Dispersion composition, dispersant, anisotropic film and its manufacturing method, and anisotropic film forming device

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

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is based on Japanese Patent Application No. 2019-149938, filed on August 19, 2019, the contents of which are incorporated herein by reference. [Technical Field]

[0002] 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. [Background technology]

[0003] Nano-sized materials such as nanocarbons and metal nanoparticles have excellent properties such as electrical properties, mechanical properties, and thermal stability, and their application and practical use in various fields as nanomaterials is being considered. These particles are generally dispersed in a dispersion medium to utilize their functions. In order to fully utilize the properties of the particles, it is desirable to uniformly disperse the particles in the dispersion medium. Therefore, various dispersion compositions containing dispersants together with the particles have been proposed to suppress particle aggregation and increase particle dispersibility (see, for example, Patent Document 1 and Patent Document 2).

[0004] Patent Document 1 discloses a dispersion composition using a polyalkylene oxide having an aryl group introduced into the side chain as a dispersant for dispersing nanocarbons, metal nanoparticles, inorganic fibers, and organic fibers. Patent Document 2 discloses a dispersion composition using a polyamic acid having a benzoxazole skeleton as a dispersant for dispersing carbon nanotubes. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2016 / 039218 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-154337 Summary of the Invention [Problem to be solved by the invention]

[0006] If a dispersed substance such as nanocarbon or metal nanoparticles exhibits good dispersibility in both aqueous and organic solvents, it will be possible to further expand the applications of the dispersed substance and further enhance its functionality.

[0007] A dispersion composition in which a dispersed substance is dispersed in a dispersion medium is applied to a substrate, and then the dispersion medium is removed from the coating solution, thereby forming a film, wiring, or the like containing the dispersed substance on the substrate. Devices equipped with films, wiring, or the like containing the dispersed substance are used in various applications, such as electronic devices and display devices. If the external force resistance of a component formed from the dispersed substance is low, this may lead to a decrease in the performance of the device. Therefore, such components are required to have high external force resistance.

[0008] The present disclosure has been made in consideration of the above-mentioned problems, and one object of the present disclosure is to provide a dispersion composition that has good dispersibility of dispersed substances regardless of whether an aqueous or organic solvent-based dispersion medium is used, and that can form a component that has good resistance to external forces, and a dispersant for obtaining the dispersion composition. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above-mentioned problems and have found that the above-mentioned problems can be solved by using, as a polymer dispersant, polyamic acids, polyamic acid esters, and polyimides obtained by using a diamine having an ionic functional group in combination with a diamine not having an ionic functional group.

[0010] <1> A dispersion composition comprising a substance to be dispersed, a dispersion medium, and a polymer [P] which is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, and which has a structural unit U1 derived from a diamine compound [D1] represented by the following formula (1), and a structural unit U2 derived from a diamine compound [D2] different from the diamine compound [D1]: [ka] (In formula (1), n ​​is 0 or 1. When n is 0, R 1 ~R 4 At least one of R is a monovalent group having an ionic functional group, and the rest are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. 1 ~R 8 At least one of the groups is a monovalent group having an ionic functional group, and the remaining groups are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. <2> A dispersant containing the polymer [P].

[0011] <3> A method for producing an anisotropic film, comprising: a step of holding a dispersion composition containing a substance to be dispersed, a dispersion medium, and a compound exhibiting lyotropic liquid crystallinity on a surface of a support while applying shear stress; and a step of transferring the dispersion composition held on the surface of the support onto a substrate. <4> the above <3> An anisotropic film obtained by the manufacturing method of the above. <5> An anisotropic film forming apparatus comprising: a holding section that holds a dispersion composition containing a substance to be dispersed, a dispersion medium, and a compound exhibiting lyotropic liquid crystallinity on a surface of a holder while applying shear stress; and a transfer section that transfers the dispersion composition held on the surface of the holder onto a substrate. [Effects of the Invention]

[0012] According to the present disclosure, a dispersion composition having good dispersibility of a dispersed substance can be obtained regardless of whether an aqueous or organic solvent is used as a dispersion medium. Furthermore, by using the dispersion composition, a member having good resistance to external forces can be formed. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic diagram showing an example of a printing-type shear coating device. [Figure 2] FIG. 2 is a schematic diagram showing an example of a dispenser-type shear coating device. DETAILED DESCRIPTION OF THE INVENTION

[0014] First Embodiment The dispersion composition of the present disclosure contains (A) a substance to be dispersed, (B) a dispersion medium, and (C) a dispersant. Each component contained in the dispersion composition of the present disclosure, as well as other components that may be optionally blended as needed, will be described below.

