JPWO2018230222A1 - Composition, liquid crystal alignment film, retardation plate, polarizing plate, method for manufacturing alignment film, and liquid crystal element - Google Patents

Abstract

A composition having lyotropic liquid crystallinity, which is obtained by mixing a polymer (P) having a partial structure represented by the formula (1) and a solvent, is used. However, in the formula (1), at least one of R1 to R10 is a monovalent group having an ionic functional group, and the rest are each independently a hydrogen atom, a halogen atom or a monovalent organic group. is there. k is 0 or 1.

Description

Cross-reference of related applications

  This application is based on Japanese Patent Application No. 2017-115199 filed on June 12, 2017, the disclosure of which is incorporated herein by reference.

  The present disclosure relates to a composition, a liquid crystal alignment film, a retardation plate, a polarizing plate, a method for manufacturing an alignment film, and a liquid crystal element.

  The liquid crystal includes a thermotropic liquid crystal (melt type) exhibiting liquid crystallinity in a certain temperature range and a lyotropic liquid crystal (solution type) exhibiting liquid crystallinity in a certain concentration range. When the lyotropic liquid crystalline polymer is less than the critical concentration, the arrangement of molecular chains is not regular and is isotropic, but when the concentration is higher than the critical concentration, a liquid crystal state is exhibited. In this liquid crystal state, it becomes an aggregate of minute domains in which molecular chains are arranged in one direction, and exhibits optical anisotropy. Further, when the solution in the liquid crystal state undergoes shear deformation, the molecular chains are oriented in the flow direction. For example, it is known that an aromatic polyamide represented by Kevlar is dissolved in a strong acid such as concentrated sulfuric acid and the concentrated solution exhibits lyotropic liquid crystallinity. By spinning from the solution in the lyotropic liquid crystal state, the molecular chains are oriented in the fiber direction, and a high-performance fiber having a high elastic modulus can be manufactured.

  In order to realize a lyotropic liquid crystalline polymer, it is necessary to use a rigid rod-shaped polymer.However, a rigid rod-shaped polymer generally has difficulty in dissolving in water or an organic solvent. It had to be used or dissolved in a high boiling polar solvent at a high temperature.

  For polymers having a bent structure such as polyamide and polyxylylene, materials that introduce ionic functional groups to ensure solubility and exhibit lyotropic liquid crystallinity under mild conditions have been reported. Applications have been studied (Non-Patent Document 1, Patent Documents 1 to 3). In addition, materials exhibiting lyotropic liquid crystallinity have been reported for polyimides (Non-Patent Documents 2 to 4), and pioneering applied research has been conducted on polyimide precursors by Neuber et al. (Non-Patent Documents 5 to 6).

International Publication No. 2009/130675 WO 2010/0209292 International Publication No. 2010/064194

"Langmuir", 2004, Volume 20, p.6518-6520. "Macromolecular Rapid Communications", 1993, Vol. 14, p.395-400. "Macromolecules", 1991, Vol. 24, p. 1883-1889. "Journal of Polymer Science: Part A: Polymer Chemistry (J. Polym. Sci. A Polym. Chem.)", 1996, vol. 34, p. 587-595. "Macromol. Chemical. Phys.", 2002, Volume 203, p.598-604. "Advanced Functional Materials (Adv. Funct. Mater.)", 2003, Volume 13, p.387-391.

  For controlling the alignment of the liquid crystal, a polyimide-based material has been suitably used as the liquid crystal alignment film in order to develop an excellent alignment control force for the liquid crystal. If a material exhibiting lyotropic liquid crystallinity can be obtained from a polyimide-based material with excellent alignment regulating force, etc., there is a possibility of alignment by shear flow by a simple coating process, and a high-performance liquid crystal alignment film, retardation plate, polarization It is expected that plates and the like can be formed at low cost.

  However, as shown in Non-Patent Documents 2 to 4, although a material exhibiting lyotropic liquid crystallinity has been reported in polyimide, a corrosive solvent such as concentrated sulfuric acid or cresol is required for dissolving polyimide (non-patent literature). Patent Documents 2 to 4) require a high temperature to develop lyotropic liquid crystallinity (Non-Patent Documents 3 and 4), and no material that exhibits lyotropic liquid crystallinity under mild conditions is known. The polyimide precursors disclosed in Non-Patent Documents 5 and 6 require thermal imidization of a coating film due to a polyamic acid ester, and have a high temperature (about 100 ° C.) and a high concentration for developing lyotropic liquid crystallinity. (About 50% by mass). In order to obtain a thin film by coating on a substrate, from the viewpoint of industrial productivity and environmental aspects, a low environmental load solvent such as water or an organic solvent is used, for example, at a temperature of less than 100 ° C. (preferably at about room temperature). It is desirable to exhibit lyotropic liquid crystallinity at a low temperature) and at a sufficiently low concentration. That is, there is a demand for a composition that exhibits lyotropic liquid crystallinity under mild conditions at a temperature, a solvent, and a concentration by using a polyimide having excellent alignment regulating force and the like.

  The present disclosure has been made in view of the above problems, and has as its object to provide a polyimide composition that exhibits lyotropic liquid crystallinity under mild conditions.

According to the present disclosure, the following means are provided.
<1> A composition exhibiting lyotropic liquid crystallinity, obtained by mixing a polymer (P) having a partial structure represented by the following formula (1) and a solvent.
(In the formula (1), at least one of R ^{1 to} R ¹⁰ is a monovalent group having an ionic functional group, and the rest are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. Where k is 0 or 1.)
<2> A liquid crystal alignment film formed using the composition.
<3> A retardation plate formed using the composition.
<4> A polarizing plate formed using the composition.
<5> A liquid crystal aligning agent obtained by mixing a polymer (P) having a partial structure represented by the above formula (1) and a solvent.
<6> A method for producing a liquid crystal alignment film, wherein the composition is applied to a substrate in a lyotropic liquid crystal state, and dried in a state where molecular chains of the polymer (P) are oriented by flow due to shear stress.

  According to the present disclosure, it is possible to obtain a composition exhibiting lyotropic liquid crystallinity under mild conditions by using a polyimide excellent in alignment regulating force and the like. In addition, since the polymer component in the composition of the present disclosure is uniformly aligned in a large area by a simple coating process, a liquid crystal alignment film, a retardation plate, a polarizing plate, and the like can be formed at low cost.

