WO2021033482A1 - Dispersion composition, dispersant, anisotropic film and method for producing same, and apparatus for forming anisotropic film - Google Patents

Abstract

A dispersion composition according to the present invention contains: a material to be dispersed; a dispersion medium; and a polymer (P) which is at least one substance selected from the group consisting of polyamic acids, polyamic acid esters and polyimides, and which has a structural unit U1 derived from a diamine compound (D1) represented by formula (1) and a structural unit U2 derived from a diamine compound (D2) that is different from the diamine compound (D1). In the formula, in cases where n is 0, at least one of R1 to R4 moieties represents a monovalent group having an ionic functional group, and in cases where n is 1, at least one of R1 to R8 moieties represents a monovalent group having an ionic functional group.

Description

Dispersion composition, dispersant, anisotropic film and method for producing the same, and anisotropic film forming apparatus Cross-reference of related applications

This application is based on Japanese Patent Application No. 2019-149938 filed on August 19, 2019, and the contents of the description are incorporated herein by reference.

The present disclosure relates to a dispersion composition, a dispersant, an anisotropic film and a method for producing the same, and an anisotropic film forming apparatus.

Nano-order-sized substances such as nanocarbons and metal nanoparticles have excellent properties in terms of electrical properties, mechanical properties, thermal stability, etc., and their application and practical application to various fields as nanomaterials are being studied. ing. These particles are generally dispersed in a dispersion medium to utilize their function. In order to fully express the characteristics of the particles, it is desirable to uniformly disperse the particles in a dispersion medium. Therefore, various dispersion compositions containing a dispersant together with the particles have been proposed in order to suppress the aggregation of the particles and enhance the dispersibility of the particles (see, for example, Patent Document 1 and Patent Document 2).

Patent Document 1 discloses a dispersion composition in which a polyalkylene oxide having an aryl group introduced into a side chain is used as a dispersant for dispersing nanocarbons, metal nanoparticles, inorganic fibers and organic fibers. .. Further, Patent Document 2 discloses a dispersion composition using a polyamic acid having a benzoxazole skeleton as a dispersant for dispersing carbon nanotubes.

International Publication No. 2016/0392218 Japanese Unexamined Patent Publication No. 2013-154337

If the dispersant such as nanocarbons and metal nanoparticles shows good dispersibility in both aqueous and organic solvent systems, the use of the dispersant can be further expanded or the function can be further enhanced. It is possible.

A film or wiring containing the dispersion can be formed on the substrate by applying the dispersion composition in which the dispersion is dispersed in the dispersion medium to the substrate and then removing the dispersion medium from the coating liquid. is there. Further, a device provided with a film or wiring containing a dispersant is used for various purposes such as an electronic device and a display device. If the external force resistance of the member formed by the disperse is low, the performance of the device may be deteriorated. Therefore, the member is required to have high resistance to external force.

The present disclosure has been made in view of the above problems, and forms a member having good dispersibility of the dispersant and good resistance to external force regardless of whether a dispersion medium of an aqueous system or an organic solvent system is used. One object of the present invention is to provide a dispersion composition capable of obtaining the dispersion composition and a dispersant for obtaining the dispersion composition.

The present inventors have diligently studied to solve the above problems, and obtained polyamic acids, polyamic acid esters, and polyamic acid esters obtained by using a diamine having an ionic functional group and a diamine having no ionic functional group in combination. It has been found that the above problems can be solved by using polyimide as a polymer dispersant. That is, according to the present disclosure, the following means are provided.

（式（１）中、ｎは０又は１である。ｎが０の場合、Ｒ^１～Ｒ^４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。ｎが１の場合、Ｒ^１～Ｒ^８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。）
＜２＞　上記重合体［Ｐ］を含有する、分散剤。 <1> At least one selected from the group consisting of a dispersant, a dispersion medium, a polyamic acid, a polyamic acid ester, and a polyimide, and derived from the diamine compound [D1] represented by the following formula (1). A dispersion composition containing a structural unit U1 to be formed and a polymer [P] having a structural unit U2 derived from a diamine compound [D2] different from the diamine compound [D1].

(If in the formula (1), n is 0 or 1 .n is zero, at least one of R 1 ^~ R ⁴ is a monovalent group having an ionic functional group, the remainder, respectively Independently, it is a hydrogen atom, a halogen atom or a monovalent organic group. When n is 1, ^{at least one of R 1} to R ⁸ is a monovalent group having an ionic functional group, and the rest. Are independently hydrogen atoms, halogen atoms or monovalent organic groups.)
<2> A dispersant containing the above polymer [P].

<3> A step of holding a dispersion composition containing a dispersion to be dispersed, a dispersion medium, and a compound exhibiting lyotropic liquid crystallinity on the surface of a retainer while applying shear stress, and a dispersion composition retained on the surface of the retainer. A method for producing an anisotropic film, which comprises a step of transferring the above-mentioned material onto a substrate.
<4> An anisotropic film obtained by the production method of <3> above.
<5> A holding portion for holding a dispersion composition containing a dispersion to be dispersed, a dispersion medium, and a compound exhibiting lyotropic liquid crystallinity on the surface of a holding body while applying shear stress, and a dispersion composition held on the surface of the holding body. An anisotropic film forming apparatus including a transfer unit for transferring an object onto a substrate.

According to the present disclosure, a dispersion composition having good dispersibility of the dispersoid can be obtained regardless of whether an aqueous system or an organic solvent system is used as the dispersion medium. Further, by using the dispersion composition, a member having good resistance to external force can be formed.

FIG. 1 is a schematic configuration diagram showing an example of a printing type shear coating device. FIG. 2 is a schematic configuration diagram showing an example of a dispenser type shear coating device.

<< First Embodiment >>
The dispersion composition of the present disclosure contains (A) a dispersion to be dispersed, (B) a dispersion medium, and (C) a dispersant. Hereinafter, each component contained in the dispersion composition of the present disclosure, and other components optionally blended will be described.

In addition, in this specification, "hydrocarbon group" means including 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 "alicyclic 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 of only an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be included in a part thereof. The "organic group" means a group having a hydrocarbon group, and may contain a heteroatom in the structure.

<(A) Dispersion>
The dispersant is not particularly limited, but at least one selected from the group consisting of inorganic particles and organic particles can be used. The shape of the object to be dispersed is also not particularly limited, and examples thereof include a spherical shape, a rod shape, a fibrous shape, a flat plate shape, and a disk shape. The primary particle size of the dispersion to be dispersed is preferably 10 μm or less, more preferably 1 μm or less, and further preferably 200 nm or less. The primary particle size of the dispersion to be dispersed is preferably 1 nm or more, more preferably 2 nm or more, and further preferably 5 nm or more. The "primary particle size of the object to be dispersed" referred to here is a value obtained by measuring the d50 value by a laser diffraction / scattering method.

Examples of the inorganic particles contained in the dispersion composition of the present disclosure include carbon, metal particles, semimetal particles, silica, inorganic salts, quantum dots and the like. Specific examples of these include, for example, carbon black, carbon fiber, carbon nanotube, graphite, fullerene, carbon nanohorn, etc. as carbon; for example, metal simple substance, metal oxide, metal carbide, metal nitride, etc. as metal particles; As semi-metal particles, for example, semi-metal oxides, semi-metal carbides, semi-metal nitrides, etc .; as silica, for example, wet silica (hydrous silicic acid), dry silica (silicic anhydride), colloidal silica, precipitated silica, silicic acid, etc. Calcium, aluminum silicate, modified silica with surface modification treatment, etc .; as inorganic salts, for example, sulfates (calcium sulfate, barium sulfate, etc.), carbonates (calcium carbonate, magnesium carbonate, barium carbonate, etc.), phosphoric acid Salts (calcium phosphate, etc.) and the like; examples of the quantum dots include perovskite quantum dots, carbon-based quantum dots, lead sulfide quantum dots, and the like.

The carbon fiber includes carbon nanofiber. Carbon nanotubes include single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes. Further, the carbon nanotube may be composed of only carbon , or may have a part of the structure substituted or chemically modified with another element, and may be a metal (for example, gold, silver, copper, aluminum). , Nickel, cobalt, titanium, platinum, etc.).

More details about metal particles include metal elements such as gold, silver, copper, zinc, aluminum, tin, nickel, palladium, platinum, cobalt, iron, manganese, chromium, molybdenum, titanium, zirconium, hafnium, yttrium, cerium. Particles can be mentioned. Specific examples of these include a single metal composed of the metal element; copper oxide, aluminum oxide, zinc oxide, iron oxide, titanium oxide, barium titanate, bismuth oxide, cerium oxide, chromium oxide, cobalt oxide, indium oxide, and oxidation. Metal oxides such as indium tin, zirconium oxide, yttrium oxide, tin oxide, indium oxide-gallium oxide-zinc oxide, indium oxide-zinc oxide, indium tin oxide; metal carbides such as titanium carbide; titanium nitride, titanium oxynitride ( Titanium black), metal nitrides such as aluminum nitride, and the like. As the metal particles, one type can be used alone or two or more types can be used in combination.

Examples of the metalloid particles include particles containing a metalloid element such as boron and silicon. Specific examples of these include a single metalloid composed of the metalloid element; a metal oxide such as silicon dioxide; a metal carbide such as boron carbide and silicon carbide; and a metal nitride such as boron nitride and silicon nitride. .. As the semimetal particles, one type can be used alone or two or more types can be used in combination. In one embodiment of the dispersion composition of the present disclosure, at least one selected from the group consisting of metal particles and semimetal particles can be preferably used as the dispersant.

Examples of organic particles include organic pigments, dichroic pigments, pigment aggregates, proteins, nucleic acids, viruses and the like. Specific examples of these include organic pigments such as anthraquinone pigments, monoazo pigments, diazo pigments, benzimidazolone pigments, quinacridone pigments, quinophthalone pigments, dioxazine pigments, phthalocyanine pigments, flavantron pigments, indantron pigments, indolinone pigments, and thioindigo. Pigments, metal complex pigments, perinone pigments, perylene pigments, etc .; as bicolor pigments, for example, disuazo compounds, trisazo compounds, tetraxazo compounds, anthraquinone compounds, dioxazine compounds, etc .; as dye aggregates, porphyrin pigments and cyanine pigments, Examples include J-aggregates such as pyrolopyrrole pigments, acene pigments, and squarylium pigments, and H-aggregates such as oxazole yellow pigments, thiazole orange pigments, cyanine pigments, and azo pigments.

Of the above, inorganic particles can be preferably used as the dispersant, and carbon nanotubes (CNTs) and metal particles can be particularly preferably used.
Further, as the dispersant, at least one selected from the group consisting of rod-shaped nanostructures and rod-shaped molecules can be preferably used. 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. When the dispersant is at least one selected from the group consisting of rod-shaped nanostructures and rod-shaped molecules, inorganic particles can be preferably used as the dispersant, and carbon nanotubes and metal nanorods are particularly preferably used. be able to.

The content ratio of the dispersion to be dispersed in the dispersion composition can be appropriately set according to the type of the dispersion to be dispersed. The content ratio of the dispersion to be dispersed is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.03% by mass or more, based on the total amount of the dispersion composition. The content of the dispersion to be dispersed is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, based on the total amount of the dispersion composition. As the dispersant, one of the above can be used alone or in combination of two or more.

