CN110662789B

CN110662789B - Composition, polymer, liquid crystal aligning agent, liquid crystal alignment film and manufacturing method thereof, phase difference plate, polarizing plate and liquid crystal element

Info

Publication number: CN110662789B
Application number: CN201880033340.0A
Authority: CN
Inventors: 村上拓也
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2017-06-12
Filing date: 2018-05-11
Publication date: 2022-05-24
Anticipated expiration: 2038-05-11
Also published as: CN110662789A; KR20190133750A; TW201903130A; JP7067555B2; KR102237291B1; TWI761521B; WO2018230222A1; JPWO2018230222A1

Abstract

The invention provides a composition, a polymer, a liquid crystal aligning agent, a liquid crystal aligning film and a manufacturing method thereof, a phase difference plate, a polarizing plate and a liquid crystal element. The present invention uses a composition that exhibits lyotropic liquid crystallinity obtained by mixing a polymer (P) having a partial structure represented by formula (1) with a solvent. Wherein, in the formula (1), R¹～R¹⁰At least one of them is a monovalent group having an ionic functional group, and the others are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. k is 0 or 1.

Description

Composition, polymer, liquid crystal aligning agent, liquid crystal alignment film and manufacturing method thereof, phase difference plate, polarizing plate and liquid crystal element

Technical Field

The present disclosure relates to a composition, a liquid crystal aligning agent, a liquid crystal alignment film and a method for producing the same, a retardation plate, a polarizing plate, and a liquid crystal element.

Background

Liquid crystals include thermotropic liquid crystals (molten type) which exhibit liquid crystallinity in a certain temperature range and lyotropic liquid crystals (solution type) which exhibit liquid crystallinity in a certain concentration range. When the concentration is less than the critical concentration, the molecular chain arrangement of the lyotropic liquid crystalline polymer is irregular and an isotropic phase, but when the concentration is not less than the critical concentration, the lyotropic liquid crystalline polymer exhibits a liquid crystal state. In the liquid crystal state, the liquid crystal layer becomes an aggregate of minute domains in which molecular chains are aligned in one direction, and exhibits optical anisotropy. Further, when the liquid-crystalline solution is shear-deformed, molecular chains are oriented in the flow direction. For example, it is known that aromatic polyamides represented by Kevlar (Kevlar) are dissolved in strong acids such as concentrated sulfuric acid, and that thick solutions thereof exhibit lyotropic liquid crystallinity. By spinning from the solution in the lyotropic liquid crystal state, a high-performance fiber having molecular chains oriented in the fiber direction and having a high elastic modulus can be produced.

In order to realize a lyotropic liquid crystalline polymer, a rigid rod polymer is required, but generally, the rigid rod polymer has difficulty in solubility in water or an organic solvent, and therefore, it is necessary to use a corrosive solvent such as sulfuric acid or to dissolve the rigid rod polymer in a polar solvent having a high boiling point at a high temperature.

In polymers having a curved structure such as polyamide or xylylene, introduction of an ionic functional group to ensure solubility and exhibit lyotropic liquid crystallinity under mild conditions has been reported, and applications to retardation plates, polarizing plates, and the like have been studied (non-patent document 1, patent document 1 to patent document 3). Further, materials showing lyotropic liquid crystallinity have been reported for polyimide (non-patent documents 2 to 4), and application studies of precursors to polyimide precursors have been conducted by naoeber (Neuber) et al (non-patent documents 5 to 6).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2009/130675

Patent document 2: international publication No. 2010/020928

Patent document 3: international publication No. 2010/064194

Non-patent document

Non-patent document 1: < < Langmuir > >, 2004, volume 20, p.6518-6520.

Non-patent document 2: < Macromolecular Rapid Communications >, 1993, volume 14, p.395-400.

Non-patent document 3: < < Macromolecules > >, 1991, volume 24, p.1883-1889.

Non-patent document 4: < journal of Polymer science: part A: polymer chemistry (j.polym.sci.a polym.chem.), 1996, volume 34, p.587-595.

Non-patent document 5: < < polymer chemico-physical (macromol. chem. Phys.), 2002, volume 203, p.598-604.

Non-patent document 6: < < advanced functional materials (adv. Funct. Mater.), 2003, Vol.13, p.387-391.

Disclosure of Invention

Problems to be solved by the invention

For alignment control of liquid crystal, a polyimide-based material is preferably used as the liquid crystal alignment film in order to exhibit excellent alignment regulating force for liquid crystal. If a material exhibiting lyotropic liquid crystal properties can be obtained using a polyimide-based material having excellent alignment restriction force or the like, alignment may be achieved by shear flow through a simple coating process, and a high-performance liquid crystal alignment film, a retardation plate, a polarizing plate, or the like can be expected to be formed at low cost.

However, as shown in non-patent documents 2 to 4, materials showing lyotropic liquid crystallinity have been reported for polyimide, but a corrosive solvent such as concentrated sulfuric acid or cresol is required for dissolving polyimide (non-patent documents 2 to 4), a high temperature is required for the development of lyotropic liquid crystallinity (non-patent documents 3 and 4), and a material showing lyotropic liquid crystallinity under mild conditions is not known. Further, the polyimide precursors disclosed in non-patent documents 5 to 6 have the following disadvantages: the polyamic acid ester requires a high temperature (about 100 ℃) and a high concentration (about 50 mass%) for thermal imidization of the coating film and for the development of lyotropic liquid crystallinity. In order to obtain a thin film by coating on a substrate, it is desirable that the solvent is a low environmental load solvent such as water or an organic solvent and exhibits lyotropic liquid crystal properties at a sufficiently low concentration at a temperature of less than 100 ℃ (preferably a low temperature around room temperature) from the viewpoint of industrial productivity, environmental aspects, and the like. That is, a composition exhibiting lyotropic liquid crystallinity under mild conditions at temperature, solvent and concentration by using a polyimide having excellent alignment restriction and the like is required.

The present disclosure has been made in view of the above problems, and an object thereof is to provide a polyimide-based composition which exhibits lyotropic liquid crystal properties under mild conditions.

Means for solving the problems

The following methods are provided in accordance with the present disclosure.

< 1 > a composition which is obtained by mixing a polymer (P) having a partial structure represented by the following formula (1) with a solvent and exhibits lyotropic liquid crystallinity.

[ solution 1]

(in the formula (1), R¹～R¹⁰At least one of them is a monovalent group having an ionic functional group, and the others are each independently a hydrogen atom, a halogen atom, or a monovalent organic group; k is 0 or 1. )

< 2 > a liquid crystal alignment film formed using the composition.

< 3 > a phase difference 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 formula (1) with a solvent.