FIG. 1 is a ¹ H-NMR spectrum of the polymer (PI-1). FIG. 2 is a ¹ H-NMR spectrum of the polymer (PI-2). FIG. 3 is a polarizing microscope photograph after the composition (C-1) was dropped on the substrate. FIG. 4 is a polarizing microscope photograph after the composition (C-1) was concentrated on a substrate. FIG. 5 is a polarization microscope photograph after applying a shearing force to the composition (C-1).

  The composition of the present disclosure is a composition obtained by mixing a polymer (P) having a partial structure represented by the above formula (1) and a solvent, and has lyotropic liquid crystallinity. Hereinafter, each component contained in the composition of the present disclosure and other components that are optionally added as needed will be described.

<Polymer (P)>
The polymer (P) is a polyimide. For example, at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic diester, and tetracarboxylic diester dihalide, and diamine are used as raw materials. It can be obtained by imidizing a polyimide precursor obtained by polymerization used for the composition.

As for R ^{1 to} R ¹⁰ in the formula (1), the monovalent organic group is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 5 carbon atoms. The monovalent group having an ionic functional group is “* -L ¹ -X ¹ ” (where L ¹ is a single bond or a divalent linking group, and X ¹ is an ionic functional group. "Represents a bond that is bonded to the benzene ring.) Here, when L ¹ is a divalent linking group, specific examples of L ¹ include an alkanediyl group having 1 to 5 carbon atoms and a group containing —O— between carbon-carbon bonds of the alkanediyl group. , ^-O-R 13 - ** ^{(However, R 13} is a divalent hydrocarbon group, "**" indicates that a bond that binds to ^{X 1.)} and the like are.

  An ionic functional group is a functional group that forms a cation or an anion in water. The ionic functional group is not particularly limited, but is preferably a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, an ammonium group, a pyridinium group, or the like, in that the solubility of the polymer (P) in a solvent containing water can be increased. It is preferably an imidazolium group or a guanidinium group, or a salt thereof. Further, the ionic functional group may be either an acidic functional group or a basic functional group, but is preferably an acidic functional group. Among these, the ionic functional group is preferably a sulfonic acid group, a phosphonic acid group or a carboxylic acid group, or a salt thereof, and particularly preferably a sulfonic acid group or a salt thereof. According to the mixture of the polymer (P) and the solvent, the ionic functional group of the polymer (P) imparts solubility to the solvent to the polymer (P), and particularly drives phase separation in a highly polar solvent. It is presumed that the self-assembly can be promoted as a force and contribute to an increase in anisotropy.

When the ionic functional group is a salt of an acidic functional group or a basic functional group, examples of the counter ion of the acidic functional group (sulfonic acid group, phosphonic acid group, carboxylic acid group, etc.) include Li ⁺ , Na ⁺ , ^{K +, Cs +, Mg 2+} , Ca 2+, Sr 2+, Ba 2+, Zn 2+, Pb 2+, Al 3+, La 3+, Ce 3+, Y 3+, Yb 3+, Gd 3+, NH 4-t Q t + ( However, Q represents a hydrocarbon group having 1 to 20 carbon atoms, and t represents an integer of 0 to 4. When t is 2 to 4, a plurality of Qs may be the same or different. And the like. As the counter ion of the basic functional group (ammonium group, pyridinium group, imidazolium group, guanidinium group, etc.), for example, Cl ⁻ , Br ⁻ , I ⁻ , R ¹⁴ COO ⁻ (where R ¹⁴ has 1 carbon atom) To 20 hydrocarbon groups). When the ionic functional group is a carboxylic acid group, the acid dissociation constant of the carboxylic acid is low, and the proton is less likely to dissociate under acidic conditions and the ionicity is reduced.

In the monovalent group having an ionic functional group, L ¹ can be appropriately selected according to the type of the ionic functional group. For example, when the ionic functional group is a sulfonic, phosphonic or carboxylic acid group, or a salt thereof, L ¹ is preferably a single bond. When the ionic functional group is an ammonium group, a pyridinium group, an imidazolium group or a guanidinium group, or a salt thereof, L ¹ is preferably a divalent linking group, more preferably 1 to 3 carbon atoms. Is an alkanediyl group.
It is sufficient that at least a part of R ^{1 to} R ¹⁰ has an ionic functional group, and the number of ionic functional groups in the above formula (1) is not particularly limited. The number of ionic functional groups in the above formula (1) (that is, the number of monovalent groups having an ionic functional group among R ^{1 to} R ¹⁰ ) is preferably 1 to 4, and 1 or More preferably, the number is two. The ionic functional group has a partial structure derived from a diamine (that is, at least a part of R ^{3 to} R ¹⁰ ) because of exhibiting good lyotropic liquid crystallinity and a high degree of freedom of material selectivity. Is preferred.

The polymer (P) includes a partial structure represented by the following formula (2), a partial structure represented by the following formula (3), and a partial structure represented by the following formula (4) as the partial structure represented by the above formula (1). It is more preferable that the polymer has at least one kind selected from the group consisting of the partial structures represented by the above formula, and it is particularly preferable that the polymer has the partial structure represented by the following formula (2).
(In the formulas (2) to (4), M is a cation. K is 0 or 1. However, when k = 1, a plurality of Ms in the formula may be the same or different. .)

Examples of the M cation include H ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Zn ²⁺ , Pb ²⁺ , Al ³⁺ , La ³⁺ , Ce ³⁺ , and Y ^3+. , Yb ³⁺ , Gd ³⁺ , NH _4-t Q _t ^{+ and the} like. As the cation of M, a monovalent cation is preferable in that the solubility of the polymer (P) in an aqueous solvent can be further increased, and among these, NH ₄ -tQ _t ⁺ is preferable, and a tertiary ammonium ion is preferable. Is more preferred.

  In addition, in this specification, "tetracarboxylic acid diester" means the compound in which two of four carboxyl groups which a tetracarboxylic acid has are esterified, and the remaining two are carboxyl groups. "Tetracarboxylic diester dihalide" refers to a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified and the remaining two are halogenated. Examples of the “polyimide precursor” include polyamic acid and polyamic acid ester. “Organic group” means a group containing a carbon atom, and may contain a hetero atom in the structure.