Specifically, the content ratio of the dispersant in the dispersion composition is preferably 0.05% by mass or more, more preferably 0.05% by mass or more, based on the total amount of the dispersion composition when the disperse is metal particles or semimetal particles. Is 0.1% by mass or more, more preferably 0.5% by mass or more. The content of the dispersion to be dispersed is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, based on the total amount of the dispersion composition.
When the dispersant is a carbon nanotube, the content ratio of the dispersant in the dispersion composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and further, based on the total amount of the dispersion composition. It is preferably 0.03% by mass or more. The content of the dispersion to be dispersed is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, based on the total amount of the dispersion composition.

<(B) Dispersion medium>
The dispersion composition of the present disclosure is a composition in which (A) the dispersant is dispersed in (B) a dispersion medium. The dispersion medium is a liquid and includes water, an organic solvent, and a mixed solvent of water and an organic solvent. (B) The organic solvent used as the dispersion medium is not particularly limited, and for example, an alcohol solvent, a ketone solvent, an ether solvent, an ester solvent, an aprotonic polar solvent, a halogenated hydrocarbon solvent, or a hydrocarbon solvent. Examples include solvents.

Specific examples of these include alcohol-based solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, 1-pentanol, 3-methyl-1-butanol, and the like. 1-hexanol, 2-hexanol, heptanol, cyclohexanol, methylcyclohexanol, diacetone alcohol, propane-1,2-diol, ethylene glycol, etc.;
Examples of the ketone solvent include cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, di-n-butyl ketone, methyl-i-butyl ketone, and the like. Methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, trimethylnonanone, etc.;
Examples of ether-based solvents include propylene glycol monomethyl ether (PGME), diethylene glycol diethyl ether (DEDG), diethylene glycol ethyl methyl ether, 3-methoxy-1-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol-n-. Many such as propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), 1-butoxy-2-propanol, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, etc. Partial ethers of valent alcohols; partial esters of polyhydric alcohols such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate; cyclic ethers such as tetrahydrofuran;
Examples of ester solvents include methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, t-butyl acetate, 3-methoxybutyl acetate, methyl acetoacetate, ethyl acetoacetate, and propion. Ethyl acetate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, ethylene carbonate, propylene carbonate, etc.;
Examples of aprotic polar solvents include 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-dimethylpropaneamide, N, N, 2-trimethylpropaneamide, acetonitrile, dimethyl sulfoxide, etc.;
As the halogenated hydrocarbon solvent, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane and the like;
Examples of the hydrocarbon solvent include hexane, heptane, octane, benzene, toluene, xylene and the like. In addition, these organic solvents can be used individually by 1 type or in combination of 2 or more types.

(B) The dispersion medium may be an organic solvent system or an aqueous system. The water system is preferably used because of its low environmental load and the like. When an aqueous dispersion medium is used, the proportion of water used is preferably 50% by mass or more, preferably 75% by mass or more, based on the total amount of the (B) dispersion medium contained in the dispersion composition. More preferably, it is 90% by mass or more, and particularly preferably.

When a mixed solvent of water and an organic solvent is used as the dispersion medium, the organic solvent used is not particularly limited as long as it is an organic solvent soluble in water, but preferably an organic solvent having a boiling point lower than that of water. Yes, more preferably at least one selected from the group consisting of methanol, ethanol, n-propanol, i-propanol, acetone and tetrahydrofuran. (B) When the dispersion medium is a mixed solvent of water and an organic solvent, the content ratio of the organic solvent in the dispersion composition is 50% by mass or less with respect to the total amount of the mixed solvent of water and the organic solvent. It is preferable, it is more preferably 25% by mass or less, and further preferably 10% by mass or less.

（式（１）中、ｎは０又は１である。ｎが０の場合、Ｒ^１～Ｒ^４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。ｎが１の場合、Ｒ^１～Ｒ^８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。） <(C) Dispersant>
[Polymer [P]]
The dispersion composition of the present disclosure contains a polymer [P] as a dispersant. The polymer [P] is at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and is a structural unit U1 derived from the diamine compound [D1] represented by the following formula (1). , A polymer having a structural unit U2 derived from a diamine compound [D2] different from the diamine compound [D1].

(If in the formula (1), n is 0 or 1 .n is zero, at least one of R 1 ^~ R ⁴ is a monovalent group having an ionic functional group, the remainder, respectively Independently, it is a hydrogen atom, a halogen atom or a monovalent organic group. When n is 1, ^{at least one of R 1} to R ⁸ is a monovalent group having an ionic functional group, and the rest. Are independently hydrogen atoms, halogen atoms or monovalent organic groups.)

(Structural unit U1)
The structural unit U1 is a structural unit obtained by removing one hydrogen atom from each of the two primary amino groups of the diamine compound [D1]. ^{For R 1} to R ⁸ in the above formula (1), 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. Yes, X ¹ is an ionic functional group. “*” Indicates that it is a bond that binds to a 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.} R ¹³ is preferably an alkanediyl group having 1 to 5 carbon atoms.

The ionic functional group is a functional group that forms a cation or an anion in water. The ionic functional group is not particularly limited, but is a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, an ammonium group, a pyridinium group, and an imidazole group in that the solubility of the polymer [P] in a solvent containing water can be further increased. It is preferably a urium 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.

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 are the same group or different groups. The same shall apply hereinafter. ) Etc. can be mentioned. 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, protons are less likely to be dissociated under acidic conditions, and the ionicity is lowered. Therefore, it is preferable 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, more preferably 1 to 3 carbon atoms. Alcandiyl group.

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, when n = 0, the number of monovalent groups having an ionic functional group among ^{R 1} to R ^{4, when n = 1)} The number of monovalent groups having an ionic functional group among R ¹ to R ⁸ ) is preferably 1 to 4, and more preferably 1 or 2.
In R ¹ to R ⁸ , the monovalent organic group is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 5 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a boron atom and an iodine atom.

Specific examples of the diamine compound [D1] include compounds represented by the following formulas (d-1) to (d-16).

The content ratio of the structural unit U1 in the polymer [P] is possessed by the polymer [P] in that the dispersibility of the compound to be dispersed (particularly, the dispersibility in the aqueous dispersion medium) can be sufficiently ensured. It is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and further preferably 50 mol% or more, based on the total amount of the structural units derived from the diamine compound. Is particularly preferred. Further, the content ratio of the structural unit U1 is such that the dispersibility of the dispersoid (particularly, the dispersibility of the organic solvent system in the dispersion medium) can be improved, and when CNT is used as the dispersant, the CNT film is used. The volume resistivity of the polymer [P] is preferably 99.5 mol% or less, and 99 mol% or less, based on the total amount of the structural units derived from the diamine compound. Is more preferable, 98 mol% or less is further preferable, and 85 mol% or less is particularly preferable. In the synthesis of the polymer [P], the diamine compound [D1] may be used alone or in combination of two or more.

(Structural unit U2)
The structural unit U2 is not particularly limited as long as it is a structural unit derived from a diamine compound [D2] different from the diamine compound [D1]. Examples of the diamine compound [D2] include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxane. Of these, the molecular chain of the polymer [P] has a rigid and highly uniaxial linear structure, and the stacking interaction between the molecules facilitates in-plane orientation of the polymer [P], thereby making it a dispersant. The diamine compound [D2] is preferably an aromatic diamine from the viewpoint of increasing the dispersibility of the diamine.

Specific examples of the diamine compound [D2] include, as aliphatic diamines, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl). Cyclohexane and the like; as an alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine) and the like;

As aromatic diamines, for example, paraphenylenediamine, metaphenylenediamine, 4,4'-diaminodiphenylmethane, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis (4-amino). Phenoxy) pentane, 1,7-bis (4-aminophenoxy) heptane, bis [2- (4-aminophenyl) ethyl] hexanedioic acid, N, N-bis (4-aminophenyl) methylamine, 1,5 -Diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4' -Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-) Aminophenyl) hexafluoropropane, 4,4'-(p-phenylenediisopropyridene) bisaniline, 4,4'-(m-phenylenediisopropyriden) bisaniline, 1,4-bis (4-aminophenoxy) benzene, Main chain diamines such as 4,4'-bis (4-aminophenoxy) biphenyl; side chain diamines in which a side chain structure having 6 or more carbon atoms is bonded to a diaminophenyl structure;
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; and the diamine described in JP-A-2010-97188 can be used.

The diamine compound [D] is preferably a side chain diamine. Specifically, the diamine compound [D] preferably has a partial structure represented by the following formula (2), and more preferably an aromatic diamine having a partial structure represented by the following formula (2). preferable.
* -L ^1- R ^1- R ^2- R ^3- R ⁴ ... (2)
(In the formula (2), ^{L 1} represents a single ^{bond, -O -, - CO -,} - COO- * 1, -OCO- * 1, -NR 5 -, - NR 5 -CO- * 1, -CO -NR ^5- * ¹ , alkanediyl group with 1 to 6 carbon atoms, -OR ^6- * ¹ , or -R ⁶ -O- * ¹ (where R ⁵ is a hydrogen atom or 1 to 10 carbon atoms It is a monovalent hydrocarbon group, and R ⁶ is an alkanediyl group having 1 to 3 carbon atoms. “* ¹ ” indicates that it is a bond with ^{R 1. ). R 1} and R. ³ is an independently single-bonded, substituted or unsubstituted phenylene group, or substituted or unsubstituted cycloalkylene group, and R ² is a single-bonded, substituted or unsubstituted phenylene group, substituted or unsubstituted. cycloalkylene group, or ^-R 7 ^-B 1 ^{-R 8} - (provided that, ^{R 7} and ^{R 8} are each independently a substituted or unsubstituted phenylene group or a cycloalkylene group, ^{B 1} is a single bond, -O-, -COO- * ² , -OCO- * ² , -OCH _2- * ² , -CH ₂ O- * ² , or an alkanediyl group having 1 to 3 carbon atoms. "* ² " is It indicates that it is a bond with R ^{8. ) R 4} is a hydrogen atom, a fluorine atom, a cyano group, and CH ₃ COO- * ³ (“* ³ ” is a bond with ^{R 3).} An alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a fluoroalkoxy group having 1 to 18 carbon atoms, and a carbon number having a steroid skeleton. It is a monovalent group in which at least one hydrogen atom of a hydrocarbon group having 17 to 51 carbon atoms or an alkyl group having 1 to 18 carbon atoms is substituted with a cyano group, except that R ¹ , R ² and R ^{3 are used.} When all of the above are single bonds, R ⁴ is an alkyl group having 6 to 18 carbon atoms, a fluoroalkyl group having 6 to 18 carbon atoms, an alkoxy group having 6 to 18 carbon atoms, and a fluoroalkoxy group having 6 to 18 carbon atoms. , a hydrocarbon group having a carbon number of 17 to 51 having a steroid skeleton, or, .R ¹ is a monovalent group in which at least one hydrogen atom is substituted with a cyano group of the alkyl group having 6 to 18 carbon atoms, When the total number of the substituted or unsubstituted phenylene group and the substituted or unsubstituted cycloalkylene group of ^{R 2} and R ^{3 is 1, R 4} is an alkyl group having 4 to 18 carbon atoms and 4 carbon atoms. ~ 18 fluoroalkyl groups, 4-18 carbon atoms alkoxy It is a monovalent group in which at least one hydrogen atom of a group, a fluoroalkoxy group having 4 to 18 carbon atoms, or an alkyl group having 4 to 18 carbon atoms is substituted with a cyano group. "*" Indicates a bond. )

In the above formula (2), the substituent bonded to the ring of the substituted phenylene group and the substituted cycloalkylene group is preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a cyano group. The number of substituents of each of the substituted phenylene group and the substituted cycloalkylene group is preferably 1 or 2, and more preferably 1.
When R ⁴ is an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluoroalkoxy group having 1 to 18 carbon atoms, R ⁴ is linear. The number of carbon atoms is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more.
The group represented by the above formula (2) has at least one ring of ^{R 1} , R ² and R ³ in that excellent dispersibility is exhibited even when the amount of the polymer [P] blended is smaller. It preferably has a structure or R ⁴ has a steroid skeleton, and ^{the total ring structure of R 1} , R ² and R ³ is two or more, or R ⁴ has a steroid skeleton. It is more preferable to have it, and it is further preferable to have a steroid skeleton.

