KR20190133750A - The composition, a liquid crystal aligning agent, a liquid crystal aligning film, a retardation plate, a polarizing plate, the manufacturing method of a liquid crystal aligning film, and a liquid crystal element - Google Patents

Abstract

The composition which shows lyotropic liquid crystalline property obtained by mixing the polymer (P) which has a partial structure represented by Formula (1), and a solvent is used. However, in Formula (1), at least 1 of R <^1> -R <^10> is monovalent group which has an ionic functional group, and a remainder is a hydrogen atom, a halogen atom, or monovalent organic group each independently. k is 0 or 1;

Description

Composition, liquid crystal aligning film, retardation plate, polarizing plate, manufacturing method of alignment film and liquid crystal element

(Cross-reference of related application)

This application is based on the JP Patent application 2017-115199 of an application on June 12, 2017, and uses the content of the description here.

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

The liquid crystal includes a thermotropic liquid crystal (melt type) showing liquid crystal at a certain temperature range and a lyotropic liquid crystal (solution type) showing liquid crystal at a certain concentration range. Although the lyotropic liquid crystalline polymer is isotropic because there is no regularity in the arrangement of molecular chains below the critical concentration, the lyotropic liquid crystalline polymer expresses the liquid crystal state above the critical concentration. In this liquid crystal state, molecular chains are aggregates of minute domains arranged in one direction and exhibit optical anisotropy. In addition, when the solution in the liquid crystal state is sheared, the molecular chain is aligned in the flow direction. For example, it is known that the aromatic polyamide represented by Kevlar is dissolved in strong acids such as concentrated sulfuric acid, and the rich solution exhibits lyotropic liquid crystallinity. By spinning from the solution in the lyotropic liquid crystal state, molecular chains are oriented in the fiber direction, whereby high-performance fibers having high elastic modulus can be produced.

In order to realize a lyotropic liquid crystalline polymer, it is necessary to use a rigid rod-shaped polymer. Generally, a rigid rod-shaped polymer has difficulty in solubility in water or an organic solvent, and corrosive solvents such as sulfuric acid. It was necessary to melt | dissolve at high temperature using the high boiling point polar solvent.

In polymers having a bent structure such as polyamide or polyxylene, materials that introduce ionic functional groups to ensure solubility and exhibit lyotropic liquid crystallinity under mild conditions have been reported to have applications in retardation plates, polarizing plates, and the like. It has been examined (Non Patent Literature 1, Patent Literatures 1 to 3). Moreover, the material which shows lyotropic liquid crystalline about polyimide is reported (nonpatent literature 2-4), and pioneering application research is performed by Neuber etc. about a polyimide precursor (nonpatent literature 5-6).

International Publication No. 2009/130675 International Publication No. 2010/020928 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, Volume 34, pp. 587-595.  Macromol. Chem. Phys., 2002, Vol. 203, pp. 598-604.  Advanced Functional Materials (Adv. Funct. Mater.), 2003, Vol. 13, p. 387-391.

In order to express the excellent orientation regulation force with respect to a liquid crystal, the polyimide-type material has been used suitably for the orientation control of a liquid crystal. If a material exhibiting lyotropic liquid crystallinity can be obtained from a polyimide-based material having an excellent orientation control force or the like, it may be oriented by shear flow by a simple coating process, and thus a high-performance liquid crystal alignment film, a retardation plate, a polarizing plate, It is expected that it can be formed at low cost.

However, as shown in the non-patent documents 2 to 4, although a material exhibiting lyotropic liquid crystallinity has been reported also in polyimide, a corrosive solvent such as concentrated sulfuric acid or cresol is required for dissolution of the polyimide (Non-Patent Literature). 2-4) The material which needs high temperature for lyotropic liquid crystalline expression (nonpatent literature 3, 4), and shows lyotropic liquid crystalline on mild conditions is not known. In addition, in the polyimide precursor shown in Nonpatent Documents 5-6, the heat imidation of a coating film is necessary for polyamic acid ester, and high temperature (about 100 degreeC) and high concentration (50 mass%) are required for lyotropic liquid crystalline expression. Problem). In order to obtain a thin film by coating on a substrate, from a viewpoint of industrial productivity, an environment, etc., it is a low environmental load solvent like water and an organic solvent, for example, the temperature below 100 degreeC (preferably low temperature about room temperature). In addition, it is preferable to express lyotropic liquid crystallinity at a sufficiently low concentration. That is, the composition which shows lyotropic liquid crystalline on the conditions which are mild in temperature, a solvent, and a density | concentration is calculated | required by the polyimide excellent in the orientation regulation force etc.

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

According to the present disclosure, the following means are provided.

The composition which shows lyotropic liquid crystallinity obtained by mixing the polymer (P) which has a partial structure represented by <1> 'following formula (1), and a solvent.

(In formula (1), at least 1 of R <^1> -R <^10> is monovalent group which has an ionic functional group, and a remainder is respectively independently a hydrogen atom, a halogen atom, or monovalent organic group. K is 0 or 1)

<2> 액정 The liquid crystal aligning film formed using the said composition.

<3> Retardation plate formed using the said composition.

<4> 편광 Polarizing plate formed using said composition.

Liquid crystal aligning agent obtained by mixing the polymer (P) which has a partial structure represented by <5> 'above formula (1), and a solvent.

<6> The manufacturing method of the liquid crystal aligning film which apply | coats the said composition to a board | substrate in a lyotropic liquid crystal state, and is dried in the state which orientated the molecular chain of the said polymer (P) by the flow by a shear stress.

According to the present disclosure, a composition exhibiting lyotropic liquid crystallinity under mild conditions by a polyimide having excellent orientation control force or the like can be obtained. Moreover, since the polymer component in the composition of this indication is orientated uniformly in a large area by a simple application | coating process, a liquid crystal aligning film, a retardation plate, a polarizing plate, etc. can be formed at low cost.

1 is a ¹ H-NMR spectrum of a polymer (PI-1).
2 is a ¹ H-NMR spectrum of a polymer (PI-2).
3 is a polarized light micrograph after dropping the composition (C-1) onto the substrate.
4 is a polarized light micrograph after the composition (C-1) is concentrated on a substrate.
5 is a polarized light micrograph after applying a shear force to the composition (C-1).