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

As the monomer used in the synthesis of the polymer (P), at least one selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic diester and tetracarboxylic diester dihalide, and diamine can be used. Preferred specific examples of the tetracarboxylic dianhydride include a compound represented by the following formula (t-1) (hereinafter, also referred to as “specific tetracarboxylic dianhydride”). In addition, a specific tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types. In R ¹ and R ² in the formula (t-1), as the monovalent organic group, a hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom of the hydrocarbon group is substituted with an ionic functional group. And the like. Among them, R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom.
(In the formula (t-1), R ¹ and R ² are a hydrogen atom, a halogen atom, an ionic functional group, or a monovalent organic group.)

The diamine used for the synthesis of the polymer (P) preferably contains a diamine having an ionic functional group (hereinafter, also referred to as “specific diamine”). Particular diamine is a monovalent group in which one or more of ^R 3 ^{to R 10} in the formula (1) has an ionic functional ^group, one or two ionic functional among R 3 ^{to R 10} More preferably, it is a monovalent group having a group.
Preferred specific examples of the specific diamine include compounds represented by the following formulas (d-1) to (d-16). In addition, a specific diamine can be used individually by 1 type or in combination of 2 or more types.

  Preferred specific examples of the tetracarboxylic diester used in the synthesis of the polymer (P) include, for example, tetracarboxylic dianhydride represented by the above formula (t-1) and alcohols such as methanol and ethanol. And the compounds obtained by ring-opening. Preferred specific examples of the tetracarboxylic diester dihalide used in the synthesis of the polymer (P) include compounds obtained by reacting the tetracarboxylic diester with a chlorinating agent such as thionyl chloride. . In addition, a tetracarboxylic acid diester and a tetracarboxylic diester dihalide can be used individually by 1 type or in combination of 2 or more types, respectively.

[Polyamic acid]
The polyamic acid (hereinafter, also referred to as “polyamic acid (P)”) as a precursor of the polymer (P) can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine. Specifically, [i] a method of directly reacting a tetracarboxylic dianhydride containing a specific tetracarboxylic dianhydride with a diamine containing a specific diamine; [ii] a tetramer containing a specific tetracarboxylic dianhydride After neutralizing a carboxylic dianhydride with a base, a method of reacting a tetracarboxylic dianhydride with a diamine containing a specific diamine may be used.

  In the above method [i], a tetracarboxylic dianhydride other than the specific tetracarboxylic dianhydride (hereinafter, also referred to as “other tetracarboxylic dianhydride”), a diamine other than the specific diamine (hereinafter, “other tetracarboxylic dianhydride”) Diamine ") can also be used in combination. From the viewpoint of sufficiently imparting lyotropic liquid crystallinity to the polymer (P), the proportion of the specific tetracarboxylic dianhydride used is based on the total amount of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid (P). Thus, it is preferably at least 50 mol%, more preferably at least 75 mol%. The upper limit of the use ratio is not particularly limited, and can be arbitrarily set in a range of 100 mol% or less.

From the viewpoint of sufficiently imparting solubility and lyotropic liquid crystallinity to the polymer (P), the specific diamine is used in an amount of 25 mol% or more based on the total amount of the diamine used in the synthesis of the polyamic acid (P). It is more preferably at least 50 mol%, even more preferably at least 75 mol%. The upper limit of the use ratio is not particularly limited, and can be arbitrarily set in a range of 100 mol% or less.

(Other tetracarboxylic dianhydrides)
Other tetracarboxylic dianhydrides used in the synthesis of polyamic acid (P) include, for example, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride and the like. Can be mentioned. Specific examples thereof include aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, and 5- (2,5-dianhydride). (Oxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8 -Methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro -3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3 , 5,6-to Carboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-2 Anhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1] 0.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-en-2, 3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), 1, 3-propylene glycol bis (anhydride Rotrimelitate);
As the aromatic tetracarboxylic dianhydride, for example, 4,4′-biphthalic dianhydride;
In addition to these, tetracarboxylic dianhydride described in JP-A-2010-97188 can be used. The other tetracarboxylic dianhydrides can be used alone or in combination of two or more.

(Other diamines)
Examples of other diamines used for the synthesis of the polyamic acid (P) include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. Specific examples thereof include aliphatic diamines such as meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and 1,3-bis (aminomethyl) cyclohexane;
Examples of the alicyclic diamine include 1,4-diaminocyclohexane and 4,4′-methylenebis (cyclohexylamine);

Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 3,5-diaminobenzoic acid, 2,4-diaminobenzenesulfonic acid, 4,4′-diaminostilbene-2,2′-disulfonic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis (4-aminophenoxy) pentane, 7-bis (4-aminophenoxy) heptane, bis [2- (4-aminophenyl) ethyl] hexanedioic acid, N, N-bis (4-aminophenyl) methylamine, 1,5-diaminonaphthalene, 2, 2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphe Nyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2, 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4, 4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl and the like;
Examples of the diaminoorganosiloxane include, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; and diamines described in JP-A-2010-97188 can be used.

(Synthesis of polyamic acid)
The polyamic acid (P) can be obtained by reacting the above-mentioned tetracarboxylic dianhydride with a diamine, if necessary, together with a molecular weight modifier. The ratio of the tetracarboxylic dianhydride and the diamine used for the synthesis reaction of the polyamic acid (P) is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 to 1 equivalent of the amino group of the diamine. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
When the tetracarboxylic dianhydride or the diamine has an acidic functional group, the reaction may be carried out after neutralization by adding a base. As the base, a tertiary amine is preferred, and triethylamine is particularly preferred. The use ratio of the base is preferably a ratio of 0.5 to 5 equivalents to the acidic functional group, and more preferably a ratio of 1 to 2 equivalents. Similarly, when the tetracarboxylic dianhydride or the diamine has a basic functional group, the reaction may be performed after neutralization by adding an acid. As the acid, a carboxylic acid is preferred. The use ratio of the acid is preferably 0.5 to 5 equivalents to the basic functional group, more preferably 1 to 2 equivalents.
Examples of the molecular weight modifier include maleic anhydride, phthalic anhydride, acid monoanhydrides such as itaconic anhydride, aniline, cyclohexylamine, monoamine compounds such as n-butylamine, phenyl isocyanate, and monoisocyanate compounds such as naphthyl isocyanate. Can be mentioned. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the total of tetracarboxylic dianhydride and diamine used.

