JP7067555B2 - Composition, liquid crystal alignment film, retardation plate, polarizing plate, method for manufacturing the alignment film, and liquid crystal element - Google Patents

Description

Cross-reference of related applications

This application is based on Japanese Application No. 2017-115199 filed on June 12, 2017, the contents of which are 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 the alignment film, and a liquid crystal element.

The liquid crystal includes a thermotropic liquid crystal (melt type) showing liquid crystal property in a certain temperature range and a riotropic liquid crystal (solution type) showing liquid crystal property in a certain concentration range. The lyotropic liquid crystalline polymer has an isotropic phase with no regularity in the arrangement of molecular chains below the critical concentration, but exhibits a liquid crystal state above the critical concentration. In this liquid crystal state, the molecular chains form an aggregate of minute domains arranged in one direction and exhibit optical anisotropy. Further, when the liquid crystal state solution is sheared and deformed, the molecular chains are oriented in the flow direction. For example, it is known that aromatic polyamides typified by Kevlar are dissolved in a strong acid such as concentrated sulfuric acid, and the concentrated solution exhibits lyotropic liquid crystallinity. By spinning from this lyotropic liquid crystal state solution, high-performance fibers having a high elastic modulus with molecular chains oriented in the fiber direction can be produced.

In order to realize a liotropic liquid crystal polymer, it is necessary to use a rigid rod-shaped polymer, but in general, the rigid rod-shaped polymer has difficulty in dissolving in water or an organic solvent, and a corrosive solvent such as sulfuric acid can be used. It was necessary to use it or dissolve it in a polar solvent having a high boiling point at a high temperature.

For polymers with 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, and have been applied to retardation plates, polarizing plates, etc. Applications have been studied (Non-Patent Document 1, Patent Documents 1 to 3). In addition, materials exhibiting lyotropic liquid crystal properties have been reported for polyimide (Non-Patent Documents 2 to 4), and pioneering applied research on polyimide precursors has been conducted by Neuber et al. (Non-Patent Documents 5 to 6).

International Publication No. 2009/130675 International Publication No. 2010/20928 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. Chem. Phys.", 2002, Vol. 203, p.598-604. "Adv. Funct. Mater.", 2003, Volume 13, p.387-391.

For the alignment control of the liquid crystal, a polyimide-based material has been preferably used as the liquid crystal alignment film in order to exhibit an excellent orientation regulating force for the liquid crystal. If a polyimide-based material with excellent orientation-regulating power can be used to obtain a material exhibiting lyotropic liquid crystal properties, it may be oriented by shear flow by a simple coating process, and a high-performance liquid crystal alignment film, retardation plate, or polarizing plate may be obtained. 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 a lyotropic liquid crystal property has been reported in polyimide, a corrosive solvent such as concentrated sulfuric acid or cresol is required to dissolve the polyimide (non-patent). Patent Documents 2 to 4) require a high temperature for the development of lyotropic liquid crystallinity (Non-Patent Documents 3 and 4), and no material exhibiting liotropic liquid crystallinity under mild conditions is known. Further, in the polyimide precursors shown in Non-Patent Documents 5 to 6, since they are polyamic acid esters, thermal imidization of the coating film is required, and high temperature (about 100 ° C.) and high concentration are required for the development of lyotropic liquid crystallinity. There is an inconvenience that (about 50% by mass) is required. In order to obtain a thin film by coating on a substrate, from the viewpoint of industrial productivity and the environment, 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 about room temperature). It is desirable to develop lyotropic liquid crystallinity at low temperature) and at a sufficiently low concentration. That is, there is a demand for a composition that exhibits liotropic liquid crystallinity under mild conditions in temperature, solvent, and concentration by using polyimide having excellent orientation regulating power and the like.

The present disclosure has been made in view of the above problems, and one object of the present invention is to provide a polyimide-based composition exhibiting lyotropic liquid crystallinity under mild conditions.

（式（１）中、Ｒ^１～Ｒ^１０のうち少なくとも一つはイオン性官能基を有する１価の基であり、残りは、それぞれ独立して、水素原子、ハロゲン原子又は１価の有機基である。ｋは０又は１である。）
＜２＞ 前記組成物を用いて形成された液晶配向膜。
＜３＞ 前記組成物を用いて形成された位相差板。
＜４＞ 前記組成物を用いて形成された偏光板。
＜５＞ 上記式（１）で表される部分構造を有する重合体（Ｐ）と、溶剤とを混合して得られる、液晶配向剤。
＜６＞ 前記組成物をリオトロピック液晶状態において基板に塗布し、前記重合体（Ｐ）の分子鎖をせん断応力による流動により配向させた状態で乾燥する、液晶配向膜の製造方法。According to the present disclosure, the following means are provided.
<1> A composition exhibiting lyotropic liquid crystallinity, which is obtained by mixing a polymer (P) having a partial structure represented by the following formula (1) with 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 independently hydrogen atoms, halogen atoms or monovalent organic groups. K is 0 or 1.)
<2> A liquid crystal alignment film formed by using the above composition.
<3> A retardation plate formed by using the composition.
<4> A polarizing plate formed by using the above composition.
<5> A liquid crystal alignment agent obtained by mixing a polymer (P) having a partial structure represented by the above formula (1) with 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 the molecular chains of the polymer (P) are dried in a state of being 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 having excellent orientation regulating power and the like. Further, since the polymer component in the composition of the present disclosure is uniformly oriented over 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 a polymer (PI-1). FIG. 2 is a ¹ H-NMR spectrum of the polymer (PI-2). FIG. 3 is a polarizing micrograph after dropping the composition (C-1) onto the substrate. FIG. 4 is a polarizing micrograph after concentrating the composition (C-1) on a substrate. FIG. 5 is a polarizing micrograph 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) with a solvent, and exhibits lyotropic liquid crystallinity. Hereinafter, each component contained in the composition of the present disclosure, and other components optionally blended will be described.