< 6 > A method for producing a liquid crystal alignment film, comprising applying the composition to a substrate in a lyotropic liquid crystal state, and drying the composition in a state in which molecular chains of the polymer (P) are aligned by a flow of shear stress.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present disclosure, a composition exhibiting lyotropic liquid crystal properties under mild conditions can be obtained using a polyimide having excellent 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.

Drawings

FIG. 1 shows the polymer (PI-1)¹H-Nuclear Magnetic Resonance (NMR) spectrum.

FIG. 2 shows the polymer (PI-2)¹H-NMR spectrum.

FIG. 3 is a photomicrograph taken with a polarizing microscope, after dropping the composition (C-1) on a substrate.

FIG. 4 is a photomicrograph of a polarizing microscope showing that the composition (C-1) was concentrated on a substrate.

FIG. 5 is a polarizing micrograph of the composition (C-1) after a shear force was applied thereto.

Detailed Description

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

< Polymer (P) >

The polymer (P) is a polyimide, and can be obtained, for example, by imidizing a polyimide precursor obtained by polymerization of a diamine and at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic acid dianhydrides, tetracarboxylic acid diesters, and tetracarboxylic acid diester dihalides in the raw material composition.

With respect to R in the formula (1)¹～R¹⁰The monovalent organic group is preferably a hydrocarbon group, and more preferably an alkyl group having 1 to 5 carbon atoms. Having an ionic functionThe monovalent radical of the energy radical can be utilized as ` -L `¹-X¹"(wherein, L¹Is a single bond or a divalent linking group, X¹Is an ionic functional group. "" indicates a bond to a benzene ring). Here, at L¹In the case of a divalent linking group, L is¹Specific examples of the (C) include alkanediyl having 1 to 5 carbon atoms, a group containing-O-between carbon-carbon bonds of the alkanediyl, and-O-R¹³- (wherein, R)¹³Is a divalent hydrocarbon group, ". X" indicates bonding to X¹The bond of (b) and the like.

The ionic functional group is a functional group that forms a cation or 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 pyridyl group, an imidazolyl group, a guanidino group, or a salt thereof, in terms of further improving the solubility of the polymer (P) in a solvent containing water. 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, a sulfonic acid group, a phosphonic acid group, or a carboxylic acid group, or a salt thereof is preferable, and a sulfonic acid group or a salt thereof is particularly preferable. From the mixture of the polymer (P) and the solvent, it is presumed that the solubility in the solvent can be imparted to the polymer (P) by the ionic functional group of the polymer (P), and in particular, the self-organization by the driving force of phase separation in a highly polar solvent is promoted, and the anisotropy is increased.

When the ionic functional group is an acidic functional group or a salt of a basic functional group, examples of the counter ion of the acidic functional group (e.g., a sulfonic acid group, a phosphonic acid group, or a carboxylic acid group) include: li⁺、Na⁺、K⁺、Cs⁺、Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺、Zn² ⁺、Pb²⁺、Al³⁺、La³⁺、Ce³⁺、Y³⁺、Yb³⁺、Gd³⁺、NH_4-tQ_t ⁺(wherein Q represents a hydrocarbon group having 1 to 20 carbon atoms, and t represents an integer of 0 to 4. in the case where t is 2 to 4, a plurality of Q's may be the same or different, and the same applies hereinafter), and the like.Examples of the counter ion of the basic functional group (ammonium group, pyridyl group, imidazolyl group, guanidino group, etc.) include: cl^-、Br^-、I^-、R¹⁴COO^-(wherein, R¹⁴A hydrocarbon group having 1 to 20 carbon atoms) and the like. When the ionic functional group is a carboxylic acid group, the acid dissociation constant of the carboxylic acid is low, and the proton is hard to dissociate under acidic conditions and the ionic property is low, and therefore, it is desirable that the ionic functional group forms a salt with a strong base.

Among monovalent groups having ionic functional groups, L¹The ionic functional group may be appropriately selected depending on the kind of the ionic functional group. For example, when the ionic functional group is a sulfonic acid group, a phosphonic acid group, or a carboxylic acid group, or a salt thereof, L¹Preferably a single bond. When the ionic functional group is an ammonium group, a pyridyl group, an imidazolyl group, a guanidino group, or a salt thereof, L is¹Preferably a divalent linking group, more preferably an alkanediyl group having 1 to 3 carbon atoms.

With respect to R¹～R¹⁰The number of ionic functional groups in the formula (1) is not particularly limited as long as at least a part of these groups has an ionic functional group. The number of ionic functional groups (i.e., R) in the formula (1)¹～R¹⁰The number of monovalent groups having an ionic functional group) is preferably 1 to 4, more preferably 1 or 2. The ionic functional group preferably has a partial structure derived from a diamine (i.e., R) from the viewpoint of exhibiting good lyotropic liquid crystallinity and having a high degree of freedom in material selectivity³～R¹⁰At least a portion of).

The polymer (P) is more preferably a polymer having at least one partial structure represented by the above formula (1) selected from the group consisting of 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), and particularly preferably a polymer having a partial structure represented by the following formula (2).

[ solution 2]

(in formulae (2) to (4), M is a cation, k is 0 or 1, and when k is 1, M's in formulae may be the same or different from each other.)

Examples of the cation of M include: h⁺、Li⁺、Na⁺、K⁺、Cs⁺、Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺、Zn²⁺、Pb²⁺、Al³⁺、La³⁺、Ce³⁺、Y³⁺、Yb³⁺、Gd³⁺、NH_4-tQ_t ⁺And the like. The cation of M is preferably a monovalent cation in that the solubility of the polymer (P) in an aqueous solvent can be further improved, and among these, NH is preferred_4-tQ_t ⁺More preferably, tertiary ammonium ions.

In the present specification, the term "tetracarboxylic diester" refers to a compound in which two of the four carboxyl groups of a tetracarboxylic acid are esterified and the remaining two are carboxyl groups. The "tetracarboxylic acid diester dihalide" refers to a compound in which two of the four carboxyl groups of a tetracarboxylic acid are esterified and the remaining two are halogenated. Examples of the "polyimide precursor" include polyamic acids and polyamic acid esters. By "organic group" is meant a group containing carbon atoms, and may also contain heteroatoms within the structure.

The term "hydrocarbon group" as used herein 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 having no cyclic structure in the main chain and consisting of only a chain structure. The polymer may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. The alicyclic hydrocarbon may not be composed of only the alicyclic hydrocarbon structure, but may have a chain structure in a part thereof. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. In addition, the structure may not necessarily be composed of only an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in a part thereof.

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") and the like. Further, the specific tetracarboxylic dianhydride may be used singly or in combination of two or more. R in the formula (t-1)¹And R²In the above formula, the monovalent organic group includes a hydrocarbon group having 1 to 20 carbon atoms, a group in which a hydrogen atom of the hydrocarbon group is substituted with an ionic functional group, and the like. In these, R¹And R²Preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom.