(Form to carry out invention)

The composition of this indication is a composition obtained by mixing the polymer (P) which has a partial structure represented by said Formula (1), and a solvent, and shows lyotropic liquid crystalline. Below, each component contained in the composition of this indication and other components mix | blended arbitrarily as needed are demonstrated.

<Polymer (P)>

The polymer (P) is a polyimide, and for example, at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester and tetracarboxylic acid diester dihalide, It can obtain by imidating the polyimide precursor obtained by superposition | polymerization which used diamine for the raw material composition.

As R <^1> -R <^10> in Formula (1), as a monovalent organic group, a hydrocarbon group is preferable and a C1-C5 alkyl group is more preferable. The monovalent group having an ionic functional group is "* -L ¹ -X ¹ " (wherein L ¹ is a single bond or a divalent linking group and X ¹ is an ionic functional group. "*" Is a bond bonded to a benzene ring. Hand). If here, L ¹ is a divalent connecting group, and specific examples of L ^1, alkanediyl group, the art alkanediyl group having 1 to 5 carbon atoms of the carbon-carbon bond between a group containing -O-, -OR ¹³ - * * (However, R ¹³ is a divalent hydrocarbon group, and "**" represents a bond which is bonded to X ^1. ), Etc. are mentioned.

An ionic functional group is a functional group which forms a cation or an anion in water. Although it does not specifically limit as an ionic functional group, Since the solubility of the polymer (P) with respect to the solvent containing water can be made higher, a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, an ammonium group, a pyridinium group, and imidazole It is preferable that they are a cerium group or a guanidinium group, or their salts. 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, as an ionic functional group, it is preferable that they are a sulfonic acid group, a phosphonic acid group, or a carboxylic acid group, or their salts, and it is especially preferable that they are a sulfonic acid group or its salt. 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 in particular, phase separation is carried out in a high polar solvent. It is speculated that self-organization made by driving force can be promoted and contribute to increase of anisotropy.

When the ionic functional group is a salt of an acidic functional group or a basic functional group, for example, as a pair ion of an acidic functional group (sulfonic acid group, phosphonic acid group, carboxylic acid group, etc.), for example, Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Zn ²⁺ , Pb ²⁺ , Al ³⁺ , La ³⁺ , Ce ³⁺ , Y ³⁺ , Yb ³⁺ , Gd ³⁺ , NH _4-t Q _t ⁺ (where Q is 1 to 20 carbon atoms) And a hydrocarbon group, 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. In addition, as a counter ion of the basic functional groups (ammonium, pyridinium nyumgi, such as imidazole ryumgi guanidinyl nyumgi), for example, ^{Cl -, Br -, I -} , R 14 COO - ( However, R ¹⁴ is C 1 The hydrocarbon group of -20.) Etc. are mentioned. In the case where the ionic functional group is a carboxylic acid group, the acid dissociation constant of the carboxylic acid is low, and since the proton is difficult to dissociate under acidic conditions and the ionicity is lowered, a salt is preferably formed with a strong base.

In the monovalent group which has an ionic functional group, L <^1> can be suitably selected according to the kind of 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, more preferably an alkanediyl group having 1 to 3 carbon atoms. to be.

At least ^{one of} R ¹ to R ¹⁰ may have an ionic functional group, and the number of ionic functional groups in the formula (1) is not particularly limited. The number of ionic functional groups (that is, the number of monovalent groups having an ionic functional group in R ¹ to R ¹⁰ ) in the formula (1) is preferably 1 to 4, and more preferably 1 or 2 . The ionic functional group preferably has a partial structure derived from the diamine (that is, at least a part of R ³ to R ¹⁰ ) from the point of showing good lyotropic liquid crystallinity and the high degree of freedom of selectivity of the material.

Polymer (P) is a partial structure represented by the above formula (1), and is composed 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). It is more preferable that it is a polymer which has at least 1 sort (s) selected, and it is especially preferable that it is a polymer which has the partial structure represented by following formula (2).

(M is a cation in Formula (2)-Formula (4). K is 0 or 1. However, when k = 1, some M in a formula may mutually be same or different.)

As the cation of M, 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 Q _t ⁺ and the like. As a cation of M, since the solubility of the polymer (P) with respect to an aqueous solvent can be made higher, a monovalent cation is preferable, Among these, NH4 _{- tQt} ⁺ is preferable and tertiary ammonium ion This is more preferable.

In addition, in this specification, "tetracarboxylic acid diester" means the compound in which two out of four carboxyl groups which tetracarboxylic acid has are esterified, and the remaining two are carboxyl groups. The term "tetracarboxylic acid diester dihalide" means a compound in which two of the four carboxyl groups possessed by tetracarboxylic acid are esterified and the remaining two are halogenated. Examples of the "polyimide precursor" include polyamic acid and polyamic acid ester. The "organic device" means a group containing a carbon atom, and may contain a hetero atom in the structure.

In this specification, a "hydrocarbon group" is a meaning containing a linear hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" means a straight chain hydrocarbon group and a branched hydrocarbon group composed only of a chain structure without including a cyclic structure in the main chain. However, saturated or unsaturated may be sufficient. An "alicyclic hydrocarbon group" means a hydrocarbon group which contains only the structure of an alicyclic hydrocarbon as a ring structure, and does not contain an aromatic ring structure. However, it does not need to consist only of the structure of an alicyclic hydrocarbon, but also includes the thing which has a linear structure in one part. An "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be comprised only with an aromatic ring structure, and the structure of a linear structure and an alicyclic hydrocarbon may be included in the one part.

As a monomer used in the synthesis | combination of a polymer (P), at least 1 sort (s) chosen from the group which consists of tetracarboxylic dianhydride, tetracarboxylic acid diester, and tetracarboxylic acid diester dihalide, and diamine can be used. Preferable specific examples of the tetracarboxylic dianhydride include compounds represented by the following formula (t-1) (hereinafter also referred to as "specific tetracarboxylic dianhydride"). In addition, specific tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types. In R <^1> and R <^2> in formula (t-1), a monovalent organic group is a C1-C20 hydrocarbon group, the group in which the hydrogen atom which the said hydrocarbon group has substituted by the ionic functional group, etc. are mentioned. Among 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 formula (t-1), R <^1> and R <^2> is a hydrogen atom, a halogen atom, an ionic functional group, or monovalent organic group.)