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

Regarding R ¹ to R ¹⁰ in the formula (1), the hydrocarbon group is preferable as the monovalent organic group, and the alkyl group having 1 to 5 carbon atoms is more preferable. 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. "Is represented by a bond that binds 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. , -OR ¹³ -** (however, R ¹³ is a divalent hydrocarbon group, and "**" indicates a bond that binds to X ¹ ) and the like.

Ionic functional groups are functional groups that form cations or anions in water. The ionic functional group is not particularly limited, but is a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, an ammonium group, a pyridinium group, in that the solubility of the polymer (P) in a solvent containing water can be further increased. It is preferably an imidazolium group or a guanidinium group, or a salt thereof. 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 drives phase separation especially in a highly polar solvent. It is presumed that it can promote self-organization with force and contribute to the increase of anisotropy.

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 (sulfonic acid group, phosphonic acid group, carboxylic acid group, etc.) include Li ⁺ , Na ⁺ , and the like. 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 Qt} ⁺ 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. The same shall apply hereinafter.) And so on. As the counterion 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). It represents ~ 20 hydrocarbon groups.) And the like. When the ionic functional group is a carboxylic acid group, the acid dissociation constant of the carboxylic acid is low, the protons are difficult to dissociate under acidic conditions, and the ionicity is lowered. Therefore, it is desirable to form a salt with a strong base.

Among the monovalent groups having an ionic functional group, L ¹ can be appropriately selected depending on the type 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, 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, and more preferably 1 to 3 carbon atoms. It is an arcandyl group of.
R ¹ to R ¹⁰ may have at least a part thereof having 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 ionic functional groups among R ¹ to R ¹⁰ ) is preferably 1 to 4, and is 1 or 1. It is more preferable that 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 ) in that it exhibits good lyotropic liquid crystallinity and has a high degree of freedom in material selectivity. Is preferable.

（式（２）～式（４）中、Ｍはカチオンである。ｋは０又は１である。ただし、ｋ＝１の場合、式中の複数のＭは、互いに同じでも異なっていてもよい。）The polymer (P) has, as the partial structure represented by the above formula (1), the partial structure represented by the following formula (2), the partial structure represented by the following formula (3), and the following formula (4). A polymer having at least one selected from the group consisting of the represented partial structures is more preferable, and a polymer having a partial structure represented by the following formula (2) is particularly preferable.

(In 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 from each other. .)

The cations of M are H ⁺ , 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 Qt} ⁺ and the like. As the cation of M, a monovalent cation is preferable because the solubility of the polymer (P) in an aqueous solvent can be further increased, and among these, NH _4-t Q _t ⁺ is preferable, and a tertiary ammonium ion is preferable. Is more preferable.

As used herein, the term "tetracarboxylic acid diester" means a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified and the remaining two are carboxyl groups. The "tetracarboxylic acid diester dihalogenate" means 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 acids and polyamic acid esters. "Organic group" means a group containing a carbon atom and may contain a heteroatom in the structure.

As used herein, the term "hydrocarbon group" means 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 which do not contain a cyclic structure in the main chain and are composed only of a chain structure. However, it may be saturated or unsaturated. The "aliphatic hydrocarbon group" means a hydrocarbon group containing only the alicyclic hydrocarbon structure as the ring structure and not containing the aromatic ring structure. However, it does not have to be composed only of the alicyclic hydrocarbon structure, and some of them have a chain structure. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not have to be composed only of an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure as a part thereof.

（式（ｔ－１）中、Ｒ^１及びＲ^２は、水素原子、ハロゲン原子、イオン性官能基又は１価の有機基である。）As the monomer used in the synthesis of the polymer (P), at least one selected from the group consisting of tetracarboxylic acid dianhydride, tetracarboxylic acid diester and tetracarboxylic acid diester dihalide, and diamine can be used. Preferred specific examples of the tetracarboxylic acid dianhydride include a compound represented by the following formula (t-1) (hereinafter, also referred to as “specific tetracarboxylic acid dianhydride”) and the like. The specific tetracarboxylic acid dianhydride may be used alone or in combination of two or more. 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 contained in the hydrocarbon group were substituted with an ionic functional group. The group etc. can be mentioned. Of these, R ¹ and R ² are preferably hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and more preferably hydrogen atoms.

(In the formula (t-1), R ¹ and R ² are hydrogen atoms, halogen atoms, ionic functional groups or monovalent organic groups.)

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”). The specific diamine is a monovalent group in which one or more of R ³ to R ¹⁰ in the above formula (1) has an ionic functional group, and one or two of R ³ to R ¹⁰ are ionic functional groups. It is more preferably 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). The specific diamine may be used alone or in combination of two or more.