  The synthesis reaction of the polyamic acid (P) is preferably performed in an organic solvent. The reaction temperature at this time is preferably from -20C to 150C, more preferably from 0C to 100C. Further, the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

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

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

  As described above, a reaction solution containing the polyamic acid (P) is obtained. This reaction solution may be subjected to a dehydration ring closure reaction as it is, may be subjected to a dehydration ring closure reaction after isolating the polyamic acid contained in the reaction solution, or may be subjected to dehydration after purifying the isolated polyamic acid. It may be subjected to a ring closure reaction. Isolation and purification of the polyamic acid can be performed according to a known method.

[Polyamic acid ester]
The polyamic acid ester (hereinafter, also referred to as “polyamic acid ester (P)”) as a precursor of the polymer (P) is, for example, [I] a polyamic acid (P) obtained by the above polymerization reaction and an esterifying agent. [II], a method of reacting a tetracarboxylic diester with a diamine, and [III] a method of reacting a tetracarboxylic diester dihalide with a diamine.

  The polymer (P) can be obtained by dehydrating and cyclizing the polyimide precursor (polyamic acid (P) and polyamic acid ester (P)) synthesized as described above to obtain an imidization. The polymer (P) may be a completely imidized product obtained by dehydrating and ring-closing all of the amic acid structure or amic acid ester structure of the polyimide precursor as the precursor, and the amic acid structure and the amic acid ester It may be a partially imidized product in which only a part of the structure is dehydrated and ring-closed, and an amic acid structure or an amic acid ester structure and an imide ring structure coexist. The polymer (P) preferably has an imidization ratio of 50% or more, more preferably 75% or more, in order to obtain a coating film having a sufficiently high alignment control force in a liquid crystal device application. It is more preferably at least 85%, particularly preferably at least 90%. The imidation ratio is a percentage of the number of imide ring structures with respect to the total of the number of amic acid ester structures and the number of imide ring structures of the polyimide.

  The dehydration ring closure of the polyimide precursor is preferably performed by heating the polyamic acid, or dissolving the polyamic acid in an organic solvent, adding at least one of a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating as necessary. It is done by the method of doing.

  In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of a polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 mol per 1 mol of the amic acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, a base catalyst such as pyridine, triethylamine, 1-methylpiperidine and the like, and an acid catalyst such as methanesulfonic acid and benzoic acid can be used. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol per 1 mol of the dehydrating agent used. As the organic solvent used for the dehydration ring closure reaction, the organic solvents exemplified as those used for the synthesis of the polyamic acid (P) can be mentioned. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 200 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

  As described above, a reaction solution containing the polymer (P) is obtained. This reaction solution may be used for preparing the composition as it is, or may be used for preparing the composition after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and isolating the polymer (P). May be used to prepare a composition, or the isolated polymer (P) may be purified and then used to prepare a composition. These purification operations can be performed according to a known method.

The polymer (P) obtained as described above preferably has a solution viscosity of 10 to 2000 mPa · s when it is used as a solution having a concentration of 10% by mass, and preferably has a solution viscosity of 20 to 1000 mPa · s. More preferably, it has a solution viscosity. In addition, the solution viscosity (mPa · s) of the above polymer was determined by using an E-type rotational viscometer for a polymer solution having a concentration of 10% by mass prepared using a good solvent (eg, water) of the polymer. It is a value measured at ° C.
The weight average molecular weight ( _Mw ) in terms of polystyrene of the polymer (P) measured by gel permeation chromatography (GPC) is preferably from 1,000 to 500,000, more preferably from 2,000 to 300,000. 000. The molecular weight distribution (M _w / M _n ) represented by the ratio of Mw to the number average molecular weight (M _n ) in terms of polystyrene measured by GPC is preferably 15 or less, more preferably 10 or less. is there. Having the molecular weight in such a range is preferable because the composition can easily maintain the concentration range and the temperature range in which the composition exhibits lyotropic liquid crystallinity.

<Other ingredients>
The composition of the present disclosure may contain other components other than the polymer (P) as long as the objects and effects of the present disclosure are not impaired.

[Other polymers]
Examples of the other components include polymers other than the polymer (P) (hereinafter, also referred to as “other polymers”). Other polymers can be used to improve solution properties and electrical properties. Specific examples of such other polymers include, for example, a polyamic acid obtained by reacting the above other tetracarboxylic dianhydride with the above other diamine, an imidized polymer of the polyamic acid, an ester of the polyamic acid Polymer, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like.
When other polymers are blended in the composition, the blending ratio is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less, based on 100 parts by mass of the total of the polymers contained in the composition. More preferably, it is more preferably 10 parts by mass or less.

[Rod-like molecules, etc.]
Examples of the other components include rod-shaped molecules and rod-shaped nanostructures (hereinafter, also referred to as “rod-shaped molecules and the like”). By applying a shear stress to the composition, the orientation of the rod-like molecules and the like can be controlled together with the uniaxial orientation of the polymer (P). Examples of the rod-shaped molecule include a dichroic dye, and examples of the rod-shaped nanostructure include a dye aggregate, a quantum rod, a metal nanorod, a carbon nanotube, a protein, a nucleic acid, and a virus. Various functionalities can be provided by controlling the orientation of rod-like molecules and the like. For example, a composition containing a dichroic dye can form a guest-host type polarizing plate, and a composition containing a quantum rod can form a wavelength conversion plate capable of emitting polarized light, The composition containing the carbon nanotube can form a wire or an actuator having conductive anisotropy. When a rod-like molecule or the like is blended in the composition, the blending ratio can be appropriately set according to the type of the rod-like molecule or the like as long as the effects of the present disclosure are not impaired.

  Other components include, in addition to the above, for example, a compound having at least one epoxy group in a molecule, a functional silane compound, a surfactant, a filler, a pigment, an antifoaming agent, a sensitizer, a dispersant, and an antioxidant. Agents, adhesion aids, antistatic agents, leveling agents, antibacterial agents and the like. In addition, the mixing ratio of these can be appropriately set according to each compound to be mixed, as long as the effects of the present disclosure are not hindered.

[solvent]
The composition of the present disclosure is prepared as a liquid composition in which the polymer (P) and other components used as necessary are preferably dissolved in a solvent.

