristics of Example 31 were particularly favorable, and the adhesiveness of Example 41 was particularly favorable.

Moreover, Example 29 - Example 37 were especially excellent in heat resistance, and even if the ratio of the polymer 1 was small, but the composition of 10 parts showed favorable liquid crystal orientation and AC afterimage characteristics. The reason for this is considered to be that the polyimide of the polymer 1 has high hydrophobicity and promotes layer separation from the polyimide of the polymer 2, so that the polyimide derived from the polymer 1 tends to exist in the alignment film in a biased manner. surface layer. In addition, it is considered that when the ratio of the polymer 1 is small, the generation amount of photodecomposed products decreases, so that contamination of the sintering furnace can be reduced, and the amount of photodecomposed products remaining in the alignment film decreases. In this case, the generation of minute bright spots is small, and the heat resistance is improved.

Although the present invention has been disclosed above by the embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field can make some changes and modifications without departing from the spirit and scope of the present invention. Therefore, The protection scope of the present invention shall be determined by the scope of the appended patent application.

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Claims (10)

A liquid crystal aligning agent containing a polymer (P) having a partial structure represented by the following formula (1);

In formula (1), R ¹ is a tetravalent tetravalent cyclobutane ring structure containing an optionally substituted group derived from 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride Organic group, R ² is a divalent organic group; X ¹ and X ² are each independently a hydroxyl group or a monovalent organic group with a carbon number of 1-40; wherein, at least one of ^{X 1} and X ^{2 is a reactive group} of monovalent organic radicals. The liquid crystal aligning agent according to claim 1, wherein in the formula (1), ^{at least one of X 1} and X ² is selected from the following formula (2-1) to (2-10) ) the structure represented by each and one in the group formed by (meth)acryloyloxy;

In formulas (2-1) to (2-10), R ⁴ is a divalent aliphatic group having 1 to 6 carbon ^{atoms that may have a substituent, and R 5 is} each independently a hydrogen atom or a group that may have a substituent. A monovalent aliphatic group with 1 to 6 carbon atoms; wherein, ^{any two aliphatic groups in R 4} and R ⁵ can be bonded to each other to form a ring structure; in formula (2-1) and formula (2-9) A plurality of R ⁵ may be the same or different from each other; "*" represents a bond. The liquid crystal aligning agent as described in Claim 1 or Claim 2 which further contains the polymer which does not have the structure represented by the said formula (1). The liquid crystal aligning agent according to claim 3, wherein the polymer not having the structure represented by the formula (1) is at least one selected from the group consisting of polyamic acid and polyimide a type of polymer. The liquid crystal aligning agent as described in claim 1 or claim 2 of the claimed scope, which contains at least one selected from the group consisting of a functional silane compound, an acid generator, a base generator, and a radical generator. A liquid crystal aligning film formed using the liquid crystal aligning agent according to any one of the first to fifth claims. The manufacturing method of a liquid crystal aligning film which forms a coating film using the liquid crystal aligning agent as described in any one of Claims 1-5, and irradiates the said coating film with light, and provides a liquid crystal aligning ability. A liquid crystal element including the liquid crystal aligning film as described in claim 6. A polymer having a partial structure represented by the following formula (1);

In formula (1), R ¹ is a tetravalent tetravalent cyclobutane ring structure containing an optionally substituted group derived from 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride Organic group, R ² is a divalent organic group; X ¹ and X ² are each independently a hydroxyl group or a monovalent organic group with a carbon number of 1-40; wherein, at least one of ^{X 1} and X ^{2 is a reactive group} of monovalent organic radicals. A compound or a salt thereof represented by the following formula (1-1) or the following formula (1-2);

In formula (1-1) and formula (1-2), X ¹¹ and X ¹² are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms; wherein, at least one of ^{X 11} and X ¹² is a monovalent organic group with a reactive group; R ^{3 is} independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or a monovalent aliphatic group with a carbon number of 1 to 10 that may have a substituent; X is an optional One of the group consisting of a free hydroxyl group, a chlorine atom, a bromine atom, and a structure represented by each of the following formulae (4-1) to (4-6)

In formula (4-1) to formula (4-6), "*" represents a bond.