Further, as a preferable specific example of the tetracarboxylic acid diester used in the synthesis of the polymer (P), for example, the tetracarboxylic acid dianhydride represented by the above formula (t-1) is used as an alcohol such as methanol or ethanol. Examples thereof include compounds obtained by opening the ring using. Moreover, as a preferable specific example of the tetracarboxylic acid diester dihalide used in the synthesis of the polymer (P), a compound obtained by reacting the tetracarboxylic acid diester with a chlorinating agent such as thionyl chloride can be mentioned. .. The tetracarboxylic acid diester and the tetracarboxylic acid diester dihalide can be used alone or in combination of two or more.

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

In the above method [i], a tetracarboxylic acid dianhydride other than the specific tetracarboxylic acid dianhydride (hereinafter, also referred to as “other tetracarboxylic acid dianhydride”) and a diamine other than the specific diamine (hereinafter, “other”). It can also be used in combination with "diamine". The ratio of the specific tetracarboxylic acid dianhydride used is the total amount of the tetracarboxylic acid dianhydride used for the synthesis of the polyamic acid (P) from the viewpoint of sufficiently imparting lyotropic liquid liquidity to the polymer (P). It is preferably 50 mol% or more, and more preferably 75 mol% or more. The upper limit of the usage ratio is not particularly limited and can be arbitrarily set within the range of 100 mol% or less.

The ratio of the specific diamine used is 25 mol% or more with respect to the total amount of diamine used for the synthesis of polyamic acid (P) from the viewpoint of sufficiently imparting solubility and lyotropic liquid crystallinity to the polymer (P). It is preferably 50 mol% or more, more preferably 75 mol% or more, and further preferably 75 mol% or more. The upper limit of the usage ratio is not particularly limited and can be arbitrarily set within the range of 100 mol% or less.

(Other tetracarboxylic acid dianhydrides)
Other tetracarboxylic acid dianhydrides used for the synthesis of polyamic acid (P) include, for example, aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, aromatic tetracarboxylic acid dianhydrides and the like. Can be mentioned. Specific examples of these include, for example, butane tetracarboxylic acid dianhydride as an aliphatic tetracarboxylic acid dianhydride;
Examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-di). Oxotetratetra-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetra-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'-(tetratetra-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-franyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3 , 5,6-tricarboxy-2-carboxymethylnorbornan-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 acid dianhydride, Bicyclo [2.2.2] Octo- 7-En-2,3,5,6-tetracarboxylic acid dianhydride, ethylenediamine tetraacetic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, ethylene glycol bis (anhydrotri) Melitate), 1,3-propylene glycol bis (anhydrotrimeritate), etc .;
As the aromatic tetracarboxylic acid dianhydride, for example, 4,4'-biphthalic acid dianhydride, etc.;
In addition to these, the tetracarboxylic acid dianhydride described in JP-A-2010-97188 can be used. As for other tetracarboxylic acid dianhydrides, one of these can be used alone or in combination of two or more.

(Other diamines)
Examples of 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, as aliphatic diamines, for example, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane and the like;
As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), etc.;

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

(Synthesis of polyamic acid)
The polyamic acid (P) can be obtained by reacting the tetracarboxylic acid dianhydride as described above with a diamine, if necessary, with a molecular weight adjusting agent. The ratio of the tetracarboxylic acid dianhydride used in the synthesis reaction of the polyamic acid (P) to the diamine was 0 for the acid anhydride group of the tetracarboxylic acid dianhydride with respect to 1 equivalent of the amino group of the diamine. The ratio of 2 to 2 equivalents is preferable, and the ratio of 0.3 to 1.2 equivalents is more preferable.
When the tetracarboxylic acid dianhydride or 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 preferable, and triethylamine is particularly preferable. The ratio of the base used is preferably 0.5 to 5 equivalents with respect to the acidic functional group, and more preferably 1 to 2 equivalents. Similarly, if the tetracarboxylic acid dianhydride or diamine has a basic functional group, the reaction may be carried out after neutralization by adding an acid. As the acid, a carboxylic acid is preferable. The ratio of the acid used is preferably 0.5 to 5 equivalents with respect to the basic functional group, and more preferably 1 to 2 equivalents.
Examples of the molecular weight adjusting agent 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 phenylisocyanate and naphthylisocyanate. Can be mentioned. The proportion of the molecular weight adjusting agent used 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 acid dianhydride and the diamine used.

The synthetic reaction of the polyamic acid (P) is preferably carried out in an organic solvent. The reaction temperature at this time is preferably −20 ° C. to 150 ° C., more preferably 0 to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Examples of the organic solvent used in the reaction include an aprotonic polar solvent, a phenol solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. Among these organic solvents, one or more selected from the group consisting of aprotonic polar solvents and phenolic solvents (organic solvents of the first group), or one or more selected from the organic solvents of the first group. It is preferable to use a mixture of 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 used in the second group to the total amount of the organic solvent in the first group and the organic solvent in the second group is preferably 50% by mass or less, more preferably 40% by mass. It is less than or equal to, more preferably 30% by mass or less.

Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol. It is preferable to use one or more selected from the group consisting of and halogenated phenol as a solvent, or to use a mixture of one or more of these with another organic solvent in the above ratio range. The amount (a) of the organic solvent used shall be such that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50% by mass with respect to the total amount (a + b) of the reaction solution. Is preferable.

As described above, a reaction solution containing a polyamic acid (P) can be 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 a dehydration ring closure reaction, or the isolated polyamic acid may be purified and then dehydrated. It may be subjected to a ring closure reaction. Isolation and purification of polyamic acids can be performed according to known methods.