（式（３）中、Ｌ^１、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、上記式（２）と同義である。） Of the above, the group represented by the above formula (2) is diamino in the diamine compound [D2] in that the in-plane orientation of the polymer [P] can be made higher and the dispersibility of the dispersion to be dispersed can be made higher. An aromatic diamine bonded to a phenyl group (that is, a compound represented by the following formula (3)) is particularly preferable. In this case, the bonding positions of the two primary amino groups are not particularly limited, and for example, the 2,4-position, 2,5-position, and 3,5-position with respect to the group represented by the above formula (2). Is.

(In formula (3), L ¹ , R ¹ , R ² , R ³ and R ⁴ are synonymous with the above formula (2).)

（式（Ｅ－１）中、Ｘ^I及びＸ^IIは、それぞれ独立に、単結合、－Ｏ－、＊－ＣＯＯ－又は＊－ＯＣＯ－（ただし、「＊」はＸ^Ｉとの結合手を示す。）であり、Ｒ^Ｉは炭素数１～３のアルカンジイル基であり、Ｒ^ＩＩは単結合又は炭素数１～３のアルカンジイル基であり、Ｒ６は水素原子、炭素数１～２０のアルキル基、炭素数１～２０のフルオロアルキル基、炭素数１～２０のアルコキシ基又は炭素数１～２０のフルオロアルコキシ基であり、ａは０～２の整数であり、ｂは０～２の整数であり、ｄは０又は１である。但し、ａ及びｂが同時に０になることはない。）
で表される化合物等を挙げることができる。 Specific examples of the diamine compound [D2] include hexanoxy-3,5-diaminobenzene, heptanoxy-2,4-diaminobenzene, dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, and hexadecanoxy-. 2,4-Diaminobenzene, Octadecanoxy-2,4-Diaminobenzene, Pentadecanoxy-2,5-Diaminobenzene, Octadecanoxy-2,5-Diaminobenzene, Cholestanyloxy-3,5-Diaminobenzene, Cholestenyloxy-3 , 5-Diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, 3,5- Ranostanyl diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholesterol, 3,6-bis (4-aminophenoxy) cholesterol, 2,4-diamino-N, N-diallylaniline, 4- (4' -Trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 3,5-diaminobenzoic acid = 5ξ- Benzene-3-yl, the following formula (E-1)

(In the formula (E-1), X ^I and X ^II are independently single-bonded, -O-, * -COO- or * -OCO- (where "*" is a bond with ^{X I.} shown.), and, ^{R I} is an alkanediyl group having 1 to 3 carbon ^{atoms, R II} is a single bond or an alkanediyl group having a carbon number of 1-3, R6 is hydrogen, 1 to 20 carbon atoms It is an alkyl group, a fluoroalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a fluoroalkoxy group having 1 to 20 carbon atoms, where a is an integer of 0 to 2 and b is 0 to 2. It is an integer and d is 0 or 1. However, a and b cannot be 0 at the same time.)
Examples thereof include compounds represented by.

（式（Ｅ－１－１）～式（Ｅ－１－１１）中、Ｘ^１は、－Ｏ－、－ＯＣＨ_２－、－ＣＨ_２Ｏ－、－ＣＯＯ－ＣＨ_２－又は－ＣＨ_２－ＯＣＯ－であり、Ｒ^６は上記式（Ｅ－１）と同義である。） Specific examples of the compound represented by the above formula (E-1) include compounds represented by each of the following formulas (E-1-1) to (E-1-11).

(In formulas (E-1-1) to (E-1-11), X ¹ is -O-, -OCH _2- , -CH ₂ O-, -COO-CH _2- or -CH _2- It is OCO-, and R ⁶ is synonymous with the above formula (E-1).)

The content ratio of the structural unit U2 in the polymer [P] is such that the dispersibility of the dispersant (particularly, the dispersibility of the organic solvent system in the dispersion medium) can be sufficiently ensured. It is preferably 0.5 mol% or more, and more preferably 1 mol% or more, based on the total amount of the structural units derived from the diamine compound (that is, the total amount of the structural unit U1 and the structural unit U2). Preferably, it is more preferably 2 mol% or more, and particularly preferably 15 mol% or more. Further, the content ratio of the structural unit U2 is a structural unit derived from the diamine compound of the polymer [P] in that the dispersibility of the dispersant (particularly, the dispersibility in the aqueous dispersion medium) can be improved. It is preferably 95 mol% or less, more preferably 90 mol% or less, further preferably 80 mol% or less, and particularly preferably 50 mol% or less, based on the total amount of the above. In the synthesis of the polymer [P], the diamine compound [D2] may be used alone or in combination of two or more.

The polymer [P] is at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide. The polymer [P] uses, for example, at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester and tetracarboxylic acid diester dihalide, and a diamine compound as a raw material composition. It can be obtained by the polymerization.

[Polyamic acid]
When the polymer [P] is a polyamic acid, the polyamic acid (hereinafter, also referred to as “polyamic acid [P]”) can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine compound. ..

(Tetracarboxylic dianhydride)
The tetracarboxylic dianhydride used for the synthesis of the polymer [P] is not particularly limited, and is, for example, an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, or an aromatic tetracarboxylic dianhydride. You can mention things. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-di). Oxo tetrahydrofuran-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-spirio -3'-( tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -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 dianhydride, bicyclo [2.2.2] Octo- 7-ene-2,3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, 1,2,3,4-cyclopentantetracarboxylic dianhydride, ethylene glycolbis (annehydrotri) Meritate), 1,3-propylene glycol bis (anhydrotrimeritate), etc .;
Aromatic tetracarboxylic dianhydrides include, for example, pyromellitic dianhydride, 4,4'-biphthalic dianhydride, 4,4'-carbonyldiphthalic dianhydride, 4,4'-oxydiphthalic dianhydride. Anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,4,5,6-tetracarboxylic dianhydride, etc.;
In addition to each, the tetracarboxylic dianhydride described in JP-A-2010-97188 can be used.

（式（ｔ－１）～（ｔ－２１）中、「＊」は、酸無水物基（－ＣＯ－Ｏ－ＣＯ－）が有するカルボニル基に結合する結合手であることを表す。） The tetracarboxylic dianhydride used for the synthesis of the polymer [P] has a structure in which the molecular chain of the polymer [P] is rigid and highly uniaxially linear, so that the polymer [P] can be easily oriented in the plane. Therefore, among the above, the compound has a partial structure represented by each of the following formulas (t-1) to (t-21) (hereinafter, also referred to as "specific tetracarboxylic dianhydride"). preferable.

(In the formulas (t-1) to (t-21), "*" indicates a bond that binds to the carbonyl group of the acid anhydride group (-CO-O-CO-).)

In the polymer [P], the content ratio of the structural unit derived from the specific tetracarboxylic dianhydride is the tetracarboxylic dianhydride contained in the polymer [P] from the viewpoint of increasing the dispersibility of the dispersant. It is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% or more, based on the total amount of the structural unit derived from. The content ratio of the structural unit derived from the specific tetracarboxylic dianhydride shall be 100 mol% or less with respect to the total amount of the structural unit derived from the tetracarboxylic dianhydride contained in the polymer [P]. Can be done. As the tetracarboxylic dianhydride, one of these can be used alone or in combination of two or more.

The tetracarboxylic acid derivative used for the synthesis of the polymer [P] has a structure in which the molecular chain of the polymer [P] is rigid and highly uniaxially linear, and facilitates in-plane orientation of the polymer [P] (riotropic liquid crystal). It is preferable to contain an aromatic tetracarboxylic acid derivative in that the dispersibility of the dispersant can be further enhanced, and the above formulas (t-1) to (t-6) are used. It is particularly preferable to contain an aromatic tetracarboxylic acid derivative having the represented partial structure. The content ratio of the structural unit derived from the aromatic tetracarboxylic acid derivative in the polymer [P] is 20 mol% or more with respect to the total amount of the structural unit derived from the tetracarboxylic acid derivative contained in the polymer [P]. It is preferably 30 mol% or more, more preferably 50 mol% or more. In the synthesis of the polymer [P], one aromatic tetracarboxylic acid derivative may be used alone or two or more thereof may be used in combination.

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

When the diamine compound has an acidic functional group, the above reaction may be carried out after neutralizing 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, when the diamine compound has a basic functional group, the above 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 ratio of the molecular weight adjusting agent used is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the total of the tetracarboxylic dianhydride and the diamine used.

The synthetic reaction of 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 aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. 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 alcohol, ketone, ester, ether, halogenated hydrocarbon and hydrocarbon (organic solvent 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 and another organic solvent in the above ratio range. The amount of the organic solvent used (a) is such that the total amount (b) of the tetracarboxylic 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.

[Polyamic acid ester]
When the polymer [P] is a polyamic acid ester, the polyamic acid ester (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, [II] a method of reacting a tetracarboxylic acid diester with a diamine, [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine, and the like. The polyamic acid ester [P] may have only the amic acid ester structure, or the amic acid structure and the amic acid ester structure may coexist.

[Polyimide]
When the polymer [P] is a polyimide, the polyimide (hereinafter, also referred to as "polyimide [P]") dehydrates the polyamic acid [P] or the polyamic acid ester [P] synthesized as described above. It can be obtained by ring closure and imidization. The polyimide [P] may be a completely imidized product obtained by dehydrating and closing all of the amic acid structure or the amic acid ester structure of the polyamic acid [P] or the polyamic acid ester [P] which is the precursor thereof. , Only a part of the amic acid structure and the amic acid ester structure may be dehydrated and ring-closed, and the amic acid structure or the partially imidized product in which the amic acid ester structure and the imide ring structure coexist may be used. The imidization ratio of polyimide [P] is preferably 50% or more, more preferably 75% or more, and more preferably 85% or more in order to sufficiently increase the dispersibility of the dispersoid. Is more preferable, and 90% or more is particularly preferable. 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.

Dehydration ring closure to obtain polyimide [P] is preferably done by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent and adding at least one of a dehydrating agent and a dehydration ring closure catalyst to this solution. It is carried out by a method of heating according to the above.