As a diamine used for the synthesis | combination of a polymer (P), it is preferable to contain the diamine (henceforth "specific diamine") which has an ionic functional group. Specific diamine is a monovalent group in which at least one of R ³ to R ¹⁰ in the formula (1) is an ionic functional group, and one or two of R ³ to R ¹⁰ are a monovalent group having an ionic functional group. More preferred.

As a preferable specific example of a specific diamine, the compound etc. which are represented by following formula (d-1)-(d-16) are mentioned. In addition, specific diamine can be used individually by 1 type or in combination of 2 or more types.

Moreover, as a preferable specific example of the tetracarboxylic-acid diester used in the synthesis | combination of a polymer (P), the tetracarboxylic dianhydride represented by said formula (t-1) uses alcohol, such as methanol and ethanol, for example. The compound etc. which are obtained by ring-opening are mentioned. Moreover, as a preferable specific example of the tetracarboxylic-acid diester dihalide used in the synthesis | combination of a polymer (P), the compound obtained by making the said tetracarboxylic-acid diester react with chlorinating agents, such as thionyl chloride, etc. are mentioned. . Moreover, tetracarboxylic acid diester and tetracarboxylic acid diester dihalide can be used individually by 1 type or in combination of 2 or more types, respectively.

[Polyamic acid]

Polyamic acid (henceforth "polyamic acid (P)") as a precursor of a polymer (P) can be obtained, for example by making tetracarboxylic dianhydride and diamine react. Specifically, [i] a method of directly reacting a tetracarboxylic dianhydride containing a specific tetracarboxylic dianhydride and a diamine containing a specific diamine; [ii] a tetracarboxylic acid containing a specific tetracarboxylic dianhydride; After neutralizing a dianhydride with a base, the method of making tetracarboxylic dianhydride and the diamine containing a specific diamine, etc. are mentioned.

In the said method [i], tetracarboxylic dianhydride other than specific tetracarboxylic dianhydride (henceforth "other tetracarboxylic dianhydride"), diamine other than specific diamine (henceforth "other diamine"). May be used together). The use ratio of specific tetracarboxylic dianhydride is 50 mol with respect to the total amount of tetracarboxylic dianhydride used for the synthesis | combination of a polyamic acid (P) from a viewpoint of fully providing a lyotropic liquid crystalline property to a polymer (P). It is preferable to set it as% or more, and it is more preferable to set it as 75 mol% or more. The upper limit of the said use ratio is not specifically limited, It can set arbitrarily in the range of 100 mol% or less.

It is preferable that the use ratio of specific diamine shall be 25 mol% or more with respect to the total amount of the diamine used for the synthesis | combination of a polyamic acid (P) from a viewpoint of fully providing solubility and lyotropic liquid crystalline property to a polymer (P). It is more preferable to set it as 50 mol% or more, and it is still more preferable to set it as 75 mol% or more. The upper limit of the said use ratio is not specifically limited, It can set arbitrarily in the range of 100 mol% or less.

(Other tetracarboxylic dianhydride)

As other tetracarboxylic dianhydride used for the synthesis of polyamic acid (P), aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, butane tetracarboxylic dianhydride etc .;

As alicyclic tetracarboxylic dianhydride, For example, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, 5- (2,5-di Oxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran- 3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2, 4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclo Hexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, bicyclo [3.3.0] octane-2,4 , 6,8-tetracarboxylic acid 2: 4,6: 8-2 anhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-2 anhydride, 4,9- dioxa-tricyclo [5.3.1.0 ^2,6] undecane -3,5,8,10- tetrahydro-one, 1,2,4,5-cyclohexane Tet Carbonic acid dianhydride, bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, ethylenediamine tetraacetic acid dianhydride, 1,2,3,4-cyclopentanetetra Carboxylic acid dianhydride, ethylene glycol bis (anhydro trimellitate), 1,3-propylene glycol bis (anhydro trimellitate) and the like;

As aromatic tetracarboxylic dianhydride, For example, 4,4'-biphthalic acid dianhydride etc .;

In addition to these, tetracarboxylic dianhydride described in JP 2010-97188 A can be used. In addition, other tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

(Other diamine)

As other diamine used for the synthesis of polyamic acid (P), an aliphatic diamine, an alicyclic diamine, an aromatic diamine, diamino organosiloxane, etc. are mentioned, for example. Specific examples of these include aliphatic diamines such as metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, and the like;

As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), etc .;

As the aromatic diamine, for example, p-phenylenediamine, m-phenylenediamine, 3,5-diaminobenzoic acid, 2,4-diaminobenzenesulfonic acid, 4,4'-diaminostilbene-2,2 ' -Disulfonic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 1, 5-bis (4-aminophenoxy) pentane, 1,7-bis (4-aminophenoxy) heptane, bis [2- (4-aminophenyl) ethyl] hexanoic acid, N, N-bis (4- Aminophenyl) methylamine, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-dia Minobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4 -Aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'- (p-phenylenediisopropylidene) bisanyl The (m- phenylenedimaleimide isopropylidene) bis aniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, etc. -, 4,4 '

As the diamino organosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like; each of the diamines described in Japanese Patent Application Laid-Open No. 2010-97188 can be used. have.

Synthesis of Polyamic Acid

Polyamic acid (P) can be obtained by making above-mentioned tetracarboxylic dianhydride and diamine react with a molecular weight modifier as needed. As for the usage ratio of tetracarboxylic dianhydride and diamine used for the synthesis reaction of polyamic acid (P), the ratio in which the acid anhydride group of tetracarboxylic dianhydride is 0.2-2 equivalent with respect to 1 equivalent of amino group of diamine, , And the ratio which becomes 0.3-1.2 equivalent is more preferable.

In addition, when tetracarboxylic dianhydride or diamine has an acidic functional group, you may make it react after adding and neutralizing a base. As the base, tertiary amines are preferred, and triethylamine is particularly preferred. The proportion of the base used is preferably 0.5 to 5 equivalents, more preferably 1 to 2 equivalents relative to the acidic functional group. Similarly, when tetracarboxylic dianhydride or diamine has a basic functional group, you may make it react after adding an acid and neutralizing. As the acid, carbonic acid is preferable. The ratio of the acid to be used is preferably 0.5 to 5 equivalents, more preferably 1 to 2 equivalents to the basic functional group.