  Examples of the solvent used include water, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, ethylene glycol, acetone, methyl ethyl ketone, tetrahydrofuran, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-1-imidazolidinone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 3-methoxy-N, N- Dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, N, N, 2-trimethylpropanamide, 1-butoxy-2-propanol, diacetone alcohol, dipropylene glycol monomethyl ether, 4-hydroxy-4- Methyl-2-pe Tanthanone, butyl lactate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Examples include ethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene carbonate, and propylene carbonate. These can be used alone or in combination of two or more.

The solvent used preferably contains water. The proportion of water used is preferably at least 50% by mass, more preferably at least 75% by mass, particularly preferably at least 90% by mass, based on the total amount of the solvent in the composition.
When a mixed solvent of water and an organic solvent is used as the solvent, the organic solvent used is not particularly limited as long as it is an organic solvent that can be dissolved in water, but is preferably an organic solvent having a lower boiling point than water. And more preferably at least one selected from the group consisting of methanol, ethanol, n-propanol, i-propanol, acetone and tetrahydrofuran. When a mixed solvent of water and an organic solvent is used, the content ratio of the organic solvent is preferably 50% by mass or less, more preferably 25% by mass or less, based on the total amount of the mixed solvent. More preferably, the content is 10% by mass or less.

  The concentration of the polymer (P) in the composition of the present disclosure is not particularly limited as long as the composition exhibits lyotropic liquid crystallinity, and is preferably, but not limited to, the total amount of the solvent and the polymer (P). 1 to 30% by mass. The polymer (P) is preferable in that a composition exhibiting lyotropic liquid crystallinity can be obtained at a relatively low polymer concentration. Therefore, the coatability when forming a coating film on the substrate is good, a thin film of about 0.1 μm can be formed, and the industrial productivity is excellent. The concentration of the polymer (P) is more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass, based on the total amount of the solvent and the polymer (P).

  The solid content concentration (the ratio of the total mass of components other than the solvent of the composition to the total mass of the composition) in the composition of the present disclosure is appropriately selected in consideration of viscosity, volatility, and the like, but is preferably selected. It is in the range of 1 to 30% by mass, more preferably in the range of 2 to 20% by mass, and particularly preferably in the range of 3 to 15% by mass. That is, the composition of the present disclosure is applied to the surface of a substrate as described below, and is preferably dried to form a coating film in some cases. At this time, when the solid content concentration is less than 1% by mass, the composition becomes difficult to exhibit lyotropic liquid crystallinity. On the other hand, when the solids content exceeds 30% by mass, the thickness of the coating film becomes excessively large and it is difficult to obtain a good coating film, and the viscosity of the composition tends to increase and the coating property tends to decrease. is there. The temperature at the time of preparing the composition is preferably from 10 to 90C, more preferably from 20 to 65C.

[Lyotropic liquid crystal]
The composition of the present disclosure is a mixture of the polymer (P) and a solvent, and preferably exhibits lyotropic liquid crystallinity at least at a part of the temperature in the range of 0 ° C. or more and less than 100 ° C. The temperature range exhibiting lyotropic liquid crystallinity is preferably a temperature range including 20 to 40 ° C., more preferably a temperature range including 20 to 60 ° C., more preferably a temperature range of 0 ° C. or more and less than 100 ° C. The temperature range includes 10 to 80 ° C. By applying the composition in a lyotropic liquid crystal state on a substrate and causing it to flow by shearing stress, it is possible to obtain a coating film in which the molecular chains of the polymer (P) are uniaxially oriented in a shear direction in a self-organizing manner. In the process of coating and drying, it is desirable to control the composition so that it does not deviate from the temperature range and the concentration range where the composition exhibits lyotropic liquid crystallinity. In the process of application or drying, when the temperature or concentration reaches a value that does not exhibit lyotropic liquid crystallinity despite the fluidity of the composition, the orientation may be relaxed and the anisotropy of the coating film may disappear. . When the polymer (P) and the solvent are mixed and the polymer (P) is ionized, the polymer (P) is ionized with the ionic functional group in the partial structure represented by the above formula (1) ionized. , Together with a solvent.

  The polymer (P) is a rigid rod-shaped polymer and acts as a mesogen in a solvent. Furthermore, the polymer (P) has a structure in which a benzene ring and an imide ring are linked in the main chain, and is a rigid and highly uniaxial linear aromatic polyimide. It is possible to form a liquid crystal alignment film that is easily aligned in a plane and has excellent alignment regulating force. In addition, by introducing rod-like molecules (guests) into the lyotropic liquid crystal field (host) produced by the polymer (P), the rod-like molecules can be oriented along the molecular chain of the polymer (P). , A retardation plate, a polarizing plate, a wavelength conversion plate and the like can be formed.

<Liquid crystal alignment film and liquid crystal element>
The liquid crystal alignment film of the present disclosure is formed by using the composition prepared as described above as a liquid crystal alignment agent. Further, the liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the composition (liquid crystal alignment agent). When the liquid crystal element is a liquid crystal display element, its driving mode is not particularly limited, and can be applied to various driving modes such as TN type, STN type, IPS type, FFS type, VA type, MVA type, and PSA type. .

  The liquid crystal display element can be manufactured, for example, by a method including the following steps 1 to 3. Although the substrate to be used and the like differ depending on the desired drive mode, a case of manufacturing an FFS type liquid crystal display element will be described below.

[Step 1: Formation of coating film]
First, a composition is applied on a substrate, and then the coated surface is heated to form a coating film on the substrate. In the case of manufacturing an FFS type liquid crystal display element, the electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape and one surface of an opposite substrate provided with no electrode are provided. The composition is preferably applied by a bar coater method, a die coater method or a blade coater method, respectively. These methods are preferable because the molecular chains of the polymer (P) are easily oriented by the flow caused by the shear stress.
Here, as the substrate, for example, a transparent substrate made of glass such as float glass or soda glass; or a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, or poly (alicyclic olefin) can be used. Examples of the transparent conductive film provided on one surface of the substrate include a NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG, USA) and an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ). Can be used. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo etching after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern when forming the transparent conductive film, or the like is used. be able to. As the metal film, for example, a film made of a metal such as chromium can be used. When applying the composition, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, etc. May be preliminarily applied.