[ solution 3]

(in the formula (t-1), R¹And R²Is 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) is preferably a diamine containing an ionic functional group (hereinafter, also referred to as "specific diamine"). A specific diamine is R in the formula (1)³～R¹⁰One or more of them are monovalent groups having an ionic functional group, and R is more preferably³～R¹⁰One or both of which are monovalent radicals having an ionic functional group.

Preferable specific examples of the specific diamine include compounds represented by the following formulae (d-1) to (d-16). Further, the specific diamine may be used singly or in combination of two or more.

[ solution 4]

Examples of preferred tetracarboxylic acid diesters used for synthesizing the polymer (P) include compounds obtained by ring-opening a tetracarboxylic acid dianhydride represented by the above formula (t-1) with an alcohol such as methanol or ethanol. As a preferred specific example of the tetracarboxylic acid diester dihalide used for synthesizing the polymer (P), a compound obtained by reacting the above-mentioned tetracarboxylic acid diester with a chlorinating agent such as thionyl chloride can be mentioned. The tetracarboxylic acid diester and the tetracarboxylic acid diester dihalide may be used singly or in combination.

[ Polyamic acid ]

The polyamic acid (hereinafter, also referred to as "polyamic acid (P)") which is a precursor of the polymer (P) can be obtained, for example, by reacting tetracarboxylic dianhydride with diamine. Specifically, the following are listed: [i] a method of directly reacting a tetracarboxylic dianhydride comprising a specific tetracarboxylic dianhydride with a diamine comprising a specific diamine; [ ii ] a method in which a tetracarboxylic dianhydride comprising a specific tetracarboxylic dianhydride is neutralized with a base, and then the tetracarboxylic dianhydride is reacted with a diamine comprising a specific diamine, and the like.

In the above method [ i ], tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydrides (hereinafter also referred to as "other tetracarboxylic dianhydrides") and diamines other than the specific diamines (hereinafter also referred to as "other diamines") may be used in combination. The ratio of the specific tetracarboxylic dianhydride is preferably 50 mol% or more, and more preferably 75 mol% or more, based on the total amount of the tetracarboxylic dianhydride used for synthesizing the polyamic acid (P), from the viewpoint of sufficiently imparting lyotropic liquid crystallinity to the polymer (P). The upper limit of the above-mentioned use ratio is not particularly limited, and may be arbitrarily set within a range of 100 mol% or less.

The ratio of the specific diamine to be used is preferably 25 mol% or more, more preferably 50 mol% or more, and even more preferably 75 mol% or more, based on the total amount of the diamine used for synthesizing the polyamic acid (P), from the viewpoint of sufficiently imparting solubility and lyotropic liquid crystal properties to the polymer (P). The upper limit of the above-mentioned use ratio is not particularly limited, and may be arbitrarily set within a range of 100 mol% or less.

(other tetracarboxylic dianhydrides)

Examples of other tetracarboxylic dianhydrides to be used for the synthesis of polyamic acid (P) include: aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride, and the like. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as: butane tetracarboxylic dianhydride, etc.;

examples of the alicyclic tetracarboxylic dianhydride include: 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3, 5-tricarboxylylcyclopentylglycolic dianhydride, 5- (2, 5-dioxotetrahydrofuran-3-yl) -3a,4,5,9 b-tetrahydronaphtho [1,2-c ]]Furan-1, 3-dione, 5- (2, 5-dioxotetrahydrofuran-3-yl) -8-methyl-3 a,4,5,9 b-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-tricarboxyl-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0 ]]Octane-2, 4,6, 8-tetracarboxylic acid-2: 4,6: 8-dianhydride, bicyclo [2.2.1]Heptane-2, 3,5, 6-tetracarboxylic acid 2:3,5: 6-dianhydride, 4, 9-dioxatricyclo [5.3.1.0^2,6]Undecane-3, 5,8, 10-tetraone, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2]Oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, ethylene glycol bis (trimellitic anhydride), 1, 3-propanediol bis (trimellitic anhydride), and the like;

examples of the aromatic tetracarboxylic dianhydride include: 4,4' -diphthalic dianhydride, etc.;

in addition, tetracarboxylic dianhydrides described in Japanese patent application laid-open No. 2010-97188 can be used. Further, other tetracarboxylic dianhydrides may be used singly or in combination of two or more of these.

(other diamines)

Examples of the other diamines used for the synthesis of polyamic acid (P) include: aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples of these include aliphatic diamines: m-xylylenediamine, 1, 3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1, 3-bis (aminomethyl) cyclohexane, and the like;

examples of the alicyclic diamine include: 1, 4-diaminocyclohexane, 4' -methylenebis (cyclohexylamine), and the like;

examples of the aromatic diamine include: p-phenylenediamine, m-phenylenediamine, 3, 5-diaminobenzoic acid, 2, 4-diaminobenzenesulfonic acid, 4 '-diaminostilbene-2, 2' -disulfonic acid, 4 '-diaminodiphenylmethane, 4' -diaminodiphenylsulfide, 4-aminophenyl-4 '-aminobenzoate, 4' -diaminoazobenzene, 1, 5-bis (4-aminophenoxy) pentane, 1, 7-bis (4-aminophenoxy) heptane, bis [2- (4-aminophenyl) ethyl ] adipic acid, N-bis (4-aminophenyl) methylamine, 1, 5-diaminonaphthalene, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2, 7-diaminofluorene, 4 '-diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 9-bis (4-aminophenyl) fluorene, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, 4' - (p-phenylenediisopropylidene) dianiline, 4'- (m-phenylenediisopropylidene) dianiline, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, etc.;

examples of the diaminoorganosiloxanes include: 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane and the like; in addition, diamines described in Japanese patent application laid-open No. 2010-97188 can be used.

(Synthesis of Polyamic acid)

The polyamic acid (P) can be obtained by reacting the tetracarboxylic dianhydride and the diamine as described above, optionally together with a molecular weight modifier. The ratio of the tetracarboxylic dianhydride to the diamine used in the synthesis reaction of the polyamic acid (P) is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents, of the acid anhydride group of the tetracarboxylic dianhydride to 1 equivalent of the amino group of the diamine.

In the case where the tetracarboxylic dianhydride or diamine has an acidic functional group, the reaction may be carried out after neutralization by addition of a base. The base is preferably a tertiary amine, and particularly preferably triethylamine. The proportion of the base used is preferably 0.5 to 5 equivalents, and more preferably 1 to 2 equivalents, relative to the acidic functional group. Similarly, in the case where the tetracarboxylic dianhydride or diamine has a basic functional group, the reaction may be carried out after neutralization by addition of an acid. The acid is preferably a carboxylic acid. The proportion of the acid used is preferably 0.5 to 5 equivalents, and more preferably 1 to 2 equivalents, relative to the basic functional group.