[0015] In this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Chain hydrocarbon group" refers to a straight-chain hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in the main chain and is composed only of a chain structure. However, it may be saturated or unsaturated. "Alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, it does not necessarily have to be composed only of an alicyclic hydrocarbon structure, and it also includes those that have a chain structure as part of it. "Aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, it does not necessarily have to be composed only of an aromatic ring structure, and it may contain a chain structure or an alicyclic hydrocarbon structure as part of it. "Organic group" refers to a group that has a hydrocarbon group and may contain a heteroatom in the structure.

[0016] <(A) Dispersed entity> The dispersed substance 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 dispersed substance is also not particularly limited, and examples include spherical, rod-like, fibrous, flat, and disc-like shapes. The primary particle diameter of the dispersed substance is preferably 10 μm or less, more preferably 1 μm or less, and even more preferably 200 nm or less. The primary particle diameter of the dispersed substance is preferably 1 nm or more, more preferably 2 nm or more, and even more preferably 5 nm or more. The "primary particle diameter of the dispersed substance" referred to here is a value determined by measuring the d50 value using a laser diffraction / scattering method.

[0017] Examples of inorganic particles contained in the dispersion composition of the present disclosure include carbon, metal particles, semi-metal particles, silica, inorganic salts, quantum dots, etc. Specific examples of these include carbon, such as carbon black, carbon fiber, carbon nanotubes, graphite, fullerenes, carbon nanohorns, etc.; metal particles, such as simple metals, metal oxides, metal carbides, metal nitrides, etc.; semi-metal particles, such as semi-metal oxides, semi-metal carbides, semi-metal nitrides, etc.; silica, such as wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), colloidal silica, precipitated silica, calcium silicate, aluminum silicate, surface-modified modified silica, etc.; inorganic salts, such as sulfates (calcium sulfate, barium sulfate, etc.), carbonates (calcium carbonate, magnesium carbonate, barium carbonate, etc.), phosphates (calcium phosphate, etc.); quantum dots, such as perovskite quantum dots, carbon-based quantum dots, lead sulfide quantum dots, etc.

[0018] Carbon fibers include carbon nanofibers. Carbon nanotubes include single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes. Carbon nanotubes may be made only of carbon, or may have carbon nanotubes as part of their structure. but They may be substituted with other elements or chemically modified, or may be complexes with metals (for example, gold, silver, copper, aluminum, nickel, cobalt, titanium, platinum, etc.).

[0019] More specifically, metal particles include particles containing metal elements such as gold, silver, copper, zinc, aluminum, tin, nickel, palladium, platinum, cobalt, iron, manganese, chromium, molybdenum, titanium, zirconium, hafnium, yttrium, and cerium. Specific examples of these include metals consisting of the metal elements; metal oxides such as copper oxide, aluminum oxide, zinc oxide, iron oxide, titanium oxide, barium titanate, bismuth oxide, cerium oxide, chromium oxide, cobalt oxide, indium oxide, indium tin oxide, zirconium oxide, yttrium oxide, tin oxide, indium oxide-gallium oxide-zinc oxide, indium oxide-zinc oxide, and indium tin oxide; metal carbides such as titanium carbide; and metal nitrides such as titanium nitride, titanium oxynitride (titanium black), and aluminum nitride. The metal particles can be used alone or in combination of two or more.

[0020] Examples of semi-metallic particles include particles containing semi-metallic elements such as boron and silicon. Specific examples of these include simple metalloids consisting of the semi-metallic elements; metal oxides such as silicon dioxide; metal carbides such as boron carbide and silicon carbide; and metal nitrides such as boron nitride and silicon nitride. The semi-metallic particles may be used alone or in combination of two or more. In one embodiment of the dispersion composition of the present disclosure, at least one type selected from the group consisting of metal particles and semi-metallic particles is preferably used as the dispersed substance.