In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 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-methylpiperidin, 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.

The reaction solution containing the polymer [P] may be used as it is for the preparation of the dispersion composition, or the polymer [P] contained in the reaction solution may be isolated and then used for the preparation of the dispersion composition. Alternatively, the isolated polymer [P] may be purified and then subjected to preparation of a dispersion composition. Isolation and purification of the polymer [P] can be carried out according to a known method.

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 was 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 (Mw) of the polymer [P] measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. Is. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.

Here, carbon nanotubes, which are one of the dispersoids, have excellent properties in terms of conductivity, heat resistance, toughness, weight reduction, and the like. However, carbon nanotubes have high cohesiveness and are difficult to be uniformly dispersed in both aqueous and organic solvent-based dispersion media. Further, if the dispersed state of the carbon nanotubes is not good, there is a concern that various characteristics of the carbon nanotubes may not be sufficiently exhibited in the film or wiring obtained by using the dispersed composition. In this respect, the dispersion composition of the present disclosure contains the polymer [P] as a dispersant, so that the dispersibility of carbon nanotubes is high and excellent in both aqueous and organic solvent systems. Further, by using a dispersion composition containing carbon nanotubes and a polymer [P], a film and wiring having excellent conductivity can be formed.

The content ratio of the polymer [P] in the dispersion composition is 2% by mass or more with respect to the total mass of the dispersion to be dispersed and the polymer [P] from the viewpoint of sufficiently ensuring the dispersibility of the dispersion to be dispersed. It is preferable, it is more preferably 5% by mass or more, and further preferably 10% by mass or more. Further, the content ratio of the polymer [P] is 99.5% by mass or less with respect to the total mass of the dispersion to be dispersed and the polymer [P] from the viewpoint of sufficiently obtaining the function of the dispersion to be dispersed. It is preferably 99% by mass or less, and more preferably 99% by mass or less.

The content ratio of the polymer [P] in the dispersion composition is preferably 0.05 to 30% by mass with respect to the total amount of the dispersion medium and the polymer [P]. According to the polymer [P], it is preferable in that it exhibits high dispersibility of the dispersion to be dispersed at a relatively low polymer concentration. Further, since the viscosity of the dispersion composition can be lowered, the coatability when forming a coating film on the substrate is good, and a thin film of about 0.1 μm can be produced, which is excellent in industrial productivity. The content ratio of the polymer [P] is more preferably 0.1 to 25% by mass, still more preferably 0.2 to 20% by mass, based on the total mass of the dispersion medium and the polymer [P]. is there.

The solid content concentration of the dispersion composition (that is, the ratio of the total mass of the components other than the dispersion medium of the dispersion composition to the total mass of the dispersion composition) is appropriately selected in consideration of the viscosity and the volatility of the dispersion medium. However, it is preferably in the range of 1 to 70% by mass, more preferably in the range of 3 to 50% by mass, and further preferably in the range of 5 to 40% by mass. The dispersion composition of the present disclosure may be applied to the surface of a substrate and preferably used in the form of forming a coating film by removing the dispersion medium. At this time, if the solid content concentration is 1% by mass or more, the film thickness of the coating film does not become too thin, and it becomes easy to form a coating film containing a dispersion. On the other hand, when the solid content concentration is 70% by mass or less, the film thickness of the coating film does not become excessive and it becomes easy to form a high-quality coating film. In addition, the viscosity of the dispersion composition does not become too high, and deterioration of coatability can be suppressed.

The dispersion composition of the present disclosure contains a dispersant different from the polymer [P] as a dispersant (hereinafter, also referred to as “other dispersant”) as long as the purpose and effect of the present disclosure are not impaired. You may be. The content ratio of the other dispersant is preferably 10% by mass or less, more preferably 5% by mass or less, and 1% by mass or less, based on the total amount of the dispersant contained in the dispersion composition. It is more preferable to have.

<Other ingredients>
The dispersion composition of the present disclosure contains (A) a dispersant, (B) a dispersion medium, and other components other than (C) a dispersant within a range that does not interfere with the purpose and effect of the present disclosure. May be good. Examples of other components include surfactants, fillers, pigments, defoamers, sensitizers, antioxidants, adhesion aids, antistatic agents, leveling agents, antibacterial agents and the like. The content ratio of other components can be appropriately set according to each compound to be blended within a range that does not interfere with the effects of the present disclosure.

The method for preparing the dispersion composition is not particularly limited, and the dispersion composition can be prepared according to a known method. For example, it can be prepared by mixing the dispersant, the dispersion medium, and the dispersant, and heating, stirring, or the like as necessary. The temperature at which the dispersion composition is prepared is preferably 5 to 90 ° C, more preferably 10 to 65 ° C. The treatment of mixing the dispersant, the dispersion medium, and the dispersant may be performed using, for example, a homogenizer or a bead mill.

In the dispersion composition of the present disclosure, aggregation of the object to be dispersed is suppressed by using the polymer [P] as the polymer dispersant, whereby the object to be dispersed is stably dispersed in the dispersion medium. By applying the dispersion composition of the present disclosure on a substrate and preferably heating to remove the dispersion medium, a coating film containing a dispersion can be formed on the substrate. It is also possible to use the dispersion composition of the present disclosure as it is or by mixing it with another dispersion liquid in a liquid state.

The dispersion composition of the present disclosure can be used for various purposes depending on the type of the dispersion to be dispersed. Specifically, transparent conductive film, antistatic film, insulating film, protective film, antireflection film, coloring film, field effect transistor (FET), touch panel, conductive ink, paint, printing ink, ink for inkjet coating, etc. Can be used for.

<< Second Embodiment >>
Next, the method for producing the anisotropic membrane of the present disclosure will be described. In this production method, a holding step of holding a dispersion composition containing a dispersion object, a dispersion medium, and a compound exhibiting lyotropic liquid crystallinity on the surface of a holding body while applying shear stress, and dispersion held on the surface of the holding body. It includes a transfer step of transferring the composition onto a substrate. The details of this manufacturing method will be described below.

（式（１）中、ｎは０又は１である。ｎが０の場合、Ｒ^１～Ｒ^４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。ｎが１の場合、Ｒ^１～Ｒ^８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。） (Holding process)
Regarding the dispersion to be dispersed and the dispersion medium contained in the dispersion composition, the description of (A) the dispersion to be dispersed and (B) the dispersion medium of the first embodiment can be incorporated respectively.
The compound exhibiting lyotropic liquid crystallinity (hereinafter, also referred to as “compound (L)”) is not particularly limited as long as it is a compound exhibiting liotropic liquid crystallinity, but is preferably a polymer, and is a polyamic acid, a polyamic acid ester, and a polyimide. It is preferably at least one polymer selected from the group consisting of. Further, among these, the compound (L) is particularly preferably a polymer having a structural unit U1 derived from the diamine compound [D1] represented by the following formula (1). As for the description of the diamine compound [D1], the description of the diamine compound [D1] of the first embodiment can be applied.

(If in the formula (1), n is 0 or 1 .n is zero, at least one of R 1 ^~ R ⁴ is a monovalent group having an ionic functional group, the remainder, respectively Independently, it is a hydrogen atom, a halogen atom or a monovalent organic group. When n is 1, ^{at least one of R 1} to R ⁸ is a monovalent group having an ionic functional group, and the rest. Are independently hydrogen atoms, halogen atoms or monovalent organic groups.)

The compound (L) may be a polymer in which all the structural units constituting the compound (L) are the structural unit U1, and is a polymer [P] further having a structural unit U2) different from the structural unit U1. You may. When the compound (L) further has the structural unit U2, the description of the first embodiment can be applied to the description of the structural unit U2 and the polymer [P]. In addition, the description of the first embodiment can be applied to the description of the anhydride, the polymerization method, and the like for the tetracarboxylic acid used for the synthesis of the compound (L).

The holding body for holding the dispersion composition is not particularly limited, and examples thereof include rotating bodies made of resin, rubber, metal, etc .; flat plates and the like. The holder is preferably a rotating body. In this step, the dispersion composition is made to hold the holding body by supplying the dispersion composition to the holding body while applying shear stress. In a preferred embodiment, the stress generator is placed at a position facing the surface of the holding body, and the dispersion composition is supplied so that the dispersion composition passes between the rotating body and the stress generator. At this time, shear stress is applied to the dispersion composition by making the moving speed of the surface of the holding body different from the moving speed of the surface of the stress generating body. The surface of the stress generating body may move in the same direction as the moving direction of the holding body surface (rotating direction when the holding body is a rotating body), and moves in the direction opposite to the moving direction of the holding body surface. May be good. Further, the stress generator may be, for example, a housing or a blade, and may be a member whose position is fixed.

The amount of the dispersion composition to be retained on the surface of the retainer can be appropriately adjusted according to the size of the gap between the surface of the retainer and the surface of the stress generator. The gap is, for example, 0.01 to 5 μm. It is preferable that the stress generator also functions as a holding amount adjusting unit for adjusting the amount of the dispersion composition held on the surface of the holding body.

Alternatively, by using a bar coating method, a slit coating method, or the like, the dispersion composition is applied to the flat plate as the retainer while applying shear stress to form a coating film, thereby forming the dispersion composition on the retainer. May be retained.

(Transfer process)
In this step, the dispersion composition retained on the surface of the retainer is transferred onto the substrate. Examples of the base material include glass such as float glass and soda glass; and a transparent base material made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (aliphatic olefin). The dispersion composition can be transferred to the substrate by bringing the dispersion composition on the surface of the retainer into contact with the substrate and preferably moving the substrate relative to the retainer. When the dispersion composition is transferred to the substrate, the transfer may be performed by pressing the retainer from the side opposite to the retainer across the substrate at a position facing the retainer.

An anisotropic film can be formed on the base material by preferably heating the coating film transferred to the base material. The heating temperature at this time is, for example, 30 to 180 ° C, more preferably 40 to 150 ° C. The heating time is, for example, 1 to 30 minutes. The film thickness of the anisotropic film formed is preferably 0.05 to 5 μm.

Next, an anisotropic film forming apparatus for forming an anisotropic film on a base material using the present manufacturing method will be described. The anisotropic film forming apparatus of the present disclosure includes a holding portion for holding a dispersion composition containing a dispersion object, a dispersion medium, and a compound exhibiting lyotropic liquid crystallinity on the surface of the holding body while applying shear stress, and a holding body. A transfer unit for transferring the dispersion composition held on the surface onto the substrate is provided.

An embodiment in which the anisotropic film forming apparatus of the present disclosure is embodied in a printing type shear coating apparatus will be described with reference to FIG.

As shown in FIG. 1, the shear coating device 10 is a roll coater type, and includes a coating roll 11, a doctor roll 12, and a backup roll 13. The coating roll 11 is a rotating body whose surface layer portion is, for example, a rubber layer, and the dispersion composition 20 is applied to the surface thereof.

The doctor roll 12 is, for example, a metal rotating body, and is arranged at a position facing the coating roll 11. In the shear coating device 10, the dispersion composition 20 is supplied to the gap between the coating roll 11 and the doctor roll 12, so that the dispersion composition 20 is applied to the surface of the coating roll 11 to form a coating film. The doctor roll 12 adjusts the coating amount (that is, the film thickness) on the surface of the coating roll 11 by scraping off the excess dispersion composition on the surface of the coating roll 11. The coating amount can be adjusted by adjusting the size of the gap between the coating roll 11 and the doctor roll 12, the rotation speed of the doctor roll 12, the viscosity of the dispersion composition 20, and the like.