Examples of the molecular weight regulator include: acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. 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 the tetracarboxylic dianhydride and the diamine used.

The synthesis reaction of the polyamic acid (P) is preferably carried out in an organic solvent. The reaction temperature in this case is preferably-20 to 150 ℃ and more preferably 0 to 100 ℃. 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, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and the like. Among these organic solvents, it is preferable to use one or more selected from the group consisting of aprotic polar solvents and phenolic solvents (organic solvents of the first group), or a mixture of one or more selected from the group consisting of organic solvents of the first group and one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the ratio of the organic solvent in the second group to the total amount of the organic solvents in the first group and the organic solvents in the second group is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

Particularly preferred as the organic solvent is one or more selected from the group consisting of N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, γ -butyrolactone, tetramethylurea, hexamethylphosphoric triamide, m-cresol, xylenol, and halogenated phenol, or a mixture of one or more of these solvents and another organic solvent in the above ratio. The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine is 0.1 to 50 mass% relative to the total amount (a + b) of the reaction solution.

In this manner, a reaction solution containing polyamic acid (P) can be obtained. The reaction solution may be directly supplied to the dehydration ring-closing reaction, the polyamic acid contained in the reaction solution may be separated and then supplied to the dehydration ring-closing reaction, or the separated polyamic acid may be purified and then supplied to the dehydration ring-closing reaction. The isolation and purification of the polyamic acid can be carried out according to a known method.

[ Polyamic acid ester ]

As the polyamic acid ester (hereinafter, also referred to as "polyamic acid ester (P)") as the precursor of the polymer (P), for example, it can be obtained by the following method: [I] a method of reacting polyamic acid (P) obtained by the polymerization reaction with an esterifying agent; [ II ] a method for reacting a tetracarboxylic acid diester with a diamine; [ III ] A method for reacting a tetracarboxylic acid diester dihalide with a diamine, and the like.

The polymer (P) can be obtained by subjecting the polyimide precursor (polyamic acid (P) and polyamic acid ester (P)) synthesized as described to dehydrate ring closure and imidization. The polymer (P) may be a complete imide product obtained by dehydration ring closure of the entire amic acid structure or amic acid ester structure of a polyimide precursor as a precursor thereof, or may be a partial imide product obtained by dehydration ring closure of only a part of the amic acid structure and amic acid ester structure, and coexistence of the amic acid structure or amic acid ester structure and imide ring structure. In order to obtain a coating film having a sufficiently high orientation regulating force in the application of a liquid crystal device, the imidization ratio of the polymer (P) is preferably 50% or more, more preferably 75% or more, still more preferably 85% or more, and particularly preferably 90% or more. The imidization ratio is a percentage representing the ratio of the number of imide ring structures of the polyimide to the total of the number of amic acid structures and amic acid ester structures and the number of imide ring structures.

The dehydration ring-closure of the polyimide precursor is preferably performed by the following method: a method of heating the polyamic acid; or a method in which the polyamic acid is dissolved in an organic solvent, and at least either a dehydrating agent or a dehydration cyclization catalyst is added to the solution, and the solution is heated as necessary.

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

In this way, a reaction solution containing the polymer (P) can be obtained. The reaction solution may be supplied directly to the preparation of the composition, may be supplied to the preparation of the composition after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, may be supplied to the preparation of the composition after isolating the polymer (P), or may be supplied to the preparation of the composition after purifying the isolated polymer (P). These purification operations may be carried out according to known methods.

With respect to the polymer (P) obtained in this manner, when it is made into a solution having a concentration of 10% by mass, it preferably has a solution viscosity of 10 mPas to 2000 mPas, more preferably has a solution viscosity of 20 mPas to 1000 mPas. The solution viscosity (mPa · s) of the polymer is a value measured at 25 ℃ with an E-type rotational viscometer for a 10 mass% polymer solution prepared using a good solvent for the polymer (e.g., water).

The weight average molecular weight (Mw) of the polymer (P) in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, and more preferably 10 or less. The molecular weight range is preferable because the concentration range and the temperature range in which the composition exhibits lyotropic liquid crystallinity can be easily secured.

< other ingredients >

The composition of the present disclosure may contain other components than the polymer (P) within a range not interfering with the object and effect of the present disclosure.

[ other Polymer ]

Examples of the other components include: and polymers other than the polymer (P) (hereinafter, also referred to as "other polymers"). Other polymers may be used in order to improve solution characteristics or electrical characteristics. Specific examples of the other polymer include: a polyamic acid obtained by reacting the other tetracarboxylic dianhydride with the other diamine, an imidized polymer of the polyamic acid, an esterified polymer of the polyamic acid, a polyester, a polyamide, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly (styrene-phenylmaleimide) derivative, a poly (meth) acrylate, and the like.

When another polymer is blended in the composition, the blending ratio of the other polymer is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less, with respect to 100 parts by mass of the total of the polymers contained in the composition.

[ rod-like molecules, etc. ]

Examples of the other component include a rod-like molecule and a rod-like nanostructure (hereinafter, also referred to as "rod-like molecule and the like"). By applying a shear stress to the composition, the orientation of the rod-like molecules and the like can be controlled along with the uniaxial orientation of the polymer (P). Examples of the rod-like molecule include a dichroic dye, and examples of the rod-like nanostructure include a dye association, a quantum rod, a metal nanorod, a carbon nanotube, a protein, a nucleic acid, and a virus. By controlling the orientation of the rod-like molecules and the like, various functionalities can be imparted. For example, the composition containing the dichroic dye may form a guest-host type polarizing plate, the composition containing the quantum rod may form a wavelength conversion plate that can emit polarized light, and the composition containing the carbon nanotube may form a wire or an actuator having conductive anisotropy. When the rod-like molecules and the like are blended in the composition, the blending ratio thereof may be appropriately set depending on the kinds of the rod-like molecules and the like within a range not to impair the effects of the present disclosure.

Examples of the other components other than the above include: a compound having at least one epoxy group in the molecule, a functional silane compound, a surfactant, a filler, a pigment, an antifoaming agent, a sensitizer, a dispersant, an antioxidant, an adhesion promoter, an antistatic agent, a leveling agent, an antibacterial agent, and the like. Further, the blending ratio of these compounds may be appropriately set depending on each compound to be blended within a range not to impair the effect of the present disclosure.