[0021] Examples of organic particles include organic pigments, dichroic dyes, dye aggregates, proteins, nucleic acids, viruses, etc. 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, flavanthrone pigments, indanthrone pigments, indolinone pigments, thioindigo pigments, metal complex pigments, perinone pigments, and perylene pigments; dichroic dyes such as disazo compounds, trisazo compounds, tetrakisazo compounds, anthraquinone compounds, and dioxazine compounds; and dye aggregates such as J aggregates of porphyrin dyes, cyanine dyes, pyrrolopyrrole dyes, acene dyes, squarylium dyes, and the like; and H aggregates of oxazole yellow dyes, thiazole orange dyes, cyanine dyes, and azo dyes, and the like.

[0022] Of the above, inorganic particles can be preferably used as the dispersed material, and carbon nanotubes (CNTs) and metal particles can be particularly preferably used. Furthermore, the substance to be dispersed can preferably be at least one selected from the group consisting of rod-shaped nanostructures and rod-shaped molecules. Examples of rod-shaped molecules include dichroic dyes, and examples of rod-shaped nanostructures include dye aggregates, quantum rods, metal nanorods, carbon nanotubes, proteins, nucleic acids, and viruses. When the substance to be dispersed is at least one selected from the group consisting of rod-shaped nanostructures and rod-shaped molecules, inorganic particles can preferably be used as the substance to be dispersed, and carbon nanotubes and metal nanorods can particularly preferably be used.

[0023] The content of the dispersed substance in the dispersion composition can be appropriately set depending on the type of dispersed substance. The content of the dispersed substance is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.03% by mass or more, based on the total amount of the dispersion composition. The content of the dispersed substance is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on the total amount of the dispersion composition. The dispersed substance may be one of the above substances alone or two or more of them may be used in combination.

[0024] Specifically, when the dispersed material is metal particles or semi-metal particles, the content of the dispersed material in the dispersion composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, relative to the total amount of the dispersion composition. The content of the dispersed material is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, relative to the total amount of the dispersion composition. When the dispersed substance is carbon nanotubes, the content of the dispersed substance in the dispersion composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.03% by mass or more, based on the total amount of the dispersion composition. The content of the dispersed substance in the dispersion composition is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on the total amount of the dispersion composition.

[0025] <(B) Dispersion medium> The dispersion composition of the present disclosure is a composition in which (A) a substance to be dispersed is dispersed in (B) a dispersion medium. The dispersion medium is liquid, and examples thereof include water, organic solvents, and mixed solvents of water and organic solvents. The organic solvent used as (B) the dispersion medium is not particularly limited, and examples thereof include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, aprotic polar solvents, halogenated hydrocarbon-based solvents, and hydrocarbon-based solvents.

[0026] Specific examples of these include alcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, 1-pentanol, 3-methyl-1-butanol, 1-hexanol, 2-hexanol, heptanol, cyclohexanol, methylcyclohexanol, diacetone alcohol, propane-1,2-diol, and ethylene glycol; Examples of ketone solvents 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, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, and trimethylnonanone; Examples of ether solvents include partial ethers of polyhydric alcohols such as 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, ethylene glycol-n-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, and dipropylene glycol monomethyl ether; partial esters of polyhydric alcohols such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate; and 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, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, ethylene carbonate, and propylene carbonate; Aprotic polar solvents include, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-1-imidazolidinone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N,2-trimethylpropanamide, acetonitrile, and dimethyl sulfoxide; Halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, and trichloroethane; Examples of hydrocarbon solvents include hexane, heptane, octane, benzene, toluene, xylene, etc. These organic solvents can be used alone or in combination of two or more.

[0027] The (B) dispersion medium may be an organic solvent or may be aqueous. Aqueous dispersion mediums are preferably used because of their low environmental impact. When an aqueous dispersion medium is used, the proportion of water used is preferably 50% by mass or more, more preferably 75% by mass or more, and particularly preferably 90% by mass or more, based on the total amount of the (B) dispersion medium contained in the dispersion composition.

[0028] When a mixed solvent of water and an organic solvent is used as the dispersion medium, the organic solvent to be used is not particularly limited as long as it is an organic solvent that is soluble in water, but is preferably an organic solvent having a boiling point lower than that of water, 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 of the organic solvent in the dispersion composition is preferably 50% by mass or less, more preferably 25% by mass or less, and even more preferably 10% by mass or less, based on the total amount of the mixed solvent of water and an organic solvent.