  After the application of the composition, preheating (prebaking) is preferably performed for the purpose of preventing dripping of the applied composition. The pre-bake temperature is preferably from 30 to 100 ° C, more preferably from 40 to 80 ° C, and particularly preferably from 40 to 60 ° C. The pre-bake time is preferably from 0.25 to 10 minutes, more preferably from 0.5 to 5 minutes. Thereafter, a baking (post-baking) step is performed for the purpose of completely removing the solvent and, if necessary, for thermally imidizing the amic acid structure present in the polymer. The firing temperature (post-bake temperature) at this time is preferably from 60 to 300 ° C, more preferably from 100 to 250 ° C. The post-bake time is preferably from 5 to 200 minutes, more preferably from 10 to 100 minutes. In the heating step, it is preferable that the coating film composed of the liquid crystal aligning agent applied on the substrate is in a state where the molecular chains of the polymer (P) are aligned by the flow due to the shear stress, and then dried in that state. Thereby, the liquid crystal alignment ability is given to the coating film by a simple operation, and a liquid crystal alignment film is formed. The thickness of the formed film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

  After applying the composition on the substrate, the solvent is removed to form a liquid crystal alignment film. At this time, if the polymer contained in the composition has an imide ring structure and an amic acid structure, the dehydration ring-closing reaction proceeds by further heating after the formation of the coating film, and the more imidized coating film It may be.

[Step 2: ion crosslinking treatment]
If necessary, the substrate on which the liquid crystal alignment film is formed may be immersed in a polyvalent cation aqueous solution to perform ionic crosslinking. By exchanging the counter cation of the polymer (P) with the polyvalent cation, the water resistance and mechanical properties of the liquid crystal alignment film are improved, and the electric properties of the liquid crystal cell are further improved. The polyvalent cation is not particularly limited as long as it is a divalent or higher-valent metal cation or an organic polycation, but is preferably an alkaline earth metal ion, and particularly preferably Ca ²⁺ , Sr ²⁺ , or Ba ²⁺ . The counter ion of the polyvalent cation is not particularly limited as long as it is water-soluble, but is preferably a hydroxide ion, a carbonate ion, or a halide ion. The immersion time is preferably 1 to 20 minutes, more preferably 2 to 10 minutes. Furthermore, after immersing the substrate in a polyvalent cation aqueous solution, it is desirable that the substrate taken out be rinsed with pure water and further immersed in pure water to remove excess ionic components.

[Step 3: Construction of Liquid Crystal Cell]
A liquid crystal cell is manufactured by preparing two substrates on each of which a liquid crystal alignment film is formed as described above, and disposing a liquid crystal between the two substrates that are opposed to each other. In order to manufacture a liquid crystal cell, for example, the following two methods can be used. The first method is a conventionally known method. First, two substrates are arranged to face each other with a gap (cell gap) therebetween so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded to each other using a sealant. After the liquid crystal is injected and filled in the cell gap defined by the above, the liquid crystal cell is manufactured by sealing the injection hole. The second method is a method called ODF (One Drop Fill) method. For example, an ultraviolet curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped at predetermined locations on the liquid crystal alignment film surface. After that, the other substrate is bonded so that the liquid crystal alignment film is opposed and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby producing a liquid crystal cell. . In either case, the liquid crystal cell manufactured as described above is further heated to a temperature at which the used liquid crystal takes an isotropic phase, and then gradually cooled to room temperature, whereby the liquid crystal orientation during liquid crystal filling is improved. It is desirable to remove it.

As the sealant, for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used.
Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal, and among them, a nematic liquid crystal is preferable, for example, a Schiff base liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, and biphenyl. A cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal, or the like can be used. In addition, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck & Co.) A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.

  Then, a liquid crystal display device can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell. As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film called "H film" in which polyvinyl alcohol is stretched and oriented while absorbing iodine is sandwiched by a cellulose acetate protective film or the H film itself. Can be mentioned.

<Phase plate>
The retardation plate of the present disclosure is formed by the composition prepared as described above. Specifically, first, the composition is coated on a substrate (eg, a glass substrate, triacetyl cellulose (TAC), polyethylene terephthalate, polymethyl methacrylate, etc.) by a bar coater method, a die coater method, or a blade coater method. Then, the polymer (P) is dried in a state where the molecular chains of the polymer (P) are oriented by flow caused by shear stress. Thereby, a phase difference plate is formed.

<Polarizing plate>
The polarizing plate of the present disclosure is formed by a composition containing a dichroic dye or a metal prepared as described above. For example, to prepare a guest-host type polarizing plate, first, a composition containing a polymer (P), a dichroic dye, and a solvent is added to a substrate (for example, a glass substrate, triacetyl cellulose (TAC), (Polyethylene terephthalate, polymethyl methacrylate, etc.), preferably by a bar coater method, a die coater method or a blade coater method. Next, a polarizing plate can be obtained by drying in a state where the molecular chains of the polymer (P) are oriented by flow due to shear stress. If necessary, a resin film (protective film) may be attached to one or both surfaces of the polarizing plate.
In addition, in order to manufacture a reflective polarizing plate, a composition containing a polymer (P), a metal (metal nanorods, metal nanowires, or metal ions) and a solvent is used. A polarizing plate can be obtained by applying the composition on a substrate in the same manner as in the manufacturing method, and then drying the polymer (P) in a state where the molecular chains of the polymer (P) are oriented by flow caused by shear stress. However, when a metal ion is used as the metal, a simple metal is anisotropically precipitated along the polymer (P) by reduction.

  The liquid crystal element of the present disclosure can be effectively applied to various uses, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, a smartphone, and various monitors. It can be applied to various liquid crystal display devices such as a liquid crystal television and an information display, a light control film, a retardation plate and a polarizing plate.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present disclosure is not limited to these Examples.
The structures and abbreviations of the main compounds used in the following examples are as follows.
(Specific tetracarboxylic dianhydride)
TA-1; pyromellitic dianhydride (other tetracarboxylic dianhydrides)
TB-1, 1,4,5,8-naphthalenetetracarboxylic dianhydride TB-2; 4,4'-biphthalic dianhydride TB-3; 1,2,3,4-cyclobutanetetracarboxylic dianhydride Anhydrous

(Specific diamine)
DA-1, 4,4'-diamino-2,2'-biphenyldisulfonic acid DA-2; 2,5-diaminobenzenesulfonic acid DA-3; 2,5-diaminobenzoic acid (other diamines)
DB-1, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl DB-2; 4,4'-diaminostilbene-2,2'-disulfonic acid DB-3; 2,4- Diaminobenzenesulfonic acid

The imidation ratio [%] of the polyimide was measured by the following method.
The solution of the polyimide was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethylsulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, it was determined by the formula shown by the following formula (a).
Imidation ratio [%] = (((1−A ¹ ) / A ² ) × α) × 100 (a)
(In the formula (a), A ¹ is the peak area derived from the proton of the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from the other protons, and α is the NH group in the precursor of the polymer. Is the number ratio of other protons to one proton.)