The rotation directions of the coating roll 11 and the doctor roll 12 may be the same or opposite to each other. In the present embodiment, the rotation direction of the coating roll 11 and the rotation direction of the doctor roll 12 are the same direction. Further, unlike the rotation speed V1 of the coating roll 11 and the rotation speed V2 of the doctor roll 12, the rotation speed V2 is faster than the rotation speed V1, for example. At least one of the coating roll 11 and the doctor roll 12 may be rotatable in the forward and reverse directions. The coating roll 11 corresponds to the "retainer" and the doctor roll 12 corresponds to the "stress generator".

The backup roll 13 is arranged at a position opposite to the coating roll 11 with respect to the transport path of the base material 30 and facing the coating roll 11. The arrows in FIG. 1 indicate the moving direction of the base material 30. The backup roll 13 presses the base material 30 from the surface of the base material 30 opposite to the coated surface. As a result, as the base material 30 moves relative to the coating roll 11, the coating film on the surface of the coating roll 11 becomes the surface of the base material 30 at the contact portion 19 between the coating roll 11 and the base material 30. The anisotropic film 21 is formed on the surface of the base material 30.

Here, as the coating roll 11 rotates, a coating film made of the dispersion composition 20 is formed on the surface of the coating roll 11. At that time, in the contact portion 18 where the coating roll 11 and the doctor roll 12 come into contact with each other through the layer of the dispersion composition 20, shear stress is applied to the dispersion composition 20 by the rotation of the doctor roll 12, and the coating roll 11 is subjected to shear stress. The excess dispersion composition 20 on the surface is scraped off. Due to this shear stress, in the coating film composed of the dispersion composition 20, the compound (L) in the coating film is uniaxially oriented, and the dispersion to be dispersed is arranged along the molecular chain of the compound (L). It is preferable that the coating roll 11 and the doctor roll 12 rotate in the same direction from each other in that a sufficient shear stress can be applied to the coating film made of the dispersion composition 20. After that, the coating film formed on the surface of the coating roll 11 is transferred at the contact portion 19 with the base material 30 on the coating roll 11, so that the anisotropic film 21 is formed on the base material 30.

In the shear coating device 10 described above, a dispersion composition containing the compound (L) as a dispersant is applied onto the coating roll 11 while applying shear stress to form a coating film, and then the coating film is applied to the base material 30. An anisotropic film was formed on the base material 30 by transferring it onto the substrate 30. According to this configuration, as compared with the case where the anisotropic film is directly formed on the base material by including the step of transferring the coating film temporarily formed on the coating roll 11 as the retainer to the base material 30. An anisotropic film having excellent various characteristics such as conductivity anisotropy, polarization absorption characteristics, heat transfer anisotropy, and degas resistance can be obtained. In particular, by using the coating roll 11 which is a rotating body as the holding body, it is preferable in that the effect of improving various characteristics can be enhanced.

The contact portion 18 in which the coating roll 11 and the doctor roll 12 come into contact with each other via the layer of the dispersion composition 20 corresponds to a "holding portion for holding the dispersion composition on the surface of the holding body while applying shear stress". The contact portion 19 of the coating roll 11 with the base material 30 corresponds to a “transfer portion for transferring the dispersion composition held on the surface of the retainer onto the base material”.

Next, an embodiment in which the anisotropic film forming apparatus of the present disclosure is embodied in a dispenser type shear coating apparatus will be described with reference to FIG.

In FIG. 2, the shear coating device 100 is a ballpoint pen type coating device, and includes a main body 101 and a ball 102. The main body 101 is an elongated tubular body, and a housing 103 for accommodating the dispersion composition 200 is formed inside the main body 101. Further, a ball holding portion 104 for rotatably holding the ball 102 is provided at the tip portion of the main body portion 101 in the axial direction. A slight gap is formed between the ball holding portion 104 and the circumferential surface of the ball 102, and the dispersion composition 200 filled in the accommodating portion 103 can enter the gap.

In order to form an anisotropic film on the surface of the base material 30 using the shear coating device 100, the balls 102 of the shear coating device 100 and the base material 30 are brought into contact with each other, and the shear coating device 100 is brought into contact with the base material 30. Is relatively moved (for example, in the A direction in FIG. 2). As a result, the balls 102 rotate, and along with the rotation, the dispersion composition 200 filled in the accommodating portion 103 adheres to the surface of the balls 102. At that time, in the contact portion 105 in which the balls 102 and the ball holding portion 104 come into contact with each other through the layer of the dispersion composition 20, shear stress is applied from the ball accommodating portion 104 to the dispersion composition 20 by the rotation of the balls 102. Will be done. In the coating film formed on the surface of the balls 102 due to this shear stress, the compound (L) in the dispersion composition is uniaxially oriented, and the dispersion to be dispersed is arranged along the molecular chain of the compound (L). After that, the coating film formed on the surface of the ball 102 is transferred at the contact portion 106 with the base material 30, so that the anisotropic film 201 is formed on the base material 30. In FIG. 2, the arrow B indicates the direction in which the dispersion composition 200 in the accommodating portion 103 moves in a state where the anisotropic film 201 is formed on the surface of the base material 30 by the shear coating device 100. ..

According to the shear coating apparatus 100 described above, an anisotropic film having excellent various properties can be easily formed on the base material 30. Further, even when forming an anisotropic film having a narrow width such as wiring, the shear coating device 100 is moved with respect to the base material 30 while the balls 102 are in contact with the base material 30. It is excellent in that the anisotropic film 201 can be formed on the material 30. The contact portion 105 in which the balls 102 and the ball holding portion 104 come into contact with each other via the layer of the dispersion composition 20 corresponds to "a holding portion that holds the dispersion composition on the surface of the holder while applying shear stress". The contact portion 106 of the ball 102 with the base material 30 corresponds to a “transfer portion for transferring the dispersion composition held on the surface of the holding body onto the base material”. The ball 102 corresponds to the "holding body", and the ball accommodating portion 104 corresponds to the "stress generating body".

Here, the material exhibiting lyotropic liquid crystallinity is applied to a base material while applying shear stress by using a slit coating method, a bar coating method, or the like, thereby forming a coating film in which the material exhibiting lyotropic liquid crystallinity is uniaxially oriented. Obtainable. However, when a coating film is formed on a base material by the slit coating method or the bar coating method, for example, the hydrophobic groups are oriented at a polar angle due to the influence of highly hydrophobic air on the contact surface side with air. It is conceivable that the orientation is easily disturbed on the contact surface side with air, and the anisotropy is lowered, so that the desired characteristics cannot be sufficiently obtained. As for the coatability, the slit coating method and the bar coating method make it difficult to form a coating film on a substrate having insufficient wettability, or it is difficult to coat a deformed substrate or a curved substrate. There may be.

On the other hand, according to the method for producing an anisotropic film and the anisotropic film forming apparatus of the present disclosure, by combining the shear coating method and the transfer method, conductivity anisotropy, polarization absorption characteristics, and heat transfer anisotropy An anisotropic film having excellent properties such as properties and resistance to degas can be obtained. Therefore, the anisotropic film obtained by the method for producing an anisotropic film and the anisotropic film forming apparatus of the present disclosure is, for example, a polarizing film, a retardation film, a piezoelectric film, an anisotropic conductive film, or anisotropic heat. It can be used as various anisotropic films such as a conductive film and an anisotropic magnetic film.

It is not clear why an anisotropic film having improved various properties such as conductivity anisotropy could be obtained by the production method including the transfer step, but one reason is that the compound ( It is considered that the uniaxial orientation of L) was improved, and thereby the dispersibility and orientation of the object to be dispersed were improved. In particular, when a rotating body is used as the holding body, it is considered that the uniaxial orientation is further improved and various characteristics are further improved.

Hereinafter, the contents of the present disclosure will be described in more detail with reference to Examples, but the contents of the present disclosure are not limited to these Examples.

In the following example, the weight average molecular weight Mw and the imidization rate of the polymer were measured by the following methods. The required amounts of the raw material compounds and polymers used in the following examples were secured by repeating the synthesis on the synthetic scale shown in the following synthesis examples as necessary.

[Weight average molecular weight Mw of polymer]
The weight average molecular weight Mw is a polystyrene-equivalent value measured by GPC under the following conditions.
Column: Made by Tosoh Corporation, TSKgelGRCXLII
Solvent: N, N-dimethylformamide solution containing lithium bromide and phosphoric acid Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Imidization rate of polymer]
A solution containing polyimide is put into pure water, the obtained precipitate is sufficiently dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR is measured at room temperature using tetramethylsilane as a reference substance. did. From the obtained ¹ H-NMR spectrum, the imidization ratio was determined using the following mathematical formula (EX-1).
Imidization rate (%) = (((1-E ¹ ) / E ² ) x α) x 100
… (EX-1)
(In the formula (EX-1), E ¹ is the peak area derived from the proton of the NH group appearing near the chemical shift of 10 ppm, E ² is the peak area derived from other protons, and α is the precursor of the polymer (α). The ratio of the number of other protons to one proton of the NH group in polyamic acid).
In the following, the compound represented by the formula (X) may be simply abbreviated as "compound (X)".

[First Example]
1. 1. Synthesis of polymer [Synthesis example 1: Synthesis of polyamic acid]
36.77 g (95 mol parts) of pyromellitic acid dianhydride, 6.68 g (20 mol parts) of 2,5-diaminobenzenesulfonic acid, and 31.56 g (80 mol parts) of 2,4-diamino-heptyloxybenzene. Was dissolved in 425 g of N-methyl-2-pyrrolidone (NMP), and the reaction was carried out at room temperature for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 68 g of polyamic acid (hereinafter referred to as polymer (PAA-1)).

[Synthesis Example 2: Polyimide Synthesis]
26.32 g (95 mol parts) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 23.03 g (99 mol parts) of 2,5-diaminobenzenesulfonic acid, and cholestanyl 3,5-diaminobenzoate 0. 65 g (1 mol) was dissolved in 200 g of N-methyl-2-pyrrolidone (NMP), and the reaction was carried out at room temperature for 6 hours. A polyamic acid solution having a polymer concentration of 20% by mass was obtained. After adding 250 g of NMP to the obtained polyamic acid solution, 46.4 g of pyridine and 36.0 g of acetic anhydride were added, and the mixture was reacted at 110 ° C. for 4 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried under reduced pressure at 100 ° C. to obtain 45 g of polyimide (hereinafter referred to as polymer (PI-1)). The imidization rate of the obtained polymer (PI-1) was 99%.

[Synthesis Examples 3-9]
Polyimides (polymers (PI-2) to (PI-6)) are the same as in Synthesis Example 2 except that the types and amounts of the tetracarboxylic dianhydride and the diamine compound used in the reaction are changed as shown in Table 1 below. (Pi-1) and (pi-2)) were obtained. The imidization ratio of each polyimide is also shown in Table 1 below.
[Synthesis Example 10]
A polyamic acid (polymer (paa-1)) was obtained in the same manner as in Synthesis Example 1 except that the types and amounts of the tetracarboxylic dianhydride and the diamine compound used in the reaction were changed as shown in Table 1 below.