[ solvent ]

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

Examples of the solvent to be used include: water, methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, 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-dimethylformamide, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N, 2-trimethylpropionamide, 1-butoxy-2-propanol, diacetone alcohol, dipropylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, isopropyl alcohol, tert-butyl alcohol, ethylene glycol, propylene glycol, and propylene glycol, and propylene glycol, and propylene glycol ether, and propylene glycol ether, Butyl lactate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and the like. These may be used alone or in combination of two or more.

The solvent used preferably contains water. The proportion of water used is preferably 50% by mass or more, more preferably 75% by mass or more, and particularly preferably 90% by mass or more, relative to 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 to be used is not particularly limited as long as it is an organic solvent that is soluble in water, but is preferably an organic solvent having a boiling point lower than that of water, and more preferably at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, 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, and still more preferably 10% by mass or less, relative to the total amount of the mixed solvent.

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 1 to 30% by mass relative to the total amount of the solvent and the polymer (P). According to the polymer (P), it is preferable in terms of obtaining a composition exhibiting lyotropic liquid crystallinity at a low polymer concentration. Therefore, the coating film has good coatability when formed on a substrate, and can be formed into a thin film of about 0.1 μm, and is excellent in industrial productivity. 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 in the composition of the present disclosure (the ratio of the total mass of the components other than the solvent in the composition to the total mass of the composition) may be appropriately selected in consideration of viscosity, volatility, and the like, and is preferably in the range of 1 to 30 mass%, more preferably in the range of 2 to 20 mass%, and particularly preferably in the range of 3 to 15 mass%. That is, the composition of the present disclosure may be applied to the surface of a substrate, and preferably dried, as described below, to form a coating film. In this case, when the solid content concentration is less than 1% by mass, the composition hardly exhibits lyotropic liquid crystallinity. On the other hand, when the solid content concentration exceeds 30 mass%, the film thickness of the coating film is too large to obtain a good coating film, and the viscosity of the composition tends to increase to lower the coatability. The temperature at which the composition is prepared is preferably 10 ℃ to 90 ℃, more preferably 20 ℃ to 65 ℃.

[ 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 a temperature of at least a part of the range of 0 ℃ or higher and less than 100 ℃. The temperature range in which lyotropic liquid crystallinity is exhibited is preferably a temperature range including 20 to 40 ℃, more preferably a temperature range including 20 to 60 ℃, and even more preferably a temperature range including 10 to 80 ℃ in a range of 0 ℃ or higher and less than 100 ℃. By applying the composition in a lyotropic liquid crystal state to a substrate and flowing the composition by shear stress, a coating film in which the molecular chains of the polymer (P) are self-organized in the shear direction and uniaxially oriented can be obtained. In the coating and drying processes, it is desirable to control the temperature range and the concentration range so as not to deviate from the temperature range and the concentration range in which the composition exhibits lyotropic liquid crystallinity. In the coating or drying process, regardless of the fluidity of the composition, if the temperature or concentration is reached at which lyotropic liquid crystallinity is not exhibited, the orientation may be relaxed and the anisotropy of the coating film may be lost. When the polymer (P) is mixed with a solvent and the polymer (P) is ionized, the polymer (P) is contained in the composition together with the solvent in a state where the ionic functional group in the partial structure represented by the formula (1) is ionized.

The polymer (P) is a rigid rod-like polymer and functions as a mesogen in a solvent. Further, since the polymer (P) has a structure in which benzene rings and imide rings are linked in the main chain and is a rigid aromatic polyimide having high uniaxial linearity, it is easy to perform in-plane alignment at the film interface by stacking between molecules, and a liquid crystal alignment film having excellent alignment regulating force can be formed. Further, by introducing rod-like molecules or the like (guest) into the lyotropic liquid crystal field (host) formed of the polymer (P), the rod-like molecules or the like can be oriented along the molecular chain of the polymer (P), and a retardation plate, a polarizing plate, a wavelength conversion plate, or the like can be formed.

< liquid Crystal alignment film and liquid Crystal cell >

The liquid crystal alignment film of the present disclosure is formed by using the composition prepared as described as a liquid crystal aligning agent. The liquid crystal element of the present disclosure further 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, the driving mode is not particularly limited, and the liquid crystal element can be applied to various driving modes such as a Twisted Nematic (TN) type, a Super Twisted Nematic (STN) type, an in-plane Switching (IPS) type, a Fringe Field Switching (FFS) type, a Vertical Alignment (VA) type, a Multi-domain Vertical Alignment (MVA) type, and a Polymer Stabilized Alignment (PSA) type.

The liquid crystal display element can be manufactured by a method including, for example, the following steps 1 to 3. The FFS type liquid crystal display device is manufactured by using a different substrate depending on a desired driving mode.

[ Process 1: formation of coating film ]

First, a composition is applied to a substrate, and then the coated surface is heated, thereby forming a coating film on the substrate. In the case of manufacturing an FFS type liquid crystal display element, the composition is preferably applied to the electrode-formed surface of the substrate on which the electrode including the transparent conductive film or the metal film patterned into a comb-tooth shape is provided and the surface of the opposing substrate on which the electrode is not provided, by a bar coater method, a die coater method, or a blade coater method. According to these methods, it is preferable in terms of ease of orienting the molecular chains of the polymer (P) by flow using shear stress.

Here, the substrate can be, for example: float processGlass (float glass), soda lime glass, and the like; transparent substrates comprising plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly (alicyclic olefin). The transparent conductive film provided on one surface of the substrate may contain tin oxide (SnO)₂) The NESA film (registered trademark of PPG corporation, USA) contains indium oxide-tin oxide (In)₂O₃-SnO₂) An ITO film of (2). To obtain a patterned transparent conductive film, for example,: a method of forming a transparent conductive film without a pattern and then forming a pattern by light etching, a method of using a mask having a desired pattern when forming a transparent conductive film, and the like. As the metal film, for example, a film containing a metal such as chromium can be used. In order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film when the composition is applied, the surface of the substrate on which the coating film is formed may be subjected to pretreatment such as coating with a functional silane compound or a functional titanium compound in advance.

After the composition is applied, preheating (prebaking) is preferably performed for the purpose of preventing sagging of the applied composition and the like. The pre-baking temperature is preferably 30-100 ℃, more preferably 40-80 ℃, and particularly preferably 40-60 ℃. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Then, a firing (post-baking) step is performed for the purpose of completely removing the solvent and, if necessary, for the purpose of thermally imidizing the amic acid structure present in the polymer. The calcination temperature (post-baking temperature) in this case is preferably 60 to 300 ℃, and more preferably 100 to 250 ℃. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. Preferably, in the heating step, the coating film containing the liquid crystal aligning agent applied to the substrate is brought into a state in which the molecular chains of the polymer (P) are aligned by a flow of shear stress, and is dried in the state. Thus, a liquid crystal alignment film can be formed by imparting liquid crystal alignment energy to the coating film by a simple operation. The film thickness of the formed film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5. mu.m.