Examples of the molecular weight modifier include acid-anhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate, and the like. Can be mentioned. It is preferable to set it as 20 mass parts or less with respect to a total of 100 mass parts of tetracarboxylic dianhydride and diamine to be used, and, as for the usage ratio of a molecular weight modifier, it is more preferable to set it as 10 mass parts or less.

The synthesis reaction of polyamic acid (P) is preferably performed in an organic solvent. -20 degreeC-150 degreeC is preferable, and, as for reaction temperature at this time, 0-100 degreeC is more preferable. Moreover, 0.1-24 hours are preferable and, as for reaction time, 0.5-12 hours are more preferable.

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

Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphor It is preferable to use at least one selected from the group consisting of triamide, m-cresol, xyleneol and halogenated phenol as a solvent, or to use a mixture of at least one of these and other organic solvents in the above range. Do. As for the usage-amount (a) of an organic solvent, it is preferable to set it as the amount which the total amount (b) of tetracarboxylic dianhydride and diamine becomes 0.1-50 mass% with respect to the total amount (a + b) of a reaction solution.

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

[Polyamic acid ester]

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

Polymer (P) can be obtained by dehydrating and ring-closing the polyimide precursor (polyamic acid (P) and polyamic acid ester (P)) synthesize | combined as mentioned above and imidating. The polymer (P) may be a complete imide obtained by dehydrating and closing all of the dark acid structure or the acid ester structure possessed by the polyimide precursor as the precursor thereof, and dehydrating and ringing only a part of the dark acid structure and the acid ester structure to form a dark acid structure or The partial imidate which a dark acid ester structure and an imide ring structure coexist together may be sufficient. In order for a polymer (P) to obtain the coating film with a sufficiently high orientation regulation force in the use of a liquid crystal element, it is preferable that the imidation ratio is 50% or more, It is more preferable that it is 75% or more, It is still more preferable that it is 85% or more, It is especially preferable that it is 90% or more. This imidation ratio shows the ratio which the number of the imide ring structure to the sum of the number of the female acid structure, the female ester structure, and imide ring structure of a polyimide occupies as a percentage.

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

In the method of adding a dehydrating agent and a dehydrating ring-closure catalyst to the solution of polyamic acid, acid anhydrides, such as acetic anhydride, a propionic anhydride, and trifluoroacetic anhydride, can be used as a dehydrating agent, for example. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the dark acid structure of polyamic acid. As the dehydration ring closure catalyst, for example, base catalysts such as pyridine, triethylamine, 1-methylpiperidine, and acid catalysts such as methanesulfonic acid and benzoic acid can be used. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. As an organic solvent used for a dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of polyamic acid (P) is mentioned. 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.

In this way, a reaction solution containing the polymer (P) is obtained. This reaction solution may be used for preparation of a composition as it is, may be used for preparation of a composition after removing a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, may be used for preparation of a composition after isolating a polymer (P), or After refine | purifying the isolated polymer (P), you may use for preparation of a composition. These purification operations can be performed according to a well-known method.

When the polymer (P) obtained as mentioned above is made into the solution of 10 mass% of concentration, it is preferable to have a solution viscosity of 10-2000 mPa * s, and to have a solution viscosity of 20-1000 mPa * s. It is more preferable. In addition, the solution viscosity (mPa * s) of the said polymer is 25 degreeC using the E-type rotational viscometer with respect to the polymer solution of 10 mass% of concentration prepared using the good solvent (for example, water) of the said polymer. It is a measured value.

Polymer weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of (P) (M _w) is preferably 1000-500000, more preferably 2000-300000. The molecular weight distribution (M _w / M _n ) represented by the ratio of Mw and the number average molecular weight (M _n ) in terms of polystyrene measured by GPC is preferably 15 or less, and more preferably 10 or less. By being in such a molecular weight range, it is easy to ensure the density | concentration range and temperature range which a composition shows lyotropic liquid crystalline, and it is suitable.

<Other components>

The composition of this indication may contain other components other than the said polymer (P) in the range which does not prevent the objective and effect of this indication.

[Other polymers]

As other components, polymers other than polymer (P) (henceforth "other polymer"), etc. are mentioned, for example. Other polymers can be used for the improvement of solution characteristics and electrical characteristics. As a specific example of such another polymer, For example, the polyamic acid obtained by making the said other tetracarboxylic dianhydride react with the said other diamine, the imidation polymer of the said polyamic acid, the esterification polymer of the said polyamic acid, polyester, Polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrenephenylmaleimide) derivative, poly (meth) acrylate and the like.

When mix | blending another polymer with a composition, it is preferable to set it as 30 mass parts or less with respect to a total of 100 mass parts of the polymer contained in a composition, It is more preferable to set it as 20 mass parts or less, 10 It is more preferable to set it as mass part 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 a shear stress to the composition, with the uniaxial orientation of the polymer (P), orientation of rod-shaped molecules and the like can also be controlled. Examples of the rod-shaped molecules include dichroic dyes and the like, and examples of the rod-shaped nanostructures include dye associations, quantum rods, metal nanorods, carbon nanotubes, proteins, nucleic acids, and viruses. have. Various functions can be provided by controlling the orientation of rod-shaped molecules and the like. For example, the composition containing a dichroic dye can form a guest-host type polarizing plate, and the composition containing a quantum rod can form a wavelength conversion plate which can polarize light emission, The composition to contain can form the wire and actuator which have conductive anisotropy. When mix | blending a rod-shaped molecule | numerator etc. with a composition, the compounding ratio can be suitably set in the range which does not impair the effect of this indication according to the kind of rod-shaped molecule | numerator.

As other components, the above-mentioned, for example, the compound which has at least 1 epoxy group in a molecule | numerator, a functional silane compound, surfactant, a filler, a pigment, an antifoamer, a sensitizer, a dispersing agent, antioxidant, an adhesion agent, an antistatic agent, a leveling agent Agent, an antibacterial agent, etc. are mentioned. In addition, these compounding ratio can be suitably set in the range which does not prevent the effect of this indication according to each compound to mix | blend.

[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.

As a solvent to be used, For example, water, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, ethylene glycol, acetone, methyl ethyl ketone, tetrahydrofuran, N-methyl -2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-1-imidazolidinone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, N, N, 2-trimethylpropanamide, 1-butoxy-2 Propanol, diacetone alcohol, dipropylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-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 ether, di Ethylene glycol and the like monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate. These can be used individually by 1 type or in mixture of 2 or more types.