The numerical values in Table 1 indicate the ratio (mol%) of the tetracarboxylic dianhydride used in the reaction to the total amount of the tetracarboxylic dianhydride used in the reaction, and for the diamine compound, the diamine compound used in the reaction. The usage ratio (mol%) to the total amount of. The abbreviations of the tetracarboxylic dianhydride and the diamine compound in Table 1 are as follows.
(Tetracarboxylic dianhydride)
AN-1; 2,3,5-tricarboxycyclopentyl acetate dianhydride AN-2; pyromellitic dianhydride AN-3; 1,3-propylene glycol bis (anhydrotrimeritate)
(Diamine compound)
DA-1; 2,5-diaminobenzenesulfonic acid DA-2; 2,5-diaminobenzoic acid DA-3; 3,5-diaminobenzoate cholestanyl DA-4; cholestanyloxy-2,4-diaminobenzene DA -5; Compound DA-6 represented by the following formula (DA-5); 2,4-diamino-heptyloxybenzene DA-7; Paraphenylenediamine

2. 2. Preparation and Evaluation of CNT-Containing Dispersion Composition [Example 1]
(1) Preparation of dispersion composition 400 parts by mass of distilled water as a solvent is placed in a container containing 5 parts by mass of multiwall carbon nanotubes (MWNT) and 95 parts by mass of the polymer (PI-1) obtained in Synthesis Example 2. added. Then, ultrasonic dispersion was performed for 10 minutes to prepare a dispersion composition (S-1).

(2) Evaluation of CNT dispersibility (water system)
The dispersion composition (S-1) obtained in (1) above was allowed to stand on a flat place for 1 day. The evaluation was "good (○)" if the initial dispersion state was maintained, and "poor (x)" if sedimentation or aggregation was observed. As a result, the CNT dispersibility of this dispersion composition (S-1) was "good (◯)".
(3) Evaluation of CNT dispersibility (organic solvent system)
A dispersion composition was prepared in the same manner as in (1) above, except that cyclopentanone was used instead of the distilled water used as the solvent in (1) above. The obtained dispersion composition was allowed to stand on a flat place, and the dispersion state with the passage of time was observed. The evaluation is "best (◎◎)" if the initial dispersion state is maintained after 1 week, "excellent (◎)" if the initial dispersion state is maintained until 3 days later, and the initial dispersion state until 1 day later. "Good (○)" if the condition is maintained, "Yes (△)" if the initial dispersion state is maintained until 3 hours later, and "Poor (×)" if sedimentation or aggregation is observed after 3 hours. And said. As a result, the CNT dispersibility (organic solvent system) of this dispersion composition was "possible (Δ)".

(4) Evaluation of CNT coating property The dispersion composition (S-1) obtained in the above (1) is applied onto a glass substrate using a blade and dried on a hot plate at 80 ° C. for 10 minutes to obtain an average film. A coating film having a thickness of 1 μm was formed. This coating film was observed with a microscope at a magnification of 50 times to check for uneven film thickness and the presence or absence of pinholes. The evaluation was "good (○)" when neither film thickness unevenness nor pinhole was observed, and "poor (x)" when at least one of film thickness unevenness and pinhole was clearly observed. ) ”. As a result, neither uneven film thickness nor pinhole was observed, and the coatability was "good (◯)".

(5) Evaluation of Volume resistivity The dispersion composition (S-1) was applied and dried on a glass substrate in the same manner as in (4) above except that the gap of the blade was changed, and formed into a film (thickness: about 20 μm). Specimen was obtained. Next, the volume resistivity of the obtained test piece was measured by the 4-terminal method. The volume resistivity was calculated from the surface resistivity and the film thickness using the following mathematical formula (5). Further, in the measurement, the measurement was performed 5 times while changing the measurement location, and the average value was evaluated as the volume resistivity.
Volume resistivity (μΩ ・ m) = Surface resistivity (Ω) × Film thickness (μm)… (5)
As a result, the volume resistivity of the film obtained by using this dispersion composition (S-1) was 1000 μΩ · m (0.1 Ω · cm). It can be said that the lower the volume resistivity, the higher the conductivity.

(6) Finger pressing test The dispersion composition (S-1) obtained in (1) above was applied onto a glass substrate using a blade and dried on a hot plate at 80 ° C. for 10 minutes to obtain an average film thickness of 10 μm. The coating film of was formed. By pressing the obtained coating film with a finger, it was confirmed that cracks were less likely to occur (external force resistance). The evaluation is "good (○)" if no cracks are observed by microscopic observation (magnification: 10 times), "OK (△)" if cracks are observed by a microscope, but no visual cracks are observed. Those in which cracks were observed were classified as "defective". As a result, the external force resistance of the coating film formed by using this dispersion composition (S-1) was judged to be "OK (Δ)" because cracks were not observed visually, but cracks were observed by a microscope. It was.

(7) Evaluation of Substrate Adhesion The dispersion composition (S-1) was applied and dried on a glass substrate in the same manner as in (4) above except that the dispersion composition was spray-coated, and the thickness was 0.5 μm. A substrate with carbon nanotubes was produced by forming the coating film of the above on a glass substrate. Next, a solvent prepared so that distilled water / isopropyl alcohol / propylene glycol monomethyl ether acetate = 5/25/70 (mass ratio) was poured onto the substrate with carbon nanotubes, and then the substrate was placed on a hot plate at 80 ° C. for 10 minutes. It was dried. The obtained substrate (hereinafter referred to as "adhesion evaluation test piece") was observed with a microscope (magnification: 10 times), and the substrate adhesion was evaluated by evaluating the volume resistivity. The evaluation is "excellent (◎◎)" when all of the following criteria 1, 2, and 3 are met, and "excellent (◎)" when criteria 1 and 2 are met but criteria 3 are not met. , Criteria 1 is satisfied but Criterion 2 is not met, "Good (○)", Criterion 2 is met, but Criterion 1 is not met, "Yes (△)", and both Criterion 1 and Criterion 2 are satisfied. The case where there is no such thing is regarded as "defective (x)".
Criterion 1: No cracks are observed when the test piece for adhesion evaluation is observed under a microscope.
Criterion 2: The value obtained by determining the volume resistivity of the test piece for adhesion evaluation according to the method (5) above is 0.05 Ω · cm or less (500 μ Ω · m or less).
Criterion 3: The value obtained by determining the volume resistivity of the test piece for adhesion evaluation according to the method (5) above is equal to or less than the value of the volume resistivity of (5) above.
As a result, the substrate adhesion of this dispersion composition (S-1) was "possible (Δ)".

[Examples 2 to 7, Comparative Examples 1 to 3]
Dispersion compositions (S-2) to (S-7) and the same as the dispersion composition (S-1) of Example 1 except that the composition of the dispersion composition was changed as shown in Table 2 below. (Sr-1) to (sr-3) were prepared. In addition, Example 1 except that the dispersion compositions (S-2) to (S-7) and (sr-1) to (sr-3) were used instead of the dispersion composition (S-1), respectively. Various evaluations were performed in the same manner as above. The evaluation of the CNT dispersibility (organic solvent system) was carried out using a dispersion composition prepared by using cyclopentanone instead of distilled water as the solvent, as in the above (3) of Example 1. The various evaluation results of Examples 1 to 7 and Comparative Examples 1 to 3 are summarized in Table 2 below.

In Table 2, the numerical value of "blending amount" indicates a mass part. The abbreviations of the compounds are as follows.
<CNT>
MWNT; Multi-wall carbon nanotube DWNT; Double-wall carbon nanotube SWNT; Single-wall carbon nanotube

From the results in Table 2, in Examples 1 to 7, the dispersibility of the carbon nanotubes was better in both the aqueous system and the organic solvent system as compared with Comparative Examples 1 to 3. Further, Examples 1 to 7 were excellent in external force resistance, conductivity, and adhesion to the substrate as compared with Comparative Examples 1 to 3. These results show that by introducing CNTs (guests) into the liotropic liquid crystal field (host) created by the polymer [P], the CNTs are oriented along the molecular chain of the polymer [P] and the CNTs are dispersed. It is probable that the sex was improved.

3. 3. Preparation and Evaluation of Metal Particle-Containing Dispersion Composition [Example 8]
(1) Preparation of dispersion composition 53 parts by mass of distilled water was added as a solvent to a container containing 45 parts by mass of titanium oxide as metal particles and 2 parts by mass of the polymer (PI-1) obtained in Synthesis Example 2. .. Next, the dispersion composition (S-8) was prepared by shaking with a paint shaker (shaker) for 10 minutes.

(2) Evaluation of dispersibility (water system)
The dispersion composition (S-8) obtained in (1) above was allowed to stand on a flat place for one day, and the dispersibility was evaluated in the same manner as in (2) of Example 1. As a result, the particle dispersibility of the dispersion composition (S-8) was "good (◯)".
(3) Evaluation of particle dispersibility (organic solvent system)
A dispersion composition was prepared in the same manner as in (1) above, except that cyclopentanone was used instead of the distilled water used as the solvent in (1) above. The obtained dispersion composition was allowed to stand on a flat place, the dispersion state with the passage of time was observed, and the particle dispersibility was evaluated in the same manner as in (3) of Example 1. As a result, the particle dispersibility (organic solvent system) of the dispersion composition of this example was "OK (Δ)".

(4) Evaluation of particle coatability The coatability was evaluated in the same manner as in (4) of Example 1 except that the dispersion composition (S-8) obtained in (1) above was used. As a result, neither uneven film thickness nor pinhole was observed, and the coatability was "good (◯)".
(5) Finger pressing test A finger pressing test was performed in the same manner as in (6) of Example 1 except that the dispersion composition (S-8) obtained in (1) above was used, and cracks were less likely to occur ( External force resistance and finger push resistance) were confirmed. As a result, no cracks were visually observed in the coating film formed by using this dispersion composition (S-8), but since cracks were observed by a microscope, the finger pressing resistance was "possible (Δ)". It was judged.

[Examples 9 to 19, Comparative Example 4]
Dispersion compositions (S-9) to (S-19) and the same as the dispersion composition (S-8) of Example 8 except that the composition of the dispersion composition was changed as shown in Table 3 below. (Sr-4) was prepared. In addition, various evaluations were carried out in the same manner as in Example 8 except that the dispersion compositions (S-9) to (S-19) and (sr-4) were used instead of the dispersion composition (S-8). Was done. The particle dispersibility (organic solvent system) was evaluated by using a dispersion composition prepared by using cyclopentanone instead of distilled water as a solvent, as in the above (3) of Example 8. The various evaluation results of Examples 9 to 19 and Comparative Example 4 are summarized in Table 3 below.

In Table 3, the numerical value of "blending amount" indicates a mass part. The abbreviations of the compounds are as follows.
<Dispersant>
BYK180; DISPERBYK-180 (polyacrylic dispersant) manufactured by BYK-Chemie.

From the results in Table 3, in Examples 8 to 19, the dispersibility of the metal particles was better in the organic solvent system as compared with Comparative Example 4. In addition, Examples 8 to 19 were superior in external force resistance as compared with Comparative Example 4.