[0029] <(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 polymer having a structural unit U1 derived from a diamine compound [D1] represented by the following formula (1) and a structural unit U2 derived from a diamine compound [D2] different from the diamine compound [D1]: [ka] (In formula (1), n ​​is 0 or 1. When n is 0, R 1 ~R 4 At least one of R is a monovalent group having an ionic functional group, and the rest are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. 1 ~R 8 At least one of the groups is a monovalent group having an ionic functional group, and the remaining groups are each independently a hydrogen atom, a halogen atom, or a monovalent organic group.

[0030] (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]. 1 ~R 8Regarding the above, the monovalent group having an ionic functional group is "*-L 1 -X 1 " (However, L 1 is a single bond or a divalent linking group, and X 1 is an ionic functional group. "*" indicates a bond to the benzene ring. 1 When L is a divalent linking group, 1 Specific examples of the alkanediyl group include an alkanediyl group having 1 to 5 carbon atoms, a group containing —O— between the carbon-carbon bonds of the alkanediyl group, and —OR 13 -**(However, R 13 is a divalent hydrocarbon group, and "**" is X 1 ) and so on. 13 is preferably an alkanediyl group having 1 to 5 carbon atoms.

[0031] The ionic functional group is a functional group that forms a cation or anion in water. The ionic functional group is not particularly limited, but is preferably a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, an ammonium group, a pyridinium group, an imidazolium group, a guanidinium group, or a salt thereof, in order to further increase the solubility of the polymer [P] in solvents including water. The ionic functional group may be either an acidic functional group or a basic functional group, but is preferably an acidic functional group. Among these, the ionic functional group is preferably a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, or a salt thereof, and particularly preferably a sulfonic acid group or a salt thereof.

[0032] When the ionic functional group is a salt of an acidic or basic functional group, the counter ion of the acidic functional group (sulfonic acid group, phosphonic acid group, carboxylic acid group, etc.) can be, for example, Li + , Na + , K. + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Pb 2+ , Al3+ , La 3+ , Ce 3+ , Y 3+ , Yb 3+ , Gd 3+ , N.H. 4-t Q t + (wherein 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, multiple Qs may be the same or different groups. The same applies hereinafter.) Furthermore, examples of counter ions of basic functional groups (ammonium groups, pyridinium groups, imidazolium groups, guanidinium groups, etc.) include Cl - , Br - , I - , R 14 COO - (However, R 14 represents a hydrocarbon group having 1 to 20 carbon atoms.) When the ionic functional group is a carboxylic acid group, it is preferable that the ionic functional group forms a salt with a strong base, since the acid dissociation constant of carboxylic acid is low and protons are difficult to dissociate under acidic conditions, resulting in a decrease in ionicity.

[0033] In the monovalent group having an ionic functional group, L 1 can be appropriately selected depending on the type of ionic functional group. For example, when the ionic functional group is a sulfonic acid group, a phosphonic acid group, 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, a guanidinium group, or a salt thereof, L 1 is preferably a divalent linking group, more preferably an alkanediyl group having 1 to 3 carbon atoms.

[0034] 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) (i.e., when n=0, R 1 ~R 4 The number of monovalent groups having an ionic functional group, when n=1, R 1 ~R 8The number of monovalent groups having an ionic functional group among the above is preferably 1 to 4, and more preferably 1 or 2. R 1 ~R 8 In the above formula, the monovalent organic group is preferably a hydrocarbon group, more preferably an alkyl group having a carbon number of 1 to 5. Examples of the halogen atom include a fluorine atom, a chlorine atom, a boron atom, and an iodine atom.

[0035] Specific examples of the diamine compound [D1] include compounds represented by the following formulas (d-1) to (d-16). [ka] [ka]

[0036] The content of the structural unit U1 in the polymer [P] is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and particularly preferably 50 mol% or more, based on the total amount of structural units derived from the diamine compound contained in the polymer [P], in order to ensure sufficient dispersibility of the dispersed substance (especially dispersibility in an aqueous dispersion medium). Furthermore, the content of the structural unit U1 is preferably 99.5 mol% or less, more preferably 99 mol% or less, even more preferably 98 mol% or less, and particularly preferably 85 mol% or less, based on the total amount of structural units derived from the diamine compound contained in the polymer [P], in order to improve the dispersibility of the dispersed substance (especially dispersibility in an organic solvent dispersion medium) and to sufficiently reduce the volume resistivity of the CNT film when CNTs are used as the dispersed substance. In addition, when synthesizing the polymer [P], the diamine compound [D1] may be used alone or in combination of two or more.