As a solvent to be used, it is preferable to contain water. It is preferable to set it as 50 mass% or more with respect to the whole quantity of the solvent in a composition, It is more preferable to set it as 75 mass% or more, It is especially preferable to use 90 mass% or more of water.

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 soluble in water. Preferably, the solvent is an organic solvent having a boiling point lower than that of water, methanol, ethanol, It is more preferable that it is at least 1 sort (s) chosen from the group which consists of n-propanol, i-propanol, acetone, and tetrahydrofuran. When using the mixed solvent of water and an organic solvent, it is preferable to make content rate of an organic solvent into 50 mass% or less with respect to the total amount of a mixed solvent, It is more preferable to set it as 25 mass% or less, 10 mass It is more preferable to set it as% or less.

The concentration of the polymer (P) in the composition of the present disclosure may be a concentration in which the composition exhibits lyotropic liquid crystallinity, and is not particularly limited, but is preferably 1 to 30 mass based on the total amount of the solvent and the polymer (P). %to be. According to polymer (P), it is preferable at the point which can obtain the composition which shows a lyotropic liquid crystalline at a comparatively low polymer concentration. For this reason, the coating property at the time of forming a coating film on a board | substrate is favorable, the thin film of about 0.1 micrometer can be produced, and 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 relative to the total amount of the solvent and the polymer (P).

Although solid content concentration (the ratio which the total mass of components other than the solvent of a composition occupies for the total mass of a composition) in the composition of this indication is selected suitably in consideration of viscosity, volatility, etc., Preferably it is 1-30 mass% It is the range, More preferably, it is the range of 2-20 mass%, Especially preferably, it is the range of 3-15 mass%. That is, the composition of this indication is apply | coated to the board | substrate surface as mentioned later, Preferably, a coating film may be formed by drying. At this time, when solid content concentration is less than 1 mass%, it becomes difficult for a composition to show lyotropic liquid crystalline. On the other hand, when solid content concentration exceeds 30 mass%, the film thickness of a coating film becomes excessive and it is difficult to obtain a favorable coating film, and also the viscosity of a composition increases and there exists a tendency for applicability | paintability to fall. The temperature at the time of preparing a composition becomes like this. Preferably it is 10-90 degreeC, More preferably, it is 20-65 degreeC.

[Lyotropic liquid crystal]

The composition of this disclosure is a mixture of a polymer (P) and a solvent, Preferably it shows lyotropic liquid crystalline at the temperature of at least one part of the range of 0 degreeC or more and less than 100 degreeC. The temperature range which shows lyotropic liquid crystalline is a temperature range containing 20-40 degreeC preferably in the range of 0 degreeC or more and less than 100 degreeC, More preferably, it is a temperature range containing 20-60 degreeC, Preferably it is the temperature range containing 10-80 degreeC. By apply | coating the composition of a lyotropic liquid crystal state on a board | substrate, and flowing by a shear stress, the coating film which the molecular chain of the polymer (P) uniaxially oriented self-organically to the shear direction can be obtained. In the process of application | coating and drying, it is preferable to control so that a composition may not deviate from the temperature range and concentration range which show lyotropic liquid crystalline. In the course of coating or drying, despite the fluidity of the composition, when the temperature or concentration that does not exhibit lyotropic liquid crystallinity is reached, the orientation may be relaxed and the anisotropy of the coating film may be lost. When the polymer (P) and the solvent are mixed to ionize the polymer (P), the polymer (P) is contained in the composition together with the solvent in a state in which the ionic functional group in the partial structure represented by the formula (1) is ionized.

Polymer (P) is a rigid rod-shaped polymer, and acts as a mesogen in a solvent. In addition, since the polymer (P) is an aromatic polyimide having a structure in which the benzene ring and the imide ring are connected in the main chain, and is rigid and highly uniaxial linearity, it is easy to in-plane orientation at the thin film interface by stacking between molecules, and orientation A liquid crystal aligning film excellent in regulation power can be formed. In addition, by introducing rod-like molecules or the like (guest) to the lyotropic liquid crystal field (host) produced by the polymer (P), rod-shaped molecules or the like can be oriented along the molecular chain of the polymer (P), A polarizing plate, a wavelength conversion plate, etc. can be formed.

<Liquid crystal aligning film and liquid crystal element>

The liquid crystal aligning film of this indication is formed by using the composition prepared as mentioned above as a liquid crystal aligning agent. Moreover, the liquid crystal element of this indication is equipped with the liquid crystal aligning film formed using the said composition (liquid crystal aligning agent). When a liquid crystal element is a liquid crystal display element, the drive mode is not specifically limited, It can apply to various drive modes, such as TN type, STN type, IPS type, FFS type, VA type, MVA type, and PSA type. .

A liquid crystal display element can be manufactured by the method including the following process 1-process 3, for example. Although a board | substrate etc. differ according to a desired drive mode, the case where a FFS type liquid crystal display element is manufactured is illustrated below.

[Step 1: Formation of Coating Film]

First, a composition is apply | coated on a board | substrate, and then a coating film is formed on a board | substrate by heating an application surface. When manufacturing an FFS type liquid crystal display element, a composition is preferable on the electrode formation surface of the board | substrate with which the electrode which consists of the transparent conductive film or metal film patterned by the comb-tooth shape is formed, and the one surface of the opposing board | substrate in which the electrode is not formed, is preferable. Preferably, it is applied by a bar coater method, a die coater method or a blade coater method. According to these methods, it is preferable at the point which is easy to orient the molecular chain of a polymer (P) by the flow by a shear stress.

Here, as a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film formed on one surface of the substrate, an NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. Can be. 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 a transparent conductive film, or the like can be employed. have. As a metal film, the film which consists of metals, such as chromium, can be used, for example. In the application of the composition, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, before applying the functional silane compound, the functional titanium compound, or the like to the surface forming the coating film on the substrate surface in advance ( You may also carry out pre-treatment.