[Example 1]
(1) Synthesis of Polymer In a three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen inlet tube, diamine (DA-1) (3.79 g, 11.0 mmol), m-cresol (50 mL), and triethylamine (2.43 g, 24.0 mmol) and stirred under nitrogen. After dissolution of the diamine, acid dianhydride (TA-1) (2.18 g, 10.0 mmol) and benzoic acid (1.71 g, 14.0 mmol) were added, and the mixture was stirred at 80 ° C for 3 hours, and then at 180 ° C. Stir for 12 hours. After completion of the reaction, the reaction solution was diluted with m-cresol and dropped into acetone for coagulation. The obtained coagulated product was filtered, washed in acetone, and vacuum-dried at 120 ° C. to obtain a brown powder of a polymer having a partial structure represented by the following formula (PI-1) (6.64 g, yield: 88%). FIG. 1 shows the measurement results of the ¹ H-NMR spectrum (DMSO-d ⁶ , 400 MHz) of the polymer (PI-1). The imidation ratio of the polymer (PI-1) was 99% or more.

(2) Preparation of Composition and Evaluation of Solubility The polymer (PI-1) obtained in the above (1) was dissolved by adding water and heating and stirring at 60 ° C. Was obtained. The composition (C-1) was prepared by filtering this solution through a filter having a pore size of 0.2 μm.
The solubility was evaluated as “good” when an aqueous solution having a polymer solid content of 1% by mass or more was evaluated as “good”, and was evaluated as “unsuccessful in preparing an aqueous solution having a solid content of 1% by mass or more”. Bad. " As a result, in this example, the evaluation was “good”.

(3) Evaluation of lyotropic liquid crystallinity The composition (C-1) obtained in the above (2) was dropped on a glass substrate and observed with a polarizing microscope. The evaluation is “good” when at least a part of the temperature in the range of 0 ° C. or more and less than 100 ° C., and optical anisotropy is observed under orthogonal Nicols, and at any temperature of 0 ° C. or more and less than 100 ° C. The case where no optical anisotropy was observed was regarded as “poor”. As a result, in this example, the optical anisotropy was observed in the polymer solid content concentration range of 6 to 20% by mass and in the temperature range of 10 ° C. to 90 ° C., which was evaluated as “good”. Was.
3 to 5 show polarizing microscope photographs (100 times) of the composition (C-1) in which the solid content of the polymer is 10% by mass. FIG. 3 is a photograph immediately after the composition was dropped on the glass substrate, FIG. 4 is a photograph after the composition was dropped weakly after being dropped and concentrated on the glass substrate, and FIG. 3 is a photograph after sandwiching a glass substrate from above after dropping and applying a shear stress by shifting the upper glass substrate sideways.

[Examples 2 and 3, Comparative Examples 1 to 6]
Polymers (PI-2 to PI-9) were synthesized in the same manner as in Example 1 except that the types of the acid dianhydride and the diamine were changed as described in Table 1 below. did. In addition, compositions (C-2 to C-9) were each prepared using the obtained polymers (PI-2 to PI-9), and solubility and liquid crystallinity were evaluated. The evaluation results are shown in Table 1 below. In Table 1, the numerical value (molar ratio) in the column of diamine represents the use ratio (molar part) of each compound with respect to 100 mole parts of the total amount of diamine used in the synthesis of the polymer. In Comparative Examples 1 and 4, the solubility was “poor”, and the lyotropic liquid crystallinity could not be evaluated.
FIG. 2 shows the measurement results of the ¹ H-NMR spectrum (DMSO-d ⁶ , 400 MHz) of the polymer (PI-2). The imidation ratio of the polymer (PI-2) was 99% or more. In Example 2, optical anisotropy was observed in a temperature range of 20 to 70 ° C. when the solid content concentration of the polymer was 2% by mass, and in a temperature range of 40 to 80 ° C. when the solid content concentration was 3 to 6% by mass. The evaluation was “good”.

[Example 4: Preparation and evaluation of liquid crystal alignment film]
(1) Preparation of Composition A 10% by mass solution of the composition (C-1) containing the polymer (PI-1) obtained in Example 1 was diluted with water to have a solid content of 6% by mass. Solution was obtained. This solution was filtered through a filter having a pore size of 0.2 μm to prepare a composition (C-10).
(2) Formation of Liquid Crystal Alignment Film On the respective surfaces of a glass substrate in which a flat plate electrode, an insulating layer, and a comb-like electrode are laminated in this order on one surface, and a counter glass substrate on which no electrode is provided, The composition (C-10) prepared in 1) was applied using a wire bar so that the film thickness became 0.1 μm, and dried in a 60 ° C. warm air for 5 minutes and in a 120 ° C. oven for 30 minutes. Then, a liquid crystal alignment film was formed.
(3) Manufacture of a liquid crystal display element A pair of substrates having a liquid crystal alignment film manufactured in the above (2) was filled with aluminum oxide spheres having a diameter of 5.5 μm while leaving a liquid crystal injection port at an edge of a surface on which the liquid crystal alignment film was formed. After epoxy resin adhesive is applied by screen printing, the substrates are overlapped and pressed together so that the direction of projection of the polarization axis on the substrate surface during light irradiation is antiparallel, and the adhesive is heated at 150 ° C. for 1 hour. Cured. Next, a nematic liquid crystal (MLC-7028, manufactured by Merck) was filled between the pair of substrates from the liquid crystal injection port, and the liquid crystal injection port was sealed with an epoxy-based adhesive. Further, in order to remove the flow alignment at the time of injecting the liquid crystal, it was heated at 120 ° C. and then gradually cooled to room temperature. Next, a polarizing plate was attached to both outer surfaces of the substrate to produce an FFS type liquid crystal display device.
(4) Evaluation of Liquid Crystal Alignment For the liquid crystal display device manufactured in the above (3), the presence or absence of an abnormal domain in a change in light and dark when a voltage of 5 V is turned ON / OFF (applied / cancelled) is measured by a microscope at a magnification of 50 times. Observed. The evaluation was “good” when no abnormal domain was observed, and “poor” when an abnormal domain was observed. As a result, in this example, the evaluation was “good”.