After the composition is coated on a substrate, the solvent is removed, thereby forming a liquid crystal alignment film. In this case, when the polymer contained in the composition has an imide ring structure and an amic acid structure, a more imidized coating film can be formed by further heating after the formation of the coating film to effect a dehydration ring-closure reaction.

[ step 2: ion crosslinking treatment ]

The substrate on which the liquid crystal alignment film is formed may be immersed in a polyvalent cation aqueous solution to be subjected to an ion crosslinking treatment as needed. By exchanging counter cations of the polymer (P) with polyvalent cations, the water resistance or mechanical properties of the liquid crystal alignment film are improved, and further, the electrical properties of the liquid crystal cell are improved. The polyvalent cation is not particularly limited as long as it is a divalent or higher metal cation or an organic polycation, but is preferably an alkaline earth metal ion, and particularly preferably Ca²⁺、Sr²⁺Or Ba²⁺. The counter ion of the polyvalent cation is not particularly limited if it is water-soluble, and is preferably a hydroxide ion, a carbonate ion or a halide ion. The immersion time is preferably 1 minute to 20 minutes, more preferably 2 minutes to 10 minutes. Further, it is preferable that the substrate is immersed in the polyvalent cation aqueous solution, then the substrate taken out is rinsed with pure water, and further immersed in pure water, thereby removing an excessive ionic component.

[ step 3: construction of liquid Crystal cell

A liquid crystal cell is manufactured by preparing two substrates on which liquid crystal alignment films are formed as described above and disposing liquid crystal between the two substrates disposed opposite to each other. For example, the following 2 methods are used to produce a liquid crystal cell. The first method is a method known in the art. First, two substrates are arranged to face each other through a gap (cell gap) so that the liquid crystal alignment films face each other, peripheral portions of the two substrates are bonded to each other with a sealant, a liquid crystal is injected and filled into the cell gap defined by the substrate surfaces and the sealant, and then the injection hole is sealed, thereby manufacturing a liquid crystal cell. The second method is a method called a One Drop Fill (ODF) method. For example, a sealant that is ultraviolet curable is applied to a predetermined portion of one of two substrates on which a liquid crystal alignment film is formed, liquid crystal is dropped onto predetermined portions of the liquid crystal alignment film surface, the other substrate is attached so that the liquid crystal alignment film faces each other, the liquid crystal is spread over the entire surface of the substrate, and then ultraviolet light is irradiated to the entire surface of the substrate to cure the sealant, thereby manufacturing a liquid crystal cell. In the case of using either method, it is preferable that the liquid crystal cell manufactured as described above is further heated to a temperature at which the liquid crystal used has an isotropic phase, and then gradually cooled to room temperature, whereby the flow alignment at the time of filling the liquid crystal is removed.

As the sealant, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used.

The liquid crystal includes nematic liquid crystal and smectic liquid crystal, and among them, nematic liquid crystal is preferable, and for example: schiff base (Schiff base) liquid crystals, azoxy (azo) liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, diphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane (cubane) liquid crystals, and the like. In addition, the following substances may be added to these liquid crystals: cholesteric liquid crystals such as cholesterol chloride, cholesteryl nonanoate and cholesteryl carbonate; chiral agents sold under the trade names "C-15", "CB-15" (manufactured by Merck); ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate and the like.

Further, a polarizing plate may be bonded to the outer surface of the liquid crystal cell to obtain a liquid crystal display element. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include: a polarizing plate including a polarizing film called an "H film" in which polyvinyl alcohol is oriented while absorbing iodine, or a polarizing plate including the H film itself is sandwiched between cellulose acetate protective films.

< phase difference plate >

The phase difference plate of the present disclosure is formed using the composition prepared as described above. Specifically, first, the composition is preferably coated on a substrate (for example, a glass substrate, Triacetyl Cellulose (TAC), polyethylene terephthalate, polymethyl methacrylate, or the like) by a bar coater method, a die coater method, or a blade coater method, and then dried in a state in which molecular chains of the polymer (P) are oriented by flow using shear stress. Thereby, a phase difference plate is formed.

< polarizing plate >

The polarizing plate of the present disclosure is formed using a composition containing the dichroic dye or metal prepared as described above. For example, in order to manufacture a guest-host polarizing plate, a composition containing a polymer (P), a dichroic dye, and a solvent is first coated on a substrate (e.g., a glass substrate, triacetyl cellulose (TAC), polyethylene terephthalate, polymethyl methacrylate, or the like) preferably by a bar coater method, a die coater method, or a knife coater method. Then, the polymer (P) is dried in a state in which the molecular chains thereof are oriented by the flow of shear stress, whereby a polarizing plate can be obtained. In addition, a resin film (protective film) may be bonded to one surface or both surfaces of the polarizing plate as necessary.

In order to produce a reflection-type polarizing plate, a composition containing a polymer (P), a metal (metal nanorods, metal nanowires, or metal ions), and a solvent is applied to a substrate in the same manner as in the production method of a guest-host type polarizing plate, and then dried in a state in which the molecular chains of the polymer (P) are oriented by a flow of shear stress, whereby a polarizing plate can be obtained. When metal ions are used as the metal, the monomer metal is deposited anisotropically along the polymer (P) by reduction.

The liquid crystal element of the present disclosure can be effectively applied to various applications, for example, clocks, portable game machines, word processors, notebook Personal computers, car navigation systems, camcorders, Personal Digital Assistants (PDAs), Digital cameras, mobile phones, smart phones, various monitors, liquid crystal televisions, various liquid crystal display devices such as information displays, light adjusting films, retardation plates, polarizing plates, and the like.

Examples

Hereinafter, the present disclosure will be described in more detail 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

[ solution 5]

(specific diamine)

DA-1: 4,4 '-diamino-2, 2' -biphenyldisulfonic acid

DA-2: 2, 5-diaminobenzenesulphonic 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-diaminobenzenesulphonic acid

[ solution 6]

The imidization rate [% ] of polyimide was measured by the following method.

Adding polyimide solution into pure water, drying the obtained precipitate at room temperature under reduced pressure, dissolving in deuterated dimethyl sulfoxide, measuring at room temperature with tetramethylsilane as reference substance¹H-NMR. According to the obtained¹The H-NMR spectrum was obtained by using a formula represented by the following numerical formula (a).