[0037] (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 diaminoorganosiloxanes. Among these, it is preferable that the diamine compound [D2] be an aromatic diamine, from the viewpoint of imparting a rigid and highly uniaxially linear structure to the molecular chain of the polymer [P] and facilitating in-plane orientation of the polymer [P] through intermolecular stacking interactions, thereby further enhancing the dispersibility of the dispersed substance.

[0038] Specific examples of the diamine compound [D2] include aliphatic diamines such as metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and 1,3-bis(aminomethyl)cyclohexane; alicyclic diamines such as 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine);

[0039] Examples of aromatic diamines include paraphenylenediamine, metaphenylenediamine, 4,4'-diaminodiphenylmethane, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis(4-aminophenoxy)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-diaminofluoroethane, and the like. Main-chain diamines such as olefin, 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-phenylenediisopropylidene)bisaniline, 4,4'-(m-phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, and 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 diaminoorganosiloxanes include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, and the diamines described in JP-A-2010-97188 can also be used.

[0040] The diamine compound [D] is preferably a side chain type diamine. Specifically, the diamine compound [D] preferably has a partial structure represented by the following formula (2), and more preferably is an aromatic diamine having a partial structure represented by the following formula (2). *-L 21 -R 21 -R 22 -R 23 -R 24 …(2) (In formula (2), L 21 is a single bond, -O-, -CO-, -COO-* 1 , -OCO-* 1, -NR 25 -, -NR 25 -CO-* 1 , -CO-NR 25 -* 1 , an alkanediyl group having 1 to 6 carbon atoms, -OR 26 -* 1 , or -R 26 -O-* 1 (However, R 25 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 26 is an alkanediyl group having 1 to 3 carbon atoms. 1 " is R 21 This indicates that it is a bond with R. 21 and R 23 are each independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted cycloalkylene group; R 22 represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted cycloalkylene group, or -R 27 -B 1 -R 28 -(However, R 27 and R 28 are each independently a substituted or unsubstituted phenylene group or cycloalkylene group, B 1 is a single bond, -O-, -COO-* 2 , -OCO-* 2 , -OCH2-* 2 , -CH2O-* 2 or an alkanediyl group having 1 to 3 carbon atoms. 2 " is R 28 This indicates that it is a bond with R. 24 is a hydrogen atom, a fluorine atom, a cyano group, CH3COO-* 3 ("* 3 " is R 23 ) represents a bond to 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, a hydrocarbon group having 17 to 51 carbon atoms and a steroid skeleton, or a monovalent group in which at least one hydrogen atom of an alkyl group having 1 to 18 carbon atoms has been substituted with a cyano group.21 , R 22 and R 23 When all of are single bonds, R 24 R 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, a fluoroalkoxy group having 6 to 18 carbon atoms, a hydrocarbon group having 17 to 51 carbon atoms and a steroid skeleton, or a monovalent group in which at least one hydrogen atom of an alkyl group having 6 to 18 carbon atoms has been substituted with a cyano group. 21 , R 22 and R 23 When the total number of substituted or unsubstituted phenylene groups and substituted or unsubstituted cycloalkylene groups contained in R is 1, 24 represents an alkyl group having 4 to 18 carbon atoms, a fluoroalkyl group having 4 to 18 carbon atoms, an alkoxy group having 4 to 18 carbon atoms, a fluoroalkoxy group having 4 to 18 carbon atoms, or a monovalent group in which at least one hydrogen atom of an alkyl group having 4 to 18 carbon atoms has been substituted with a cyano group. "*" represents a bond.

[0041] 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 that each of the substituted phenylene group and the substituted cycloalkylene group has is preferably 1 or 2, and more preferably 1. R 24 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, when R 24 is preferably linear, and has preferably 2 or more carbon atoms, more preferably 3 or more carbon atoms, and even more preferably 5 or more carbon atoms. In order to achieve excellent dispersibility even when the amount of the polymer [P] is small, the group represented by the above formula (2) is 21 , R 22 and R 23 At least one of R has a ring structure, or 24 has a steroid skeleton, and R 21 , R22 and R 23 The total number of ring structures is two or more, or R 24 It is more preferable that the compound has a steroid skeleton, and it is even more preferable that the compound has a steroid skeleton.