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

The polymer (P) can be obtained by dehydrating and ring-closing and imidizing the polyimide precursors (polyamic acid (P) and polyamic acid ester (P)) synthesized as described above. The polymer (P) may be a completely imidized product obtained by dehydrating and ring-closing all of the amic acid structure or the amic acid ester structure possessed by the polyimide precursor which is the precursor thereof, and the amic acid structure and the amic acid ester may be used. It may be a partially imidized product in which only a part of the structure is dehydrated and the ring is closed, and the amic acid structure or the amic acid ester structure and the imide ring structure coexist. The imidization ratio of the polymer (P) is preferably 50% or more, more preferably 75% or more, in order to obtain a coating film having a sufficiently high orientation regulating force in the use of a liquid crystal device. It is more preferably 85% or more, and particularly preferably 90% or more. This imidization ratio is expressed as a percentage of the ratio of the number of imide ring structures to the total number of amic acid structures and amic acid ester structures of polyimide and the number of imide ring structures.

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

In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of polyamic acid, acid anhydrides 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 closure catalyst, for example, a base catalyst such as pyridine, triethylamine and 1-methylpiperidine, and an acid catalyst such as methanesulfonic acid and benzoic acid can be used. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent used for the dehydration ring closure reaction include organic solvents exemplified as those used for the synthesis of polyamic acid (P). The reaction temperature of the dehydration ring closure reaction is preferably 0 to 200 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

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

The polymer (P) obtained as described above preferably has a solution viscosity of 10 to 2000 mPa · s, preferably 20 to 1000 mPa · s, when a solution having a concentration of 10% by mass is used. It is more preferable that it has a solution viscosity. The solution viscosity (mPa · s) of the polymer is 25 by using an E-type rotational viscometer for a polymer solution having a concentration of 10% by mass prepared using a good solvent (for example, water) of the polymer. It is a value measured at ° C.
The polystyrene-equivalent weight average molecular weight (M _w ) measured by gel permeation chromatography (GPC) of the polymer (P) is preferably 1,000 to 500,000, more preferably 2,000 to 300, It is 000. Further, the molecular weight distribution (M _w / M _n ) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (M _n ) measured by GPC is preferably 15 or less, more preferably 10 or less. be. Having such a molecular weight range makes it easy to secure a concentration range and a temperature range in which the composition exhibits lyotropic liquid crystallinity, which is suitable.

<Other ingredients>
The composition of the present disclosure may contain other components other than the above-mentioned polymer (P) as long as the purpose and effect of the present disclosure are not impaired.

[Other polymers]
Examples of other components include polymers other than the polymer (P) (hereinafter, also referred to as “other polymers”) and the like. Other polymers can be used to improve solution and electrical properties. Specific examples of such other polymers include polyamic acids obtained by reacting the other tetracarboxylic acid dianhydride with the other diamines, imidized polymers of the polyamic acids, and esters of the polyamic acids. Examples thereof include chemical polymers, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates and the like.
When other polymers are blended in the composition, the blending ratio is preferably 30 parts by mass or less, and 20 parts by mass or less, based on 100 parts by mass of the total amount of the polymers contained in the composition. It is more preferably 10 parts by mass or less.

[Bar-shaped molecules, etc.]
Examples of other components include rod-shaped molecules and rod-shaped nanostructures (hereinafter, also referred to as “rod-shaped molecules”). By applying shear stress to the composition, the orientation of rod-shaped molecules and the like can be controlled along with the uniaxial orientation of the polymer (P). Examples of the rod-shaped molecule include a dichroic dye and the like, 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, a virus and the like. Various functions can be imparted by controlling the orientation of rod-shaped 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 carbon nanotubes can form a wire or an actuator having conductivity anisotropy. When a rod-shaped molecule or the like is blended in the composition, the blending ratio thereof can be appropriately set according to the type of the rod-shaped molecule or the like within a range that does not impair the effects of the present disclosure.

Other components include, for example, compounds having at least one epoxy group in the molecule, functional silane compounds, surfactants, fillers, pigments, defoamers, sensitizers, dispersants, and antioxidants. Examples thereof include agents, adhesion aids, antistatic agents, leveling agents, antibacterial agents and the like. It should be noted that these blending ratios can be appropriately set according to each compound to be blended, as long as the effects of the present disclosure are not impaired.

[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, and the like. 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-trimethylpropaneamide, 1-butoxy-2-propanol, diacetone alcohol, dipropylene glycol monomethyl ether, 4-hydroxy-4- Methyl-2-pentanone, 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 Examples thereof include ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate and the like. These can be used alone or in admixture 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, 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 soluble in water, but is preferably an organic solvent having a boiling point lower than that of water. , Methanol, ethanol, n-propanol, i-propanol, acetone and tetrahydrofuran are more preferably at least one selected from the group. 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. It is more preferably 10% by mass or less.

The concentration of the polymer (P) in the composition of the present disclosure may be any concentration as long as the composition exhibits lyotropic liquid crystallinity, and is not particularly limited, but is preferably relative to the total amount of the solvent and the polymer (P). It is 1 to 30% by mass. According to the polymer (P), it 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, 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 the 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, etc., but is preferable. It is in the range of 1 to 30% by mass, more preferably 2 to 20% by mass, and particularly preferably 3 to 15% by mass. That is, the composition of the present disclosure may be applied to the surface of a substrate as described later, and preferably dried to form a coating film. At this time, when the solid content concentration is less than 1% by mass, it becomes difficult for the composition to exhibit lyotropic liquid crystallinity. On the other hand, when the solid content concentration exceeds 30% by mass, the film thickness of the coating film becomes excessive and it is difficult to obtain a good coating film, and the viscosity of the composition tends to increase and the coatability tends to decrease. be. The temperature at which the composition is prepared is preferably 10 to 90 ° C, more preferably 20 to 65 ° C.