Imidization rate [% ]]＝(((1-A¹)/A²)×α)×100...(a)

(in the formula (a), A¹A is the peak area of the NH group-derived proton appearing in the vicinity of a chemical shift of 10ppn²α is the ratio of the number of other protons in the precursor of the polymer to one proton of the NH group, which is the peak area derived from the other protons. )

[ example 1]

(1) Synthesis of polymers

Diamine (DA-1) (3.79g, 11.0mmol), m-cresol (50mL), and triethylamine (2.43g, 24.0mmol) were charged into a three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, and stirred under nitrogen. After dissolving the diamine, acid dianhydride (TA-1) (2.18g, 10.0mmol) and benzoic acid (1.71g, 14.0mmol) were added, and the mixture was stirred at 80 ℃ for 3 hours and then at 180 ℃ for 12 hours. After the reaction was completed, the reaction solution was diluted with m-cresol, dropped into acetone and solidified. The obtained coagulated product was filtered, washed with acetone, and vacuum-dried at 120 ℃ to obtain a brown powder of a polymer having a partial structure represented by the following formula (PI-1) (6.64g, yield 88%). The polymer (PI-1) is shown in FIG. 1¹H-NMR Spectroscopy (dimethyl sulfoxide, DMSO) -d⁶400 MHz). The imidization ratio of the polymer (PI-1) is 99% or more.

[ solution 7]

(2) Preparation of composition and evaluation of solubility

Dissolving the polymer (PI-1) obtained in the above (1) by adding water thereto and stirring with heating at 60 ℃ to obtain an aqueous solution of the polymer (PI-1). The composition (C-1) was prepared by filtering the solution with a filter having a pore size of 0.2 μm.

For the evaluation of solubility, the case where an aqueous solution having a solid content concentration of 1 mass% or more of the polymer can be prepared was regarded as "good", and the case where an aqueous solution having a solid content concentration of 1 mass% or more of the polymer cannot be prepared was regarded as "poor". As a result, the evaluation in the examples was "good".

(3) Evaluation of lyotropic liquid Crystal Property

The composition (C-1) obtained in the above (2) was dropped onto a glass substrate, and observed with a polarizing microscope. For the evaluation, the case where optical anisotropy was observed under crossed nicols at a temperature of at least a part of the range of 0 ℃ or higher and less than 100 ℃ was regarded as "good", and the case where optical anisotropy was not observed even at any temperature of 0 ℃ or higher and less than 100 ℃ was regarded as "poor". As a result, in the above examples, the optical anisotropy was observed in the concentration range where the solid content concentration of the polymer was 6 to 20 mass% and the temperature range of 10 to 90 ℃, which was a "good" evaluation.

FIGS. 3 to 5 show the polarization micrographs (100 times) of the composition (C-1) in which the polymer had a solid content concentration of 10% by mass. Fig. 3 is a photograph immediately after the composition is dropped on the glass substrate, fig. 4 is a photograph after the composition is slightly dried after the dropping and concentrated on the glass substrate, and fig. 5 is a photograph after the composition is dropped and the upper glass substrate is laterally moved to apply shear stress while being held by the glass substrate from above.

Examples 2 to 3 and 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 acid dianhydride and diamine were changed as described in table 1 below in example 1. Further, compositions (C-2 to C-9) were prepared using the obtained polymers (PI-2 to PI-9), respectively, and the solubility and liquid crystallinity were evaluated. The evaluation results are shown in table 1 below. In table 1, the numerical values (molar ratios) in the diamine column indicate the use ratio (molar parts) of each compound relative to 100 molar parts of the total amount of diamines used for synthesizing the polymer. In comparative example 1 and comparative example 4, the solubility was "poor", and the lyotropic liquid crystal properties could not be evaluated, and therefore, the solubility was indicated by "-" in table 1.

The polymer (PI-2) is shown in FIG. 2¹H-NMR Spectroscopy (DMSO-d)⁶400 MHz). The imidization ratio of the polymer (PI-2) is 99% or more. In example 2, optical anisotropy was observed in a temperature range of 20 to 70 ℃ with a solid content concentration of the polymer of 2 mass% and in a temperature range of 40 to 80 ℃ with a solid content concentration of 3 to 6 mass%, and liquid crystallinity was evaluated as "good".

[ solution 8]

[ Table 1]

Example 4: production and evaluation of liquid Crystal alignment film

(1) Preparation of the composition

A10% by mass solution of the composition (C-1) containing the polymer (PI-1) obtained in example 1 was diluted with water to obtain a solution having a solid content concentration of 6% by mass. The composition (C-10) was prepared by filtering the solution with a filter having a pore size of 0.2 μm.

(2) Formation of liquid Crystal alignment film

The composition (C-10) prepared in (1) was applied to the surfaces of a glass substrate having a flat electrode, an insulating layer and a comb-shaped electrode laminated in this order on one surface and a glass substrate facing the glass substrate without an electrode, respectively, using a wire bar so that the thickness thereof became 0.1 μm, and dried with a warm air at 60 ℃ for 5 minutes and then dried with an oven at 120 ℃ for 30 minutes to form a liquid crystal alignment film.

(3) Manufacture of liquid crystal display element

For a pair of substrates having the liquid crystal alignment films produced in (2), after leaving a liquid crystal injection port at the edge of the surface on which the liquid crystal alignment films were formed, an epoxy resin adhesive containing alumina balls having a diameter of 5.5 μm was screen-printed and applied, the substrates were stacked and pressure-bonded so that the projection direction of the polarizing axis at the time of light irradiation to the substrate surface became antiparallel, and the adhesive was thermally cured at 150 ℃ for 1 hour. Then, a nematic liquid crystal (MLC-7028 manufactured by Merck) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, the liquid crystal was heated at 120 ℃ and then slowly cooled to room temperature. Then, polarizing plates are bonded to both outer surfaces of the substrate to manufacture an FFS type liquid crystal display device.

(4) Evaluation of liquid Crystal alignment Properties

With respect to the liquid crystal display element manufactured in the above (3), the presence or absence of an abnormal region (domain) in the light-dark change when a voltage of 5V is turned ON/OFF (ON/OFF) (applied/released) is observed with a microscope at a magnification of 50 times. For the evaluation, the case where no abnormal domain was observed was regarded as "good", and the case where an abnormal domain was observed was regarded as "bad". As a result, the evaluation in the examples was "good".

[ example 5]

A composition (C-11) was prepared in the same manner as in example 4, except that the composition (C-2) was used in place of the composition (C-1) in the "(preparation of composition 1)" of example 4 and the concentration of the solid content after dilution with water was changed from 6% by mass to 3% by mass. Further, a liquid crystal alignment film was formed using the prepared composition (C-11), and a liquid crystal display element was manufactured and evaluated for liquid crystal alignment properties. The evaluation results are shown in table 2 below.

Comparative examples 7 to 8

In example 4, a liquid crystal alignment film was formed by preparing a composition in the same manner as in example 4, and a liquid crystal display element was manufactured and evaluated for liquid crystal alignment properties, except that the polymer contained in the composition was changed as described in table 2 below. The evaluation results are shown in table 2 below.