After application of the composition, preheating (prebaking) is preferably performed for the purpose of preventing liquid flow of the applied composition. Prebaking temperature becomes like this. Preferably it is 30-100 degreeC, More preferably, it is 40-80 degreeC, Especially preferably, it is 40-60 degreeC. Prebaking time becomes like this. Preferably it is 0.25-10 minutes, More preferably, it is 0.5-5 minutes. Thereafter, a firing (postbaking) step is carried out for the purpose of completely removing the solvent and for the purpose of thermally imidizing the dark acid structure present in the polymer as necessary. The baking temperature (post-baking temperature) at this time becomes like this. Preferably it is 60-300 degreeC, More preferably, it is 100-250 degreeC. Post-baking time becomes like this. Preferably it is 5-200 minutes, More preferably, it is 10-100 minutes. In a heating process, it is preferable to make the coating film which consists of a liquid crystal aligning agent apply | coated on the board | substrate make the molecular chain of a polymer (P) orientate by the flow by a shear stress, and to dry in that state. Thereby, liquid crystal aligning ability is provided to a coating film by simple operation, and a liquid crystal aligning film is formed. The film thickness of the film formed is preferably 0.001 to 1 m, more preferably 0.005 to 0.5 m.

After apply | coating a composition on a board | substrate, a liquid crystal aligning film is formed by removing a solvent. Under the present circumstances, when the polymer contained in a composition has an imide ring structure and a dark acid structure, it may be made into a more imidized coating film by advancing dehydration ring-closure reaction by further heating after coating film formation.

[Step 2: ion crosslinking treatment]

As needed, you may immerse the board | substrate with a liquid crystal aligning film in polyvalent aqueous solution, and ion-crosslinking-process. By exchange of the polycation of a polymer (P) with a polyvalent cation, the water resistance and a mechanical characteristic of a liquid crystal aligning film improve, and the electrical property of a liquid crystal cell further improves. 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 alkaline earth metal ions, and particularly preferably Ca ²⁺ , Sr ²⁺ , or Ba ²⁺ . The counter ion of the polyvalent cation is not particularly limited as long as it is water-soluble, but is preferably a hydroxide ion, a carbonate ion, or a halide ion. Immersion time becomes like this. Preferably it is 1-20 minutes, More preferably, it is 2-10 minutes. In addition, after immersing the substrate in a polyvalent aqueous solution, it is preferable to remove the ionic component by rinsing the extracted substrate with pure water and further immersing in pure water.

[Step 3: Construction of Liquid Crystal Cell]

The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as mentioned above, and arrange | positioning a liquid crystal between two board | substrates which oppose. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, two substrates are disposed to face each other via 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 using a sealing agent and partitioned by the substrate surface and the sealing agent. After injecting and filling a liquid crystal in a cell gap, a liquid crystal cell is manufactured by sealing an injection hole. The second method is a method called an ODF (One Drop Fill) method. After apply | coating an ultraviolet-ray curable sealing compound to the predetermined place on one board | substrate among two board | substrates which provided the liquid crystal aligning film, and further dropping a liquid crystal in predetermined several places on a liquid crystal aligning film surface, a liquid crystal A liquid crystal cell is manufactured by bonding another board | substrate so that an oriented film may oppose, pressing a liquid crystal on the whole surface of a board | substrate, then irradiating an ultraviolet-ray to the whole surface of a board | substrate, and hardening a sealing compound. In any case, the liquid crystal cell produced as described above is further preferably heated to a temperature at which the used liquid crystal takes an isotropic phase, and then slowly cooled to room temperature to remove the flow orientation during liquid crystal filling. Do.

As the sealing agent, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used.

Examples of the liquid crystals include nematic liquid crystals and smectic liquid crystals, and among them, nematic liquid crystals are preferable, and for example, a sieve base liquid crystal, a subfamily clock liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal and an ester liquid crystal , Terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cuban-based liquid crystals, and the like. Moreover, for these liquid crystals, For example, cholesteric liquid crystals, such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate; Chiral agent sold as brand names "C-15" and "CB-15" (made by Merck); You may add and use ferroelectric liquid crystals, such as p-disiloxy benzylidene-p-amino-2-methylbutyl cinnamate.

And a liquid crystal display element can be obtained by adhering a polarizing plate to the outer surface of a liquid crystal cell. As a polarizing plate adhere | attached to the outer surface of a liquid crystal cell, the polarizing plate which consists of a polarizing plate which sandwiched the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching orientation of polyvinyl alcohol by the cellulose acetate protective film, or the H film itself is mentioned. Can be.

<Phase difference board>

The retardation plate of this indication is formed of the composition prepared as mentioned above. Specifically, first of all, the composition is preferably a substrate (eg, a glass substrate, triacetyl cellulose (TAC), polyethylene terephthalate, polymethylmethacryl) by a bar coater method, a die coater method, or a blade coater method. Rate) and then dried in a state in which the molecular chain of the polymer (P) is oriented by flow due to shear stress. As a result, a retardation plate is formed.

<Polarizing plate>

The polarizing plate of this indication is formed of the composition containing the dichroic dye or metal prepared as mentioned above. For example, in order to manufacture a guest-host type polarizing plate, first, the composition containing a polymer (P), a dichroic dye, and a solvent is used for the board | substrate (for example, a glass substrate, a triacetyl cellulose (TAC), a polyethylene). Terephthalate, polymethyl methacrylate, and the like), preferably by a bar coater method, a die coater method or a blade coater method. Subsequently, the polarizing plate can be obtained by drying the molecular chain of the polymer (P) in the state oriented by the flow by a shear stress. Moreover, you may adhere a resin film (protective film) to one surface or both surfaces of a polarizing plate as needed.

In addition, in order to manufacture a reflective polarizing plate, using the composition containing a polymer (P), a metal (metal nanorod, a metal nanowire, or a metal ion), and a solvent, the manufacturing method of a guest-host type polarizing plate, The polarizing plate can be obtained by apply | coating a composition on a board | substrate similarly and then drying in the state which orientated the molecular chain of polymer (P) by the flow by a shear stress. However, when metal ion is used as a metal, a single metal is anisotropically precipitated along the polymer (P) by reduction.

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

Example

Hereinafter, although an Example demonstrates more concretely, this indication is not limited to these Examples.

The structure and symbol of the main compound used by the following examples are as follows.