[Riotropic LCD]
The composition of the present disclosure is a mixture of the polymer (P) and a solvent, and preferably exhibits liotropic liquid crystallinity at at least a part of the temperature in the range of 0 ° C. or higher and lower than 100 ° C. The temperature range exhibiting the lyotropic liquid crystal property is preferably a temperature range including 20 to 40 ° C., more preferably a temperature range including 20 to 60 ° C., and further preferably 20 ° C. or more and less than 100 ° C. It is a temperature range including 10 to 80 ° C. By applying the composition in a lyotropic liquid crystal state onto a substrate and causing it to flow by shear stress, it is possible to obtain a coating film in which the molecular chains of the polymer (P) are self-organized and uniaxially oriented in the shear direction. In the process of coating and drying, it is desirable to control the composition so as not to deviate from the temperature range and concentration range exhibiting lyotropic liquid crystallinity. In the process of coating or drying, when the composition reaches a temperature or concentration 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 in a state where the ionic functional group in the partial structure represented by the above formula (1) is ionized. , Contained in the composition together with the solvent.

The polymer (P) is a rigid rod-shaped polymer and acts as a mesogen in a solvent. Furthermore, since 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 uniaxially linear aromatic polyimide, it can be stacked between molecules at the thin film interface. It is possible to form a liquid crystal alignment film that is easily oriented in-plane and has an excellent orientation regulating force. Further, by introducing a rod-shaped molecule or the like (guest) into the lyotropic liquid crystal field (host) created by the polymer (P), the rod-shaped molecule or the like 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 by using the above composition (liquid crystal alignment agent). When the liquid crystal element is a liquid crystal display element, the drive mode thereof is not particularly limited, and can be applied to various drive 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. The substrate and the like used differ depending on the desired drive mode, but the case of manufacturing an FFS type liquid crystal display element will be illustrated below.

[Step 1: Formation of coating film]
First, the composition is applied onto the substrate, and then the coated surface is heated to form a coating film on the substrate. When manufacturing an FFS type liquid crystal display element, an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb-teeth shape and one surface of a facing substrate not provided with an electrode are formed. The composition is preferably applied by a bar coater method, a die coater method or a blade coater method, respectively. These methods are preferable in that the molecular chains of the polymer (P) are easily oriented by the flow due to shear stress.
Here, as the substrate, for example, glass such as float glass and soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (aliphatic olefin) can be used. As the transparent conductive film provided on one surface of the substrate, a NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG Corporation in the United States), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), and the like are used. 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, a film made of a metal such as chromium can be used. When applying the composition, in order to further improve the adhesiveness between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, etc. are formed on the surface of the substrate surface on which the coating film is formed. May be pretreated to be applied in advance.

After the composition is applied, preheating is preferably performed for the purpose of preventing the applied composition from dripping. The prebake temperature is preferably 30 to 100 ° C, more preferably 40 to 80 ° C, and particularly preferably 40 to 60 ° C. The prebake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Then, a firing (post-baking) step is carried out 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 firing temperature (post-baking temperature) at this time is preferably 60 to 300 ° C, more preferably 100 to 250 ° C. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. In the heating step, it is preferable that the coating film made of the liquid crystal aligning agent applied on the substrate is in a state where the molecular chains of the polymer (P) are oriented by the flow due to shear stress, and dried in that state. As a result, the liquid crystal alignment ability is imparted to the coating film by a simple operation, and the liquid crystal alignment film is formed. The film 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 liquid crystal alignment film is formed by removing the solvent. At this time, when the polymer contained in the composition has an imide ring structure and an amic acid structure, the dehydration ring closure reaction is promoted by further heating after the coating film is formed, and the more imidized coating film is formed. May be.

[Step 2: Ion cross-linking treatment]
If necessary, the substrate on which the liquid crystal alignment film is formed may be immersed in a polyvalent cation aqueous solution for ion cross-linking treatment. 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 electrical 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 metal cation or an organic poly cation, but is preferably an alkaline earth metal ion, and particularly preferably Ca ²⁺ , Sr ²⁺ , or Ba ²⁺ . The counterion 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 soaking time is preferably 1 to 20 minutes, more preferably 2 to 10 minutes. Further, it is desirable to remove excess ionic components by immersing the substrate in a polyvalent cation aqueous solution, rinsing the removed substrate with pure water, and further immersing the substrate in pure water.

[Step 3: Construction of liquid crystal cell]
A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above and arranging the liquid crystal between the two substrates arranged opposite to each other. For example, the following two methods can be mentioned for manufacturing a liquid crystal cell. The first method is a conventionally known method. First, two substrates are placed facing each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the sealant are bonded together. A liquid crystal cell is manufactured by injecting and filling the liquid crystal in the cell gap partitioned by the above and then sealing the injection hole. The second method is a method called the ODF (One Drop Fill) method. For example, an ultraviolet light-curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal is further dropped on a predetermined number of places on the liquid crystal alignment film surface. After that, the other substrate is bonded so that the liquid crystal alignment film faces each other, 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 to produce a liquid crystal cell. .. Regardless of which method is used, the liquid crystal cell manufactured as described above is further heated to a temperature at which the liquid crystal used is isotropic, and then slowly cooled to room temperature to obtain a flow orientation during liquid crystal filling. It is desirable to remove it.