[0042] Among the above, the diamine compound [D2] is particularly preferably an aromatic diamine in which a group represented by the above formula (2) is bonded to a diaminophenyl group (i.e., a compound represented by the following formula (3)) in order to further increase the in-plane orientation of the polymer [P] and the dispersibility of the dispersed substance. In this case, the bonding positions of the two primary amino groups are not particularly limited and may be, for example, the 2,4-position, 2,5-position, or 3,5-position relative to the group represented by the above formula (2). [ka] (In formula (3), L 21 , R 21 , R 22 , R 23 and R 24 is the same as the above formula (2).

[0043] Specific examples of the diamine compound [D2] include, for example, hexanoxy-3,5-diaminobenzene, heptanoxy-2,4-diaminobenzene, dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyloxy-2,5 ... oxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostaniyl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 2,4-diamino-N,N-diallylaniline, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 5ξ-cholestan-3-yl 3,5-diaminobenzoate, compounds of the following formula (E-1): [ka] (In formula (E-1), X I and X II are each independently a single bond, -O-, *-COO- or *-OCO- (where "*" represents X I ) and R I is an alkanediyl group having 1 to 3 carbon atoms, and R II represents a single bond or an alkanediyl group having 1 to 3 carbon atoms, R6 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 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, a represents an integer of 0 to 2, b represents an integer of 0 to 2, and d represents 0 or 1, provided that a and b cannot be 0 at the same time. Examples of the compound include compounds represented by the following formula:

[0044] Specific examples of the compound represented by the above formula (E-1) include compounds represented by the following formulas (E-1-1) to (E-1-11). [ka] [ka] (In formulas (E-1-1) to (E-1-11), X 1 is -O-, -OCH2-, -CH2O-, -COO-CH2- or -CH2-OCO-, and R 6 has the same meaning as formula (E-1) above.

[0045] The content of the structural unit U2 in the polymer [P] is preferably 0.5 mol% or more, more preferably 1 mol% or more, even more preferably 2 mol% or more, and particularly preferably 15 mol% or more, of the total amount of structural units derived from the diamine compound contained in the polymer [P] (i.e., the total amount of the structural units U1 and U2), in order to ensure sufficient dispersibility of the dispersed substance (especially dispersibility in an organic solvent-based dispersion medium). Furthermore, the content of the structural unit U2 is preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 80 mol% or less, and particularly preferably 50 mol% or less, in order to improve the dispersibility of the dispersed substance (especially dispersibility in an aqueous dispersion medium). In addition, when synthesizing the polymer [P], the diamine compound [D2] may be used alone or in combination of two or more.

[0046] The polymer [P] is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide. The polymer [P] can be obtained, for example, by polymerization using, as raw material compositions, at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic acid dianhydrides, tetracarboxylic acid diesters, and tetracarboxylic acid diester dihalides, and a diamine compound.

[0047] [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.

[0048] (Tetracarboxylic acid dianhydride) The tetracarboxylic acid dianhydride used in the synthesis of the polymer [P] is not particularly limited, and examples thereof include aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, aromatic tetracarboxylic acid dianhydrides, etc. Specific examples of these include butanetetracarboxylic acid dianhydride as an aliphatic tetracarboxylic acid dianhydride; Examples of alicyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione- 6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0]octane-2,4,6,8-tetracarboxylic acid 2:3,5:6-dianhydride 2,6]undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, ethylene glycol bis(anhydrotrimellitate), 1,3-propylene glycol bis(anhydrotrimellitate), etc.; Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 4,4'-biphthalic dianhydride, 4,4'-carbonyldiphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, and naphthalene-1,4,5,6-tetracarboxylic dianhydride; In addition to the above, the tetracarboxylic dianhydrides described in JP-A-2010-97188 can also be used.

[0049] The tetracarboxylic acid dianhydride used in the synthesis of the polymer [P] is preferably a compound having a partial structure represented by each of the following formulas (t-1) to (t-21) (hereinafter also referred to as "specific tetracarboxylic acid dianhydride") from among the above, from the viewpoint of making the molecular chain of the polymer [P] have a rigid and highly uniaxially linear structure and facilitating in-plane orientation of the polymer [P]. [ka] (In formulas (t-1) to (t-21), "*" represents a bond bonded to a carbonyl group of an acid anhydride group (-CO-O-CO-).)