[Second Example]
1. 1. Synthesis of polymer [Synthesis example 11: Synthesis of polyamic acid]
In a three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introduction tube, 85.5 mol parts of 2,5-diaminobenzenesulfonic acid, 9.5 mol parts of paraphenylenediamine and m-cresol were dissolved and triethylamine 218. A molar portion was added and the mixture was stirred under nitrogen. After dissolving the diamine, 100 mol parts of pyromellitic dianhydride was added, and the mixture was stirred at 80 ° C. for 3 hours. The reaction concentration was adjusted so that the solid content was 30%. After completion of the reaction, the reaction solution was diluted with m-cresol to a solid content concentration of 15% and added dropwise to acetone to coagulate. The obtained coagulated product was filtered, washed with acetone, and vacuum dried at 120 ° C. to obtain a polyamic acid (hereinafter referred to as "polymer (PAA-2)"). The weight average molecular weight of the obtained polymer (PAA-2) was 151,000.

[Synthesis Example 12: Polyimide Synthesis]
95 parts of 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 20 parts of cholestanyl 3,5-diaminobenzoate, 60 parts of 4,4'-diaminodiphenyl ether, and 20 parts of 2,5-diaminobenzenesulfonic acid. The molar part was dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a polyamic acid solution having a polymer concentration of 15% by mass. NMP was added to the obtained polyamic acid solution, diluted to a polymer concentration of 10% by mass, a predetermined amount of pyridine and acetic anhydride were added, and the mixture was reacted at 110 ° C. for 4 hours. The resulting reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried under reduced pressure at 100 ° C. to obtain a polyimide (hereinafter referred to as "polymer (PI-7)"). The weight average molecular weight of the obtained polymer (PI-7) was 202,000, and the imidization ratio was 99%.

[Synthesis Example 13: Polyimide Synthesis]
The type and amount of the tetracarboxylic dianhydride and the diamine compound used in the reaction were changed as shown in Table 4 below, and the amount of the catalyst was changed in the same manner as in Synthesis Example 1 to obtain a polyimide polymer (PI-). 8) was obtained. The imidization ratio of each polyimide is also shown in Table 4 below.

The numerical values in Table 4 indicate the ratio (mol%) of the tetracarboxylic dianhydride used in the reaction to the total amount of the tetracarboxylic dianhydride used in the reaction, and for the diamine compound, the diamine compound used in the reaction. The usage ratio (mol%) to the total amount of. The abbreviations of the tetracarboxylic dianhydride and the diamine compound in Table 4 are as follows.
(Tetracarboxylic dianhydride)
AN-1; 2,3,5-tricarboxycyclopentyl acetate dianhydride AN-2; pyromellitic dianhydride AN-4; bicyclo [3.3.0] octane-2,4,6,8-tetra Carboxic acid 2: 4,6: 8-dianhydride (diamine compound)
DA-1; 2,5-diaminobenzenesulfonic acid DA-3; 3,5-diaminobenzoate cholestanyl DA-7; para-phenylenediamine DA-8; 4,4'-diaminodiphenyl ether

2. 2. Preparation of CNT-containing dispersion composition [Preparation Example 1]
10000 parts by mass of distilled water was added as a solvent to a container containing 5 parts by mass of single-wall carbon nanotubes (SWNT) and 25 parts by mass of the polymer (PAA-2) obtained in Synthesis Example 11. Then, ultrasonic dispersion was performed for 60 minutes to prepare a dispersion composition (S-20).
[Preparation Examples 2 to 5]
Each dispersion composition was prepared in the same manner as in Preparation Example 1 except that the composition of the dispersion composition was changed as shown in Table 5 below.

In Table 5, the numerical value of "blending amount" indicates a mass part. The abbreviations for CNT are as follows.
<CNT>
MWNT; Multi-wall carbon nanotube DWNT; Double-wall carbon nanotube SWNT; Single-wall carbon nanotube SWNT-D; Single-wall carbon nanotube with many defects <Dispersant>
SDBS; sodium dodecylbenzene sulfonate

3. 3. Evaluation of CNT-Containing Dispersion Composition [Example 20]
(1) Evaluation of coatability on glass substrate The coatability on a glass substrate was evaluated using a shear coating device (see FIG. 1) equipped with a coating roll and a doctor roll. First, the coating roll and the doctor roll are rotated in the same direction (forward rotation), and the dispersion composition (S-20) obtained in Preparation Example 1 is transferred onto a glass substrate of 150 mm × 150 mm to prepare a coating film. did. The coating method in which the coating roll and the doctor roll are rotated forward is different from the normal printing method (offset printing method or the like, in which the roll is rotated in the reverse direction for coating). Then, it was dried on a hot plate at 80 ° C. for 10 minutes to form a coating film having a film thickness of 0.5 μm. The evaluation was visually judged to be "good (◯)" if there were no pinholes or cissing, and "poor (x)" if there were pinholes or cissing. As a result, no pinholes or cissing were observed in the coating film on the glass substrate, and the coatability on the glass substrate was “good (◯)”.

(2) Evaluation of abrasion resistance The dispersion composition (S-20) obtained in Preparation Example 1 is shear-transferred and coated on a glass substrate using a shear coating apparatus in the same manner as in (1) above to obtain a coating film. Was dried at 80 ° C. for 10 minutes to form a coating film having an average film thickness of 0.5 μm at the center of the substrate. The coating film was subjected to a rubbing treatment with a pressing length of 0.3 mm, and the abrasion resistance was evaluated by measuring the change in the film thickness before and after the rubbing treatment. The evaluation is that when the change in film thickness is less than 20 nm, the abrasion resistance is "good (○)", and when the change in film thickness is 20 nm or more and less than 35 nm, the abrasion resistance is "possible (Δ)", and the film thickness is The case where the change was 35 nm or more was defined as “defective (x)” abrasion resistance. In this example, since the change in film thickness due to rubbing was 5 nm, the abrasion resistance was "good (◯)".

(3) Evaluation of Conduction Anisotropy Using the shear coating device in the same manner as in (1) above, the dispersion composition (S-20) obtained in Preparation Example 1 was shear-transferred and coated on a glass substrate to form a coating film. Was dried at 80 ° C. for 10 minutes to obtain a test piece. If necessary, the number of coatings was adjusted so that the film thickness was about 20 μm by applying the coatings a plurality of times. The volume resistivity (μΩ · m) of the obtained test piece was measured by the two-terminal method. The conductive anisotropy of the test piece was measured by changing the arrangement of the two terminals with respect to the shear coating direction. In the measurement, the case where the two terminals were arranged parallel to the shear coating direction was defined as the parallel volume resistivity, and the case where the two terminals were arranged perpendicularly to the shear coating direction was defined as the vertical volume resistivity. The volume resistivity was calculated from the surface resistivity and the film thickness using the following mathematical formula (EX-2). Further, in the measurement, the measurement was performed 5 times while changing the measurement location, and the average value thereof was estimated as the volume resistivity.
Volume resistivity (μΩ ・ m) = Surface resistivity (Ω) × Film thickness (μm)
… (EX-2)
In the evaluation, when the ratio of parallel volume resistivity to vertical volume resistivity (parallel volume resistivity / vertical volume resistivity) is 100 or more, the conductivity anisotropy is "good (○)", and the parallel volume resistivity / vertical volume is evaluated. When the resistivity was 10 or more and less than 100, the conductivity anisotropy was “possible (Δ)”, and when the parallel volume resistivity / vertical volume resistivity was less than 10, the conductivity anisotropy was “poor (×)”.
As a result, the parallel volume resistivity / vertical volume resistivity of the test piece obtained by applying the dispersion composition (S-20) by shear transfer was 508, which was judged to be “good (◯)”. It can be said that the larger the value of parallel volume resistivity / vertical volume resistivity, the larger the conductive anisotropy.

(4) Evaluation of Conductive Anisotropy after Cleaning Using the same shear coating device as in (1) above, the dispersion composition (S-20) obtained in Preparation Example 1 was applied onto a glass substrate, and 80 It was dried at ° C. for 10 minutes to obtain a film-shaped test piece. If necessary, the number of coatings was adjusted so that the film thickness was about 20 μm by applying the coatings a plurality of times.
Next, the coating film was washed by immersing (dip) in distilled water for 30 seconds. The volume resistivity (μΩ · m) of the obtained test piece was measured in the same manner as in (3) above. The evaluation is when the parallel volume resistivity / vertical volume resistivity is 100 or more, the conductive anisotropy after cleaning is “good (◯)”, and the parallel volume resistivity / vertical volume resistivity is 10 or more and less than 100. Was defined as “possible (Δ)” in conductivity after cleaning, and “poor (x)” in conductivity anisotropy after cleaning when the parallel volume resistivity / vertical volume resistivity was less than 10. As a result, the ratio of the parallel volume resistivity and the vertical volume resistivity of the test piece obtained by applying the dispersion composition (S-20) by shear transfer was 1818, which was judged to be “good (◯)”.

(5) Polarization Absorption Characteristics Using the same shear coating device as in (1) above, the dispersion composition (S-20) obtained in Preparation Example 1 was applied onto a glass substrate and dried at 80 ° C. for 10 minutes. , A coating film having an average film thickness of 10 μm was formed. Arranged so that the polarization axis (polarization transmission axis) of the single Nicol and the shear application direction of the coating film are arranged in parallel and orthogonal to each other (approximately 90 ° arrangement), and the horizontal arrangement and orthogonal arrangement when omnidirectional light is incident. The polarization absorption characteristics were evaluated by measuring the transmittance difference. The evaluation is "good (○)" when the difference in transmittance between the horizontal arrangement and the orthogonal arrangement is 40% or more, "OK (Δ)" when it is 25% or more and less than 40%, and less than 25%. The case was defined as "defective (x)". As a result, the transmittance difference between the horizontal arrangement and the orthogonal arrangement of the substrate was 48%, and the polarization absorption characteristic was judged to be "good (◯)".

(6) Evaluation of Heat Transfer Anisotropy Using the same shear coating device as in (1) above, the dispersion composition (S-20) obtained in Preparation Example 1 above was applied onto a glass substrate and at 80 ° C. It was dried for 10 minutes to form a coating film having a thickness of 10 μm on a glass substrate of 120 mm × 120 mm. The measurement was performed by heating the central part of the substrate with a laser and measuring the heat propagation time by thermography. The evaluation is performed based on the time difference (heating time) required for the point 50 mm in the x-axis direction from the center and the point 50 mm in the y-axis direction from the center to reach the same temperature as the central part. It was. When the time difference of the temperature rising time was 3 seconds or more, it was evaluated as "good (◯)", when it was 1 second or more and less than 3 seconds, it was evaluated as "possible (Δ)", and when it was less than 1 second, it was evaluated as "bad (x)". As a result, the temperature rise time difference of this example was 3.4 seconds, which was judged to be "good (◯)". It can be said that the larger the temperature difference, the larger the electric anisotropy.