[Example 5]
In "(1) Preparation of composition" in Example 4, the point that the composition (C-2) was used in place of the composition (C-1) and the solid concentration after dilution with water was 6 A composition (C-11) was prepared by performing the same operation as in Example 4 except that the amount was changed from 3% by mass to 3% by mass. In addition, a liquid crystal alignment film was formed using the prepared composition (C-11), and a liquid crystal display device was manufactured to evaluate liquid crystal alignment. The evaluation results are shown in Table 2 below.

[Comparative Examples 7 to 8]
In Example 4, a composition was prepared and a liquid crystal alignment film was formed in the same manner as in Example 4, except that the polymer contained in the composition was changed as shown in Table 2 below. The device was manufactured and the liquid crystal alignment property was evaluated. The evaluation results are shown in Table 2 below.

[Example 6: Production and evaluation of retardation plate]
The composition (C-1) containing the polymer (PI-1) obtained in Example 1 was applied on a glass substrate using a bar coater so that the film thickness became 1 μm, and the temperature was reduced to 60 ° C. 5 minutes, and dried in an oven at 120 ° C. for 30 minutes to form a retardation plate.
The phase difference was evaluated by measuring the in-plane retardation (retardation) by the parallel Nicol rotation method. At a wavelength of 550 nm, when the in-plane retardation was 20 nm or more, it was regarded as “good”, and the in-plane retardation was less than 20 nm. Was judged as "poor". As a result, in this example, the result was “good”.
[Comparative Example 9]
A composition was prepared in the same manner as in Example 6 except that the polymer contained in the composition was changed as shown in Table 2 below to form a retardation plate. Was evaluated. The evaluation results are shown in Table 2 below.

[Example 7: Production and evaluation of polarizing plate]
(1) Preparation of Composition Using the composition (C-1) containing the polymer (PI-1) obtained in Example 1, two colors were used for 100 parts by mass of the polymer (PI-1). Sex dye C.I. I. One part by weight of Direct Orange 39 (manufactured by Santa Cruz Biotechnology) was added and diluted with water to obtain a solution having a solid concentration of 10% by mass. This solution was filtered through a filter having a pore size of 0.2 μm to prepare a composition (C-14).
(2) Formation of polarizing plate The composition (C-14) prepared in the above (1) was coated on a glass substrate using a bar coater so that the film thickness became 10 μm, and the temperature was raised to 60 ° C. Drying was performed in an air at 120 ° C. for 30 minutes in the air for 5 minutes to form a guest-host type polarizing plate.
(3) Evaluation of dichroic ratio The evaluation was carried out by measuring the polarization absorption spectrum. The case where the dichroic ratio was 2 or more was evaluated as “good”, and the case where the dichroic ratio was less than 2 was evaluated as “bad”. " As a result, in this example, the result was “good”. Incidentally, the dichroic ratio at the wavelength 500 nm, absorbance when the polarization axis is parallel to the shear direction (A _II), absorbance when the polarization axis and a perpendicular shear direction (A _⊥) and the ratio (A _II / _A⊥ ).
[Comparative Example 10]
A composition was prepared in the same manner as in Example 7 except that the polymer contained in the composition was changed as shown in Table 2 below to form a polarizing plate and dichroism. The ratio was evaluated. The evaluation results are shown in Table 2 below. In Table 2, "-" indicates that the corresponding evaluation was not performed.

  From the above results, the compositions of Examples using the polymer (P) exhibit optical anisotropy under orthogonal Nicols and show lyotropic liquid crystallinity in a temperature range of 0 ° C. or more and less than 100 ° C. Became clear. Further, the polymer (P) showed lyotropic liquid crystallinity in water and at a low polymer concentration of 20% by mass or less. In addition, the liquid crystal display device, the retardation plate, and the polarizing plate manufactured using the compositions of the examples exhibited good optical characteristics. On the other hand, the composition of the comparative example could not observe optical anisotropy at any temperature. From these results, it has been clarified that a composition exhibiting lyotropic liquid crystallinity can be obtained under mild conditions by using the polymer (P).

Claims (13)

A composition exhibiting lyotropic liquid crystallinity, obtained by mixing a polymer (P) having a partial structure represented by the following formula (1) and a solvent.
(In the formula (1), at least one of R ^{1 to} R ¹⁰ is a monovalent group having an ionic functional group, and the rest are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. Where k is 0 or 1.)   The composition according to claim 1, which exhibits lyotropic liquid crystallinity in at least a part of a temperature range from 0C to less than 100C.   The composition according to claim 1, wherein the composition contains water in an amount of 50% by mass or more based on the total amount of the solvent.   The ionic functional group, a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, an ammonium group, a pyridinium group, an imidazolium group or a guanidinium group, or a salt thereof, according to any one of claims 1 to 3. A composition as described.   The composition according to any one of claims 1 to 4, wherein the ionic functional group is an acidic functional group. The polymer (P) according to any one of claims 1 to 5, wherein the polymer (P) is a polymer having a partial structure represented by the following formula (2) as a partial structure represented by the formula (1). A composition as described.
(In the formula (2), M is a cation. K is 0 or 1. However, when k = 1, a plurality of Ms in the formula may be the same or different.)   The composition according to any one of claims 1 to 6, further comprising a dichroic dye, a dye aggregate, a quantum rod, a metal nanorod, or a carbon nanotube. A liquid crystal aligning agent obtained by mixing a polymer (P) having a partial structure represented by the following formula (1) and a solvent.
(In the formula (1), at least one of R ^{1 to} R ¹⁰ is a monovalent group having an ionic functional group, and the rest are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. Where k is 0 or 1.)   A liquid crystal alignment film formed using the composition according to claim 1.   A retardation plate formed using the composition according to claim 1.   A polarizing plate formed using the composition according to claim 1.   A liquid crystal alignment, wherein the composition according to any one of claims 1 to 7 is applied to a substrate in a lyotropic liquid crystal state, and dried in a state where molecular chains of the polymer (P) are aligned by flow due to shear stress. Manufacturing method of membrane.   A liquid crystal device comprising the liquid crystal alignment film according to claim 9.