As the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal, and among them, nematic liquid crystal is preferable, and for example, shift-based liquid crystal, azoxy-based liquid crystal, biphenyl-based liquid crystal, phenylcyclohexane-based liquid crystal, ester-based liquid crystal, terphenyl-based liquid crystal, and biphenyl. A cyclohexane-based liquid crystal, a pyrimidine-based liquid crystal, a dioxane-based liquid crystal, a bicyclooctane-based liquid crystal, a Cuban-based liquid crystal, or the like can be used. Further, to these liquid crystals, for example, 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). A ferroelectric liquid crystal display such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate may be added and used.

Then, a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell. As the polarizing plate attached to the outer surface of the liquid crystal cell, a polarizing plate called an "H film" in which polyvinyl alcohol is stretched and oriented to absorb iodine is sandwiched between a cellulose acetate protective film or the H film itself. A polarizing plate made of the above can be mentioned.

<Phase difference plate>
The retardation plate of the present disclosure is formed by the composition prepared as described above. Specifically, first, the above composition is first placed on a substrate (eg, 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. It is applied, and then the molecular chain of the polymer (P) is dried in a state of being oriented by the flow due to shear stress. As a result, a retardation plate is formed.

<Polarizer>
The polarizing plate of the present disclosure is formed of a composition containing a dichroic dye or a metal prepared as described above. For example, in order to prepare a guest-host type polarizing plate, first, a composition containing a polymer (P), a dichroic dye and a solvent is applied to a substrate (for example, a glass substrate, triacetyl cellulose (TAC)). It is preferably applied onto polyethylene terephthalate, polymethylmethacrylate, etc. by the bar coater method, the die coater method, or the blade coater method. Next, a polarizing plate can be obtained by drying the molecular chain of the polymer (P) in a state of being oriented by flow due to shear stress. Further, if necessary, a resin film (protective film) may be attached to one surface or both surfaces of the polarizing plate.
Further, in order to produce a reflective polarizing plate, a composition containing a polymer (P), a metal (metal nanorod, metal nanowire, or metal ion) and a solvent is used to form a guest-host type polarizing plate. A polarizing plate can be obtained by applying the composition on the substrate in the same manner as in the production method, and then drying the molecular chains of the polymer (P) in a state of being oriented by the flow due to shear stress. However, when metal ions are used as the metal, the elemental metal is anisotropically precipitated along the polymer (P) by reduction.

The liquid crystal element of the present disclosure can be effectively applied to various applications, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcoder, 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 liquid crystal televisions and information displays, dimming films, retardation plates, polarizing plates and the like.

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 acid dianhydride)
TA-1; pyromellitic acid dianhydride (other tetracarboxylic acid dianhydrides)
TB-1; 1,4,5,8-naphthalenetetracarboxylic acid dianhydride TB-2; 4,4'-biphthalic acid dianhydride TB-3; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride Anhydride

(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- Diaminobenzene sulfonic acid

The imidization ratio [%] of the polyimide was measured by the following method.
The polyimide solution was poured into pure water, the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, 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 represented by the following formula (a).
Imidization rate [%] = (((1-A ¹ ) / A ² ) x α) x 100 ... (a)
(In formula (a), A ¹ is the proton-derived peak area of the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the NH group in the precursor of the polymer. The ratio of the number of other protons to one proton of.)

[Example 1]
(1) Synthesis of polymer In a three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introduction tube, diamine (DA-1) (3.79 g, 11.0 mmol), m-cresol (50 mL), and triethylamine. (2.43 g, 24.0 mmol) was added and stirred under nitrogen. After dissolving 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. The mixture was stirred for 12 hours. After completion of the reaction, the reaction solution was diluted with m-cresol and added dropwise to acetone to coagulate. The obtained coagulated product was filtered, washed in acetone, and vacuum dried at 120 ° C. to obtain a polymer (6.64 g, yield) having a partial structure represented by the following formula (PI-1) of a brown powder. A rate of 88%) was obtained. FIG. 1 shows the measurement results of the ¹ H-NMR spectrum (DMSO-d ⁶ , 400 MHz) of the polymer (PI-1). The imidization rate of the polymer (PI-1) was 99% or more.

(2) Preparation of composition and evaluation of solubility The polymer (PI-1) obtained in (1) above is dissolved by adding water and heating and stirring at 60 ° C. to dissolve the polymer (PI-1). Was obtained. The composition (C-1) was prepared by filtering this solution with a filter having a pore size of 0.2 μm.
The solubility was evaluated as "good" when an aqueous solution having a solid content concentration of 1% by mass or more could be prepared, and "good" when an aqueous solution having a solid content concentration of 1% by mass or more could not be prepared. "Bad". As a result, it was evaluated as "good" in this example.