(7) Evaluation of Heat Transfer Anisotropy After Cleaning Using the same shear coating device as in (1) above, the dispersion composition (S-20) obtained in Preparation Example 1 was applied onto a glass substrate. It was dried at 80 ° C. for 10 minutes to form a coating film having a thickness of 10 μm on a glass substrate of 120 mm × 120 mm. Next, the coating film was washed by immersing (dip) the substrate on which the coating film was formed in distilled water for 30 seconds. The heat transfer anisotropy of the obtained test piece was measured in the same manner as in (6) above. The evaluation is performed based on the time difference (heating time) required for the point 50 mm in the x-axis direction from the center and the point 50 mm in the y-axis direction from the center to reach the same temperature as the central part. It was. When the time difference of the temperature rising time was 3 seconds or more, it was regarded as "good", when it was 1 second or more and less than 3 seconds, it was regarded as "OK", and when it was less than 1 second, it was regarded as "bad". As a result, the temperature rise time difference of this example was 3.2 seconds, which was judged to be "good".

(8) Evaluation of Degas Resistance Using the same shear coating device as in (1) above, the dispersion composition (S-20) obtained in Preparation Example 1 was applied onto an 8-inch silicon substrate, and at 80 ° C. It was dried for 10 minutes to form a coating film having a thickness of 10 μm on a silicon substrate. A silicon substrate was cut into 1 cm x 5 cm pieces, and the four cut silicon substrates were subjected to a silicon wafer analyzer device ("Heat Desorption Device JTD-505" by Nippon Analytical Industry Co., Ltd., "Gas Chromatograph Mass Spectrometer GCMS-" by Shimadzu Corporation. ^{Using QP2010Plus), the amount of outgas (ng / cm 2} ) when the temperature was raised to 230 ° C. at a heating rate of 10 ° C./min and held at the same temperature for 15 minutes was determined. In evaluation, the case outgassing amount was less than 200ng / cm ² "good (○)", the case was less than 200ng / cm ² or more 600ng / cm ² "possible (△)", 600ng / cm2 or more If there was, it was regarded as "defective (x)". As a result, the temperature rise time difference of this example was 150 ng / cm ² , which was judged to be “good”.

[Examples 21 to 23, 25, 26, Comparative Examples 5 to 7]
Various evaluations were carried out in the same manner as in Example 20 except that the type of the dispersion composition and the coating method on the substrate were changed as shown in Table 6 below. The evaluation results are shown in Table 6 below.
[Example 24]
The ink of a ballpoint pen having a ball diameter of 1.2 mm is sucked out from the ink containing portion with a syringe, acetone is injected into the ink containing portion to wash and dry the ink, and then the dispersion composition (S-20) is placed in the empty ink containing portion. ) Was injected and drawn, and shear transfer coating was performed on the glass substrate (see FIG. 2), and the coatability and polarization absorption characteristics on the glass substrate were evaluated. The applicability to the glass substrate was evaluated by visually observing the presence or absence of pinholes and cissing on the drawn lines in the same manner as in Example 20. Regarding the polarization absorption characteristics, when the drawn lines are visually observed through the polarizing plate, the polarization absorption characteristics are "good (○)" when the blackening can be confirmed by the rotation of the polarizing plate, and when the blackening cannot be confirmed. The polarization absorption characteristic was evaluated as "poor (x)". The evaluation results are shown in Table 6 below.

In Table 6, the details of the coating method are as follows.
Transfer coating A: Shear coating was performed by rotating the coating roll and the doctor roll in the forward direction using a shear coating device.
Transfer coating B: Shear coating was performed by a ballpoint pen type method.
Transfer coating C: The same as transfer coating A was performed except that the coating roll and the doctor roll were rotated in the reverse direction by the shear coating apparatus to perform shear coating.
Transfer coating D: Instead of a shear coating device provided with a coating roll and a doctor roll, the dispersion composition is shear-coated on a glass substrate by bar coating, and the obtained coating film is transferred to another substrate to form a coating film. Obtained.

As shown in Table 6, by forming an anisotropic film by shear transfer coating using a dispersion composition containing a compound exhibiting lyotropic liquid crystallinity, conduction anisotropy, polarization absorption characteristics, and heat transfer anisotropy are formed. And an anisotropic film having excellent various properties of degas resistance could be obtained (Examples 20 to 26). Further, the anisotropic films of Examples 20 to 26 were also excellent in coatability and abrasion resistance to the glass substrate. In particular, Examples 20 to 25 in which shear transfer coating was performed with a rotating body were "○" or "Δ" in all evaluations, and among these, Examples 20 to 22 were "○" in all evaluations. there were.

Claims (15)

With the dispersed body,
Dispersion medium and
A structural unit U1 that is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide and is derived from the diamine compound [D1] represented by the following formula (1), and the diamine compound [D1]. A polymer [P] having a structural unit U2 derived from a diamine compound [D2] different from the above,
A dispersion composition containing.

(If in the formula (1), n is 0 or 1 .n is zero, at least one of R 1 ^~ R ⁴ is a monovalent group having an ionic functional group, the remainder, respectively Independently, it is a hydrogen atom, a halogen atom or a monovalent organic group. When n is 1, ^{at least one of R 1} to R ⁸ is a monovalent group having an ionic functional group, and the rest. Are independently hydrogen atoms, halogen atoms or monovalent organic groups.) The first aspect of the present invention, wherein the content ratio of the structural unit U2 in the polymer [P] is 1 mol% or more and 80 mol% or less with respect to the total amount of the structural unit U1 and the structural unit U2. Dispersion composition. The dispersion composition according to claim 1 or 2, wherein the diamine compound [D2] has a partial structure represented by the following formula (2).
* -L ^1- R ^1- R ^2- R ^3- R ⁴ ... (2)
(In the formula (2), ^{L 1} represents a single ^{bond, -O -, - CO -,} - COO- * 1, -OCO- * 1, -NR 5 -, - NR 5 -CO- * 1, -CO -NR ^5- * ¹ , alkanediyl group with 1 to 6 carbon atoms, -OR ^6- * ¹ , or -R ⁶ -O- * ¹ (where R ⁵ is a hydrogen atom or 1 to 10 carbon atoms It is a monovalent hydrocarbon group, and R ⁶ is an alkanediyl group having 1 to 3 carbon atoms. “* ¹ ” indicates that it is a bond with ^{R 1. ). R 1} and R. ³ is an independently single-bonded, substituted or unsubstituted phenylene group, or substituted or unsubstituted cycloalkylene group, and R ² is a single-bonded, substituted or unsubstituted phenylene group, substituted or unsubstituted. cycloalkylene group, or ^-R 7 ^-B 1 ^{-R 8} - (provided that, ^{R 7} and ^{R 8} are each independently a substituted or unsubstituted phenylene group or a cycloalkylene group, ^{B 1} is a single bond, -O-, -COO- * ² , -OCO- * ² , -OCH _2- * ² , -CH ₂ O- * ² , or an alkanediyl group having 1 to 3 carbon atoms. "* ² " is It indicates that it is a bond with R ^{8. ) R 4} is a hydrogen atom, a fluorine atom, a cyano group, and CH ₃ COO- * ³ (“* ³ ” is a bond with ^{R 3).} An alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a fluoroalkoxy group having 1 to 18 carbon atoms, and a carbon number having a steroid skeleton. It is a monovalent group in which at least one hydrogen atom of a hydrocarbon group having 17 to 51 carbon atoms or an alkyl group having 1 to 18 carbon atoms is substituted with a cyano group, except that R ¹ , R ² and R ^{3 are used.} When all of the above are single bonds, R ⁴ is an alkyl group having 6 to 18 carbon atoms, a fluoroalkyl group having 6 to 18 carbon atoms, an alkoxy group having 6 to 18 carbon atoms, and a fluoroalkoxy group having 6 to 18 carbon atoms. , a hydrocarbon group having a carbon number of 17 to 51 having a steroid skeleton, or, .R ¹ is a monovalent group in which at least one hydrogen atom is substituted with a cyano group of the alkyl group having 6 to 18 carbon atoms, When the total number of the substituted or unsubstituted phenylene group and the substituted or unsubstituted cycloalkylene group of ^{R 2} and R ^{3 is 1, R 4} is an alkyl group having 4 to 18 carbon atoms and 4 carbon atoms. ~ 18 fluoroalkyl groups, 4-18 carbon atoms alkoxy It is a monovalent group in which at least one hydrogen atom of a group, a fluoroalkoxy group having 4 to 18 carbon atoms, or an alkyl group having 4 to 18 carbon atoms is substituted with a cyano group. "*" Indicates a bond. ) The dispersion composition according to any one of claims 1 to 3, wherein the diamine compound [D2] is an aromatic diamine. The polymer [P] is a reaction product of at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic dianester compound and tetracarboxylic acid diester dihalide, and a diamine compound. And
The dispersion composition according to any one of claims 1 to 4, wherein the tetracarboxylic acid derivative is an aromatic tetracarboxylic acid derivative. The dispersion composition according to any one of claims 1 to 5, wherein the dispersant is at least one selected from the group consisting of inorganic particles and organic particles. The dispersion composition according to any one of claims 1 to 6, wherein the dispersant is at least one selected from the group consisting of rod-shaped nanostructures and rod-shaped molecules. The dispersion composition according to any one of claims 1 to 6, wherein the dispersant is at least one selected from the group consisting of metal particles and semimetal particles. A structural unit U1 that is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide and is derived from the diamine compound [D1] represented by the following formula (1), and the diamine compound [D1]. A dispersant containing a polymer [P] having a structural unit U2 derived from a diamine compound [D2] different from the above.

(If in the formula (1), n is 0 or 1 .n is zero, at least one of R 1 ^~ R ⁴ is a monovalent group having an ionic functional group, the remainder, respectively Independently, it is a hydrogen atom, a halogen atom or a monovalent organic group. When n is 1, ^{at least one of R 1} to R ⁸ is a monovalent group having an ionic functional group, and the rest. Are independently hydrogen atoms, halogen atoms or monovalent organic groups.) A step of holding a dispersion composition containing a dispersion to be dispersed, a dispersion medium, and a compound exhibiting lyotropic liquid crystallinity on the surface of the retainer while applying shear stress.
The step of transferring the dispersion composition held on the surface of the retainer onto the substrate, and
A method for producing an anisotropic membrane, including. The method for producing an anisotropic membrane according to claim 10, wherein the compound is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide. The method for producing an anisotropic membrane according to claim 11, wherein the polymer has a structural unit derived from the diamine compound [D1] represented by the following formula (1).

(If in the formula (1), n is 0 or 1 .n is zero, at least one of R 1 ^~ R ⁴ is a monovalent group having an ionic functional group, the remainder, respectively Independently, it is a hydrogen atom, a halogen atom or a monovalent organic group. When n is 1, ^{at least one of R 1} to R ⁸ is a monovalent group having an ionic functional group, and the rest. Are independently hydrogen atoms, halogen atoms or monovalent organic groups.) The method for producing an anisotropic membrane according to any one of claims 10 to 12, wherein the dispersant is at least one selected from the group consisting of inorganic particles and organic particles. An anisotropic membrane obtained by the production method according to any one of claims 10 to 14. A holding portion that holds a dispersion composition containing a dispersion to be dispersed, a dispersion medium, and a compound exhibiting lyotropic liquid crystallinity on the surface of the holding body while applying shear stress.
A transfer unit that transfers the dispersion composition held on the surface of the retainer onto the substrate, and
An anisotropic film forming apparatus.

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