[0050] In order to improve the dispersibility of the dispersed substance, the content of the structural units derived from the specific tetracarboxylic dianhydride in the polymer [P] is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 50 mol% or more, based on the total amount of structural units derived from the tetracarboxylic dianhydride contained in the polymer [P]. Furthermore, the content of the structural units derived from the specific tetracarboxylic dianhydride can be 100 mol% or less, based on the total amount of structural units derived from the tetracarboxylic dianhydride contained in the polymer [P]. The tetracarboxylic dianhydride may be one of these alone or a combination of two or more thereof.

[0051] The tetracarboxylic acid derivative used in the synthesis of polymer [P] preferably contains an aromatic tetracarboxylic acid derivative, since this provides the polymer [P] with a rigid and highly uniaxially linear molecular chain structure, facilitating in-plane orientation of the polymer [P] (exhibiting lyotropic liquid crystallinity), and further enhancing the dispersibility of the dispersed substance. It is particularly preferred that the tetracarboxylic acid derivative contains an aromatic tetracarboxylic acid derivative having a partial structure represented by each of the above formulas (t-1) to (t-6). The content of structural units derived from aromatic tetracarboxylic acid derivatives in polymer [P] is preferably 20 mol % or more, more preferably 30 mol % or more, and even more preferably 50 mol % or more, based on the total amount of structural units derived from tetracarboxylic acid derivatives contained in polymer [P]. In addition, when synthesizing polymer [P], the aromatic tetracarboxylic acid derivatives may be used alone or in combination of two or more.

[0052] (Synthesis of polyamic acid [P]) The polyamic acid [P] can be obtained by reacting the above-mentioned tetracarboxylic dianhydride with a diamine compound, optionally together 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 preferably such that 0.2 to 2 equivalents, and more preferably 0.3 to 1.2 equivalents, of the acid anhydride groups of the tetracarboxylic dianhydride are used per equivalent of the amino groups of the diamine compound.

[0053] When the diamine compound has an acidic functional group, the reaction may be carried out after neutralizing it by adding a base. As the base, a tertiary amine is preferred, and triethylamine is particularly preferred. The base is preferably used in an amount of 0.5 to 5 equivalents relative to the acidic functional group, and more preferably 1 to 2 equivalents. Similarly, when the diamine compound has a basic functional group, the reaction may be carried out after neutralizing it by adding an acid. As the acid, a carboxylic acid is preferred. The acid is preferably used in an amount of 0.5 to 5 equivalents relative to the basic functional group, and more preferably 1 to 2 equivalents.

[0054] Examples of molecular weight modifiers include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. The proportion of the molecular weight modifier used is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the total of the tetracarboxylic dianhydride and diamine used.

[0055] The synthesis reaction of the polyamic acid [P] is preferably carried out in an organic solvent. The reaction temperature 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.

[0056] Examples of organic solvents used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Among these organic solvents, it is preferable to use one or more selected from the group consisting of aprotic polar solvents and phenolic solvents (Group 1 organic solvents), or a mixture of one or more selected from Group 1 organic solvents with one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (Group 2 organic solvents). In the latter case, the proportion of the Group 2 organic solvent used is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on the total amount of the Group 1 organic solvents and the Group 2 organic solvents.

[0057] Particularly preferred organic solvents are one or more selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol, and halogenated phenols, or a mixture of one or more of these with other organic solvents in the above-mentioned proportions. The amount (a) of the organic solvent used is preferably an amount such that the total amount (b) of the tetracarboxylic dianhydride and the diamine is 0.1 to 50% by mass relative to the total amount (a+b) of the reaction solution.

[0058] [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]") can be obtained, for example, by a method such as [I] reacting the polyamic acid [P] obtained by the above polymerization reaction with an esterifying agent, [II] reacting a tetracarboxylic acid diester with a diamine, or [III] reacting a tetracarboxylic acid diester dihalide with a diamine. The polyamic acid ester [P] may have only an amic acid ester structure, or may have both an amic acid structure and an amic acid ester structure.