(Specific tetracarboxylic dianhydride)

TA-1; Pyromellitic dianhydride

(Other tetracarboxylic dianhydride)

TB-1; 1,4,5,8-naphthalenetetracarboxylic acid dianhydride

TB-2; 4,4'-biphthalic acid dianhydride

TB-3; 1,2,3,4-cyclobutanetetracarboxylic dianhydride

(Specific diamine)

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

DA-2; 2,5-diaminobenzenesulfonic acid

DA-3; 2,5-diaminobenzoic acid

(Other diamine)

DB-1; 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl

DB-2; 4,4'-diaminostilbene-2,2'-disulfonic acid

DB-3; 2,4-diaminobenzenesulfonic acid

The imidation ratio [%] of polyimide was measured by the following method.

The solution of polyimide was put into pure water, the obtained precipitate was dried under reduced pressure sufficiently at room temperature, dissolved in heavy hydrogenated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. H-NMR spectrum obtained from ^1, was determined by the following equation appears to formula (a).

Imidation ratio [%] = (((1-A ¹ ) / A ² ) × α) × 100. (a)

(In Formula (a), A ¹ is the peak area derived from the protons of the NH group which appears in the vicinity of the chemical shift of 10 ppm, A ² is the peak area derived from the other protons, and α is the proton of the NH group in the precursor of the polymer. It is the number ratio of other protons to one.)

Example 1

(1) Synthesis of Polymer

Diamine (DA-1) (3.79 g, 11.0 mmol), m-cresol (50 mL), and triethylamine (2.43 g, 24.0 mmol) were added to a three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube. It stirred under nitrogen. After diamine dissolution, tetracarboxylic dianhydride (TA-1) (2.18 g, 10.0 mmol) and benzoic acid (1.71 g, 14.0 mmol) were added and stirred at 80 ° C for 3 hours, followed by stirring at 180 ° C for 12 hours. After the completion of the reaction, the reaction solution was diluted with m-cresol and dipped in 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 88%) having a partial structure represented by the following formula (PI-1) of brown powder. In FIG. 1, the measurement result of the ¹ H-NMR spectrum (DMSO-d ⁶ , 400 MHz) of the polymer (PI-1) is shown. The imidation ratio of the polymer (PI-1) was 99% or more.

(2) Evaluation of Preparation and Solubility of Composition

Water was added to the polymer (PI-1) obtained in the above (1) and dissolved by heating and stirring at 60 ° C to obtain an aqueous solution of the polymer (PI-1). The composition (C-1) was prepared by filtering this solution with the filter of 0.2 micrometer of pore diameters.

The evaluation of solubility makes "good | favorableness" the case where the solid content concentration of a polymer becomes 1 mass% or more, and makes "good" the case where the aqueous solution which solid content concentration becomes 1 mass% or more cannot be prepared. I did. As a result, it was evaluation of "good" in this Example.

(3) Evaluation of lyotropic liquid crystalline

The composition (C-1) obtained by said (2) was dripped on the glass substrate, and it observed by the polarization microscope. The evaluation sets "good" the case where optical anisotropy was observed under orthogonal nicotine at least in the temperature of 0 degreeC or more and less than 100 degreeC, and optical anisotropy is observed also in any temperature of 0 degreeC or more and less than 100 degreeC. When not, it was made into "bad". As a result, in this Example, the solid content concentration of the polymer was 6-20 mass%, the optical anisotropy was observed in the temperature range of 10 degreeC-90 degreeC, and it was evaluation of "good."

3-5, the polarization micrograph (100 times) of the composition (C-1) whose solid content concentration of a polymer is 10 mass% is shown. 3 is a photograph immediately after dropping a composition onto a glass substrate, and FIG. 4 is a photograph after lightly drying and concentrating on the glass substrate after dropping the composition, and FIG. 5 shows a glass substrate from above after dropping the composition. It is a photograph after sandwiching between and putting the upper glass substrate to the side and giving a shear stress.

[Examples 2-3 and Comparative Examples 1-6]

In Example 1, polymers (PI-2 to PI-9) were synthesized in the same manner as in Example 1 except that the types of tetracarboxylic dianhydride and diamine were changed as shown in Table 1, respectively. did. In addition, the composition (C-2-C-9) was prepared using the obtained polymers (PI-2-PI-9), respectively, and the solubility and liquid crystalline evaluation were performed. The evaluation results are shown in Table 1 below. In addition, in Table 1, the numerical value (molar ratio) of diamine column shows the usage ratio (mol part) of each compound with respect to 100 mol part of total amounts of the diamine used for the synthesis | combination of a polymer. In Comparative Example 1 and 4, since solubility was "poor" and lyotropic liquid crystalline was not able to be evaluated, it showed with "-" in Table 1.

In FIG. 2, the measurement result of the ¹ H-NMR spectrum (DMSO-d ⁶ , 400 MHz) of the polymer (PI-2) is shown. The imidation ratio of the polymer (PI-2) was 99% or more. In Example 2, optical anisotropy was observed in the temperature range of 20-70 degreeC at 2 mass%, and the temperature range of 40-80 degreeC at 3-6 mass% in solid content concentration of a polymer, and liquid crystal was evaluated as "good." It was.

Example 4: Preparation and Evaluation of Liquid Crystal Alignment Film

(1) Preparation of Composition

The 10 mass% solution of the composition (C-1) containing the polymer (PI-1) obtained in Example 1 was diluted with water, and the solution which solid content concentration became 6 mass% was obtained. The composition (C-10) was prepared by filtering this solution with the filter of 0.2 micrometer of pore diameters.

(2) Formation of Liquid Crystal Alignment Film

The composition (C-10) prepared in the above (1) was prepared on each surface of the glass substrate in which the flat electrode, the insulating layer and the comb-tooth shaped electrode were laminated on one side in this order, and the opposite glass substrate on which the electrode was not formed. It applied using the wire bar so that a film thickness might be set to 0.1 micrometer, it dried for 5 minutes by the 60 degreeC warm air for 30 minutes in 120 degreeC oven, and formed the liquid crystal aligning film.

(3) Preparation of Liquid Crystal Display Element

After screen printing coating of the epoxy resin adhesive which put the 5.5-micrometer-diameter aluminum oxide sphere into the edge of the surface where the liquid crystal aligning film was formed, about the pair of board | substrates which have the liquid crystal aligning film produced by said (2), The substrates were overlapped and pressed so that the projection direction of the polarization axis to the substrate surface at the time of light irradiation was antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, after filling a nematic liquid crystal (MLC-7028 by Merck Co., Ltd.) between a pair of board | substrates, the liquid crystal injection hole was sealed with the epoxy adhesive. In addition, in order to remove the flow orientation at the time of liquid crystal injection, it cooled to room temperature after heating to 120 degreeC. Next, the polarizing plate was stuck to the outer both surfaces of the board | substrate, and the FFS type liquid crystal display element was manufactured.