(3) Evaluation of Riotropic Liquid Crystal Properties The composition (C-1) obtained in (2) above was dropped onto a glass substrate and observed with a polarizing microscope. The evaluation is "good" when optical anisotropy is observed under orthogonal Nicol at at least a part of the temperature in the range of 0 ° C or higher and lower than 100 ° C, and at any temperature of 0 ° C or higher and lower than 100 ° C. The case where no optical anisotropy was observed was regarded as "defective". As a result, in this example, optical anisotropy was observed in the solid content concentration range of 6 to 20% by mass and the temperature range of 10 ° C. to 90 ° C., which was evaluated as "good". rice field.
FIGS. 3 to 5 show polarized micrographs (100 times) of the composition (C-1) in which the solid content concentration of the polymer is 10% by mass. FIG. 3 is a photograph immediately after the composition is dropped onto the glass substrate, FIG. 4 is a photograph after the composition is weakly dried after dropping and concentrated on the glass substrate, and FIG. 5 is a photograph of the composition. It is a photograph after the glass substrate is sandwiched between the glass substrates from above after dropping, and the upper glass substrate is laterally displaced to apply shear stress.

[Examples 2 to 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 acid dianhydride and diamine were changed as shown in Table 1 below. bottom. Further, the compositions (C-2 to C-9) were prepared using the obtained polymers (PI-2 to PI-9), and their 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 diamine column represents the ratio (molar portion) of each compound to 100 mol parts of the total amount of diamine used for the synthesis of the polymer. In Comparative Examples 1 and 4, the solubility was "poor" and the lyotropic liquid crystallinity could not be evaluated, so they are shown as "-" in Table 1.
FIG. 2 shows the measurement results of the ¹ H-NMR spectrum (DMSO-d ⁶ , 400 MHz) of the polymer (PI-2). The imidization rate of the polymer (PI-2) was 99% or more. In Example 2, optical anisotropy was observed in the temperature range of 20 to 70 ° C. when the solid content concentration of the polymer was 2% by mass, and 40 to 80 ° C. in the temperature range of 3 to 6% by mass, and the liquid crystallinity was high. 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 obtain a solid content concentration of 6% by mass. Was obtained. The composition (C-10) was prepared by filtering this solution through a filter having a pore size of 0.2 μm.
(2) Formation of liquid crystal alignment film On each surface of a glass substrate in which a flat plate electrode, an insulating layer and a comb-shaped electrode are laminated on one side in this order, and a facing glass substrate on which no electrode is provided, the above ( The composition (C-10) prepared in 1) is applied using a wire bar so that the film thickness is 0.1 μm, and dried with warm air at 60 ° C. for 5 minutes and in an oven at 120 ° C. for 30 minutes. , A liquid crystal alignment film was formed.
(3) Manufacture of liquid crystal display element With respect to the pair of substrates having the liquid crystal alignment film produced in (2) above, an aluminum oxide ball having a diameter of 5.5 μm is contained, leaving a liquid crystal injection port on the edge of the surface on which the liquid crystal alignment film is formed. After applying the epoxy resin adhesive by screen printing, the substrates are overlapped and crimped so that the projection direction of the polarization axis on the substrate surface at the time of light irradiation is antiparallel, and the adhesive is heated at 150 ° C. for 1 hour. It was 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 then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of liquid crystal injection, this was heated at 120 ° C. and then slowly cooled to room temperature. Next, a polarizing plate was attached to both outer surfaces of the substrate to manufacture an FFS type liquid crystal display element.
(4) Evaluation of liquid crystal orientation With respect to the liquid crystal display element manufactured in (3) above, the presence or absence of anomalous domains in the change in brightness when a voltage of 5 V is turned on / off (applied / released) is determined by a microscope at a magnification of 50 times. Observed. The evaluation was "good" when no abnormal domain was observed, and "poor" when no abnormal domain was observed. As a result, it was evaluated as "good" in this example.

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

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

[Example 6: Fabrication and evaluation of retardation plate]
Using the composition (C-1) containing the polymer (PI-1) obtained in Example 1, the composition (C-1) was applied onto a glass substrate with a bar coater so that the film thickness was 1 μm, and the temperature was 60 ° C. The mixture was dried with warm air for 5 minutes and in an oven at 120 ° C. for 30 minutes to form a retardation plate.
In the evaluation of the phase difference, the in-plane phase difference (literation) is measured by the parallel Nicol rotation method, and when the in-plane phase difference is 20 nm or more at a wavelength of 550 nm, it is regarded as “good”, and the in-plane phase difference is less than 20 nm. If it was, it was regarded as "defective". As a result, the result was "good" in this example.
[Comparative Example 9]
In Example 6 above, the composition is prepared in the same manner as in Example 6 except that the polymer contained in the composition is changed as shown in Table 2 below, and a retardation plate is formed and a retardation difference is formed. Was evaluated. The evaluation results are shown in Table 2 below.

[Example 7: Preparation 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 are used with respect to 100 parts by mass of the polymer (PI-1). Sex dye C. I. 1 part by mass of Direct Orange 39 (manufactured by Santa Cruz Biotechnology) was added and diluted with water to obtain a solution having a solid content concentration of 10% by mass. The composition (C-14) was prepared by filtering this solution through a filter having a pore size of 0.2 μm.
(2) Formation of polarizing plate Using the composition (C-14) prepared in (1) above, the composition (C-14) was applied onto a glass substrate with a bar coater so that the film thickness was 10 μm, and the temperature was 60 ° C. Drying was carried out in the wind for 5 minutes and in an oven at 120 ° C. for 30 minutes to form a guest-host type polarizing plate.
(3) Evaluation of dichroism ratio Evaluation is performed by measuring the polarization absorption spectrum, and when the dichroism ratio is 2 or more, it is regarded as "good", and when the dichroism ratio is less than 2, it is "poor". ". As a result, the result was "good" in this example. The bichromatic ratio is the ratio of the absorbance (A _II ) when the polarization axis is parallel to the shear direction and the absorbance (A _⊥ ) when the polarization axis is perpendicular to the shear direction at a wavelength of 500 nm (A _II ). / A _⊥ ).
[Comparative Example 10]
In Example 7, the 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, and a polarizing plate was formed, and dichroism was formed. The ratio was evaluated. The evaluation results are shown in Table 2 below. In Table 2, "-" indicates that the corresponding evaluation was not carried out.