Example 6: production and evaluation of retardation film

Using the composition (C-1) containing the polymer (PI-1) obtained in example 1, a glass substrate was coated with a film thickness of 1 μm using a bar coater, and dried with warm air at 60 ℃ for 5 minutes and then dried in an oven at 120 ℃ for 30 minutes, thereby forming a retardation film.

For the evaluation of retardation, the in-plane retardation (retardation) was measured by the parallel nicols rotation method, and the case where the in-plane retardation was 20nm or more at a wavelength of 550nm was regarded as "good", and the case where the in-plane retardation was less than 20nm was regarded as "bad". As a result, this example shows a "good" result.

Comparative example 9

In example 6, a retardation plate was formed and a retardation was evaluated in the same manner as in example 6, except that the polymer contained in the composition was changed as described in table 2 below. The evaluation results are shown in table 2 below.

Example 7: production and evaluation of polarizing plate

(1) Preparation of the composition

Using the composition (C-1) containing the polymer (PI-1) obtained in example 1, 1 part by mass of a dichroic dye index (color index, c.i.) Direct Orange (Direct Orange)39 (manufactured by Santa Cruz Biotechnology) was added to 100 parts by mass of the polymer (PI-1), and diluted with water, thereby obtaining a solution having a solid content concentration of 10 mass%. The composition (C-14) was prepared by filtering the solution with a filter having a pore size of 0.2 μm.

(2) Formation of polarizing plate

The composition (C-14) prepared in (1) was applied to a glass substrate with a thickness of 10 μm using a bar coater, dried with warm air at 60 ℃ for 5 minutes, and dried in an oven at 120 ℃ for 30 minutes, to form a guest-host polarizing plate.

(3) Evaluation of dichroic ratio

The evaluation was carried out by polarized light absorption spectroscopy measurement, and the case where the dichroic ratio was 2 or more was regarded as "good", and two were regarded asThe color rendering ratio is less than 2, which is "poor". As a result, this example shows a "good" result. Further, the dichroic ratio is defined as the absorbance (A) at a wavelength of 500nm when the polarization axis is parallel to the shearing direction_‖) And absorbance (A) when the polarization axis is perpendicular to the shear direction_⊥) Ratio of (A)_‖/A_⊥)。

Comparative example 10

In example 7, a polarizing plate was formed and the dichroic ratio was evaluated by preparing a composition in the same manner as in example 7, except that the polymer contained in the composition was changed as described in table 2 below. The evaluation results are shown in table 2 below. In table 2, "-" indicates that no evaluation was performed.

[ Table 2]

As is clear from the above results, the composition of the example using the polymer (P) exhibited lyotropic liquid crystal properties, in which optical anisotropy was observed at a temperature of 0 ℃ or higher and less than 100 ℃ under crossed nicols. The polymer (P) exhibits lyotropic liquid crystallinity in water at a low polymer concentration of 20% by mass or less. In addition, the liquid crystal display element, the retardation plate and the polarizing plate manufactured using the composition of the example showed good optical characteristics. In contrast, the compositions of the comparative examples also showed no optical anisotropy at any temperature. As is clear from these results, by using the polymer (P), a composition exhibiting lyotropic liquid crystallinity under mild conditions can be obtained.

Claims

1. A composition which is obtained by mixing a polymer (P) having a partial structure represented by the following formula (1) with a solvent and exhibits lyotropic liquid crystallinity;

the polymer (P) is a polymer in which 75 mol% or more of the compound represented by the following formula (t-1) is contained relative to the total amount of tetracarboxylic dianhydride used for synthesizing the polymer (P);

the composition contains water in an amount of 50% by mass or more based on the total amount of the solvent;

in the formula (1), R¹～R¹⁰At least one of them is a monovalent group having an ionic functional group, and the others are each independently a hydrogen atom, a halogen atom, or a monovalent organic group; k is 0 or 1;

in the formula (t-1), R¹And R²Is a hydrogen atom, a halogen atom, an ionic functional group or a monovalent organic group.

2. The composition according to claim 1, which exhibits lyotropic liquid crystallinity at least in part of a temperature range of 0 ℃ or more and less than 100 ℃.

3. The composition according to claim 1 or 2, wherein the ionic functional group is a sulfonic, phosphonic, carboxylic, ammonium, pyridyl, imidazolyl or guanidino group, or a salt of these.

4. The composition of claim 1 or 2, wherein the ionic functional group is an acidic functional group.

5. The composition according to claim 1 or 2, wherein the polymer (P) is a polymer having a partial structure represented by the following formula (2) as the partial structure represented by the formula (1);

in the formula (2), M is a cation; k is 0 or 1; where k is 1, M in the formula may be the same as or different from each other.

6. A composition is obtained by mixing a polymer (P) having a partial structure represented by the following formula (1), a solvent, and at least one selected from the group consisting of dichroic dyes, dye aggregates, quantum rods, metal nanorods, and carbon nanotubes;

the polymer (P) is a polymer in which 75 mol% or more of the compound represented by the following formula (t-1) is contained relative to the total amount of tetracarboxylic acid dianhydride used for synthesizing the polymer (P);

7. A liquid crystal aligning agent is obtained by mixing a polymer (P) having a partial structure represented by the following formula (1) with a solvent;

the liquid crystal aligning agent contains water in an amount of 50 mass% or more of the total amount of the solvent;

8. A liquid crystal alignment film formed using the composition according to any one of claims 1 to 6.

9. A phase difference plate formed using the composition according to any one of claims 1 to 6.

10. A polarizing plate formed using the composition according to any one of claims 1 to 6.

11. A method for producing a liquid crystal alignment film, comprising applying the composition according to any one of claims 1 to 6 onto a substrate in a lyotropic liquid crystal state, and drying the composition in a state in which molecular chains of the polymer (P) are aligned by a flow of shear stress.

12. A liquid crystal device comprising the liquid crystal alignment film according to claim 8.

13. A composition obtained by mixing an imide polymer obtained by reacting a tetracarboxylic dianhydride with a diamine with a solvent,

75 mol% or more of a compound represented by the following formula (t-1) relative to the total amount of the tetracarboxylic dianhydride;

at least one selected from the group consisting of compounds represented by the following formulae (d-1) to (d-16) in an amount of 50 mol% or more based on the total amount of the diamines;

in the formula (t-1), R¹And R²Is a hydrogen atom, a halogen atom, an ionic functional group or a monovalent organic group;

14. a composition obtained by mixing an imide polymer obtained by reacting a tetracarboxylic dianhydride with a diamine with a solvent,

the tetracarboxylic dianhydride is a compound represented by the following formula (TA-1);

the diamine is at least one selected from the group consisting of compounds represented by the following formulas (DA-1) to (DA-3);