(4) Evaluation of liquid crystal alignment

About the liquid crystal display element manufactured by said (3), the presence or absence of the abnormal domain in the change of the contrast at the time of turning ON / OFF (appliance / release) of the voltage of 5V was observed by 50 times the magnification with a microscope. The evaluation made "good" the case where the abnormal domain was not observed, and made the "bad" the case where the abnormal domain was observed. As a result, it was evaluation of "good" in this Example.

Example 5

In "Preparation of (1) composition" of the said Example 4, the point which used composition (C-2) instead of composition (C-1), and solid content concentration after dilution with water are 3 mass% from 3 mass%. A composition (C-11) was prepared by performing the same operation as in Example 4 except changing to the mass%. Furthermore, the liquid crystal aligning film was formed using the prepared composition (C-11), the liquid crystal display element was produced, and liquid crystal alignability was evaluated. The evaluation results are shown in Table 2 below.

[Comparative Examples 7-8]

In Example 4, except that the polymer contained in the composition was changed as described in Table 2 below, a composition was prepared in the same manner as in Example 4, a liquid crystal alignment film was formed, and a liquid crystal display device was produced to provide a 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, it was applied on a glass substrate using a bar coater so that the film thickness was 1 μm. It dried for 30 minutes in 120 degreeC oven, and formed the retardation plate.

The evaluation of the phase difference measured the in-plane phase difference (retardation) by the parallel Nicole rotation method, and makes "good" the case where in-plane phase difference was 20 nm or more in wavelength 550nm, and in-plane phase difference is 20 nm When it was less, we made "bad". As a result, in the present Example, it was a result of "good".

Comparative Example 9

In the said Example 6, except having changed the polymer contained in a composition as described in following Table 2, it carried out similarly to Example 6, the composition was prepared, the retardation plate was formed, and the phase difference was evaluated. The evaluation results are shown in Table 2 below.

Example 7: Preparation and Evaluation of Polarizing Plate

(1) Preparation of Composition

By using the composition (C-1) containing the polymer (PI-1) obtained in Example 1, the dichroic dye C.I. 1 mass part 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 mass%. The composition (C-14) was prepared by filtering this solution with the filter of 0.2 micrometer of pore diameters.

(2) Formation of Polarizing Plate

Using the composition (C-14) adjusted in the above (1), the coating was applied on a glass substrate using a bar coater so that the film thickness was 10 μm, and the oven was heated at 120 ° C. for 5 minutes with 60 ° C. warm air. It dried for 30 minutes and formed the guest-host type polarizing plate.

(3) Evaluation of dichroic ratio

Evaluation was performed by polarization absorption spectrum measurement, the case where the dichroic ratio was 2 or more was "good", and the case where the dichroic ratio was less than 2 was "bad". As a result, in the present Example, it was a result of "good". The dichroic ratio is a ratio of absorbance (A _II ) when the polarization axis is parallel to the shear direction at a wavelength of 500 nm and absorbance (A _⊥ ) when the polarization axis is perpendicular to the shear direction (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 described in Table 2 below, and the dichroic ratio was evaluated while forming a polarizing plate. The evaluation results are shown in Table 2 below. In addition, in Table 2, "-" shows that the said evaluation was not performed.

From the above result, it became clear that the composition of the Example using the polymer (P) observed the optical anisotropy under orthogonal Nicole within the temperature range of 0 degreeC or more and less than 100 degreeC, and shows lyotropic liquid crystallinity. In addition, the polymer (P) exhibited lyotropic liquid crystallinity in water at a low polymer concentration of 20% by mass or less. Moreover, the liquid crystal display element, the retardation plate, and the polarizing plate which were produced using the composition of the Example showed favorable optical characteristic. In contrast, the composition of the comparative example could not observe optical anisotropy at any temperature. From these results, it became clear that the composition which shows a lyotropic liquid crystalline on mild conditions is obtained by using a polymer (P).

Claims (13)

A composition showing lyotropic liquid crystallinity obtained by mixing a polymer (P) having a partial structure represented by the following formula (1) and a solvent:

(In formula (1), at least 1 of R <^1> -R <^10> is a monovalent group which has an ionic functional group, and remainder is respectively independently a hydrogen atom, a halogen atom, or monovalent organic group; k is 0 or 1). The method of claim 1,
The composition which shows lyotropic liquid crystalline in at least one part of the temperature range of 0 degreeC or more and less than 100 degreeC. The method according to claim 1 or 2,
The composition containing 50 mass% or more of whole quantity of the said solvent. The method according to any one of claims 1 to 3,
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 method according to any one of claims 1 to 4,
The ionic functional group is an acidic functional group. The method according to any one of claims 1 to 5,
The said polymer (P) is a partial structure represented by said formula (1), Comprising: The composition which is a polymer which has a partial structure represented by following formula (2):

(In Formula (2), M is a cation; k is 0 or 1; However, in the case of k = 1, some M in a formula may mutually be same or different.). The method according to any one of claims 1 to 6,
Furthermore, a composition containing a dichroic dye, a dye association, a quantum rod, a metal nanorod, or a carbon nanotube. Liquid crystal aligning agent obtained by mixing the polymer (P) which has a partial structure represented by following formula (1), and a solvent:

(In formula (1), at least 1 of R <^1> -R <^10> is a monovalent group which has an ionic functional group, and remainder is respectively independently a hydrogen atom, a halogen atom, or monovalent organic group; k is 0 or 1). The liquid crystal aligning film formed using the composition of any one of Claims 1-7. The retardation plate formed using the composition in any one of Claims 1-7. The polarizing plate formed using the composition of any one of Claims 1-7. The liquid crystal which apply | coats the composition in any one of Claims 1-7 to a board | substrate in a lyotropic liquid crystal state, and is dried in the state which orientated the molecular chain of the said polymer (P) by the flow by a shear stress. Method for producing an alignment film. The liquid crystal element provided with the liquid crystal aligning film of Claim 9.

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