From the above results, the composition of the example using the polymer (P) is observed to have optical anisotropy under orthogonal Nicol in a temperature range of 0 ° C. or higher and lower than 100 ° C., and exhibits lyotropic liquid crystallinity. Became clear. Further, the polymer (P) exhibited lyotropic liquid crystallinity in water and at a low polymer concentration of 20% by mass or less. Moreover, the liquid crystal display element, the retardation plate and the polarizing plate produced by using the composition of the example showed good optical characteristics. On the other hand, in the composition of the comparative example, optical anisotropy could not be observed at any temperature. From these results, it was clarified that the composition exhibiting lyotropic liquid crystallinity can be obtained under mild conditions by using the polymer (P).

Claims (14)

A composition exhibiting lyotropic liquid crystallinity, which is obtained by mixing a polymer (P) having a partial structure represented by the following formula (1) and a solvent.
The polymer (P) is a compound represented by the following formula (t-1) in an amount of 75 mol% or more based on the total amount of the tetracarboxylic acid dianhydride used for the synthesis of the polymer (P). Is a polymer that is
A composition exhibiting lyotropic liquid crystallinity, which contains water in an amount of 50% by mass or more based on the total amount of the 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 independently hydrogen atoms, halogen atoms or monovalent organic groups. K is 0 or 1.)

(In the formula (t-1), R ¹ and R ² are hydrogen atoms, halogen atoms, ionic functional groups or monovalent organic groups.) The composition according to claim 1, which exhibits lyotropic liquid crystallinity in at least a part of a temperature range of 0 ° C. or higher and lower than 100 ° C. The composition according to claim 1 or 2 , wherein the ionic functional group is 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. The composition according to any one of claims 1 to 3 , wherein the ionic functional group is an acidic functional group. The polymer (P) is a polymer having a partial structure represented by the following formula (2) as a partial structure represented by the above formula (1), according to any one of claims 1 to 4 . The composition described.

(In 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 from each other.) A polymer (P) having a partial structure represented by the following formula (1), at least one selected from the group consisting of a solvent, a dichroic dye, a dye aggregate, a quantum rod, a metal nanorod, and a carbon nanotube. It is a composition obtained by mixing
The polymer (P) is a compound represented by the following formula (t-1) in an amount of 75 mol% or more based on the total amount of the tetracarboxylic acid dianhydride used for the synthesis of the polymer (P). Is a polymer that is
A composition containing water in an amount of 50% by mass or more based on the total amount of the 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 independently hydrogen atoms, halogen atoms or monovalent organic groups. K is 0 or 1.)

(In the formula (t-1), R ¹ and R ² are hydrogen atoms, halogen atoms, ionic functional groups or monovalent organic groups.) A liquid crystal alignment agent obtained by mixing a polymer (P) having a partial structure represented by the following formula (1) and a solvent.
The polymer (P) is a compound represented by the following formula (t-1) in an amount of 75 mol% or more based on the total amount of the tetracarboxylic acid dianhydride used for the synthesis of the polymer (P). Is a polymer that is
A liquid crystal alignment agent containing water in an amount of 50% by mass or more of the total amount of the 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 independently hydrogen atoms, halogen atoms or monovalent organic groups. K is 0 or 1.)

(In the formula (t-1), R ¹ and R ² are hydrogen atoms, halogen atoms, ionic functional groups or monovalent organic groups.) A liquid crystal alignment film formed by using the composition according to any one of claims 1 to 6 . A retardation plate formed by using the composition according to any one of claims 1 to 6 . A polarizing plate formed by using the composition according to any one of claims 1 to 6 . The composition according to any one of claims 1 to 6 is applied to a substrate in a lyotropic liquid crystal state, and the molecular chain of the polymer (P) is dried in a state of being oriented by flow due to shear stress. Method of manufacturing a membrane. A liquid crystal element comprising the liquid crystal alignment film according to claim 8 . A composition obtained by mixing an imidized polymer obtained by reacting a tetracarboxylic acid dianhydride with a diamine and a solvent.
More than 75 mol% with respect to the total amount of the tetracarboxylic acid dianhydride is a compound represented by the following formula (t-1).
50 mol% or more based on the total amount of the diamine is at least one selected from the group consisting of the compounds represented by the following formulas (d-1) to (d-16).
A composition containing water in an amount of 50% by mass or more based on the total amount of the solvent .

(In the formula (t-1), R ¹ and R ² are hydrogen atoms, halogen atoms, ionic functional groups or monovalent organic groups.)

A composition obtained by mixing an imidized polymer obtained by reacting a tetracarboxylic acid dianhydride with a diamine and a solvent.
The tetracarboxylic acid 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).
A composition containing water in an amount of 50% by mass or more based on the total amount of the solvent .

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