[0059] [Polyimide] When the polymer [P] is a polyimide, the polyimide (hereinafter also referred to as "polyimide [P]") can be obtained by imidizing the polyamic acid [P] or polyamic acid ester [P] synthesized as described above through dehydration and cyclization. The polyimide [P] may be a fully imidized product in which all of the amic acid structures or amic acid ester structures contained in its precursor polyamic acid [P] or polyamic acid ester [P] have been dehydrated and cyclized, or a partially imidized product in which only a portion of the amic acid structures and amic acid ester structures have been dehydrated and cyclized, resulting in both amic acid structures or amic acid ester structures and imide ring structures. In order to sufficiently enhance the dispersibility of the dispersed substance, the polyimide [P] preferably has an imidization rate of 50% or more, more preferably 75% or more, even more preferably 85% or more, and particularly preferably 90% or more. The imidization ratio is the ratio, expressed as a percentage, of the number of imide ring structures to the total number of amic acid structures and amic acid ester structures and the number of imide ring structures in the polyimide.

[0060] The dehydration ring-closure to obtain the polyimide [P] is preferably carried out by a method of heating the polyamic acid, or by a method of dissolving the polyamic acid in an organic solvent, adding at least one of a dehydrating agent and a dehydration ring-closure catalyst to the solution, and heating as necessary.

[0061] In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a polyamic acid solution, the dehydrating agent can be, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride. The amount of the dehydrating agent used is preferably 0.01 to 20 mol per mol of the amic acid structure of the polyamic acid. The dehydration ring-closing catalyst can be, for example, a base catalyst such as pyridine, triethylamine, or 1-methylpiperidine, or an acid catalyst such as methanesulfonic acid or benzoic acid. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol per mol of the dehydrating agent used. Examples of organic solvents used in the dehydration ring-closing reaction include the organic solvents exemplified for use in the synthesis of polyamic acid [P]. The reaction temperature for the dehydration ring-closing 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.

[0062] The reaction solution containing the polymer [P] may be used directly for preparing the dispersion composition, or the polymer [P] contained in the reaction solution may be isolated and then used for preparing the dispersion composition, or the isolated polymer [P] may be purified and then used for preparing the dispersion composition. The isolation and purification of the polymer [P] may be carried out according to known methods.

[0063] The polymer [P] obtained as described above preferably has a solution viscosity of 10 to 2000 mPa·s, and more preferably 20 to 1000 mPa·s, when made into a 10% by mass solution. The solution viscosity (mPa·s) of the polymer is a value measured at 25°C using an E-type rotational viscometer for a 10% by mass polymer solution prepared using a good solvent for the polymer (e.g., water).

[0064] The weight average molecular weight (Mw) of the polymer [P] measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn), which is expressed as the ratio of Mw to the number average molecular weight (Mn) measured by GPC in terms of polystyrene, is preferably 15 or less, more preferably 10 or less.

[0065] Here, carbon nanotubes, which are one of the dispersed substances, have excellent properties such as electrical conductivity, heat resistance, toughness, and lightweight. However, carbon nanotubes have a high tendency to aggregate, making them difficult to uniformly disperse in both aqueous and organic solvent-based dispersion media. Furthermore, if the carbon nanotubes are not well dispersed, there is a concern that the various properties of the carbon nanotubes may not be fully exhibited in films and wiring obtained using the dispersion composition. In this regard, the dispersion composition of the present disclosure contains a polymer [P] as a dispersant, thereby achieving high dispersibility of the carbon nanotubes in both aqueous and organic solvent systems. Furthermore, by using a dispersion composition containing carbon nanotubes and a polymer [P], films and wiring with excellent electrical conductivity can be formed.

[0066] The content of the polymer [P] in the dispersion composition is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total mass of the dispersed substance and the polymer [P], from the viewpoint of ensuring sufficient dispersibility of the dispersed substance. Furthermore, the content of the polymer [P] is preferably 99.5% by mass or less, more preferably 99% by mass or less, based on the total mass of the dispersed substance and the polymer [P], from the viewpoint of obtaining sufficient functionality of the dispersed substance.

[0067] The content of the polymer [P] in the dispersion composition is preferably 0.05 to 30% by mass relative to the total amount of the dispersion medium and the polymer [P]. The polymer [P] is preferred because it exhibits high dispersibility of the dispersed substance even at a relatively low polymer concentration. Furthermore, since the viscosity of the dispersion composition can be reduced, the coating properties when forming a coating film on a substrate are good, and a thin film of about 0.1 μm can be formed, resulting in excellent industrial productivity. The content of the polymer [P] is more preferably 0.1 to 25% by mass, and even more preferably 0.2 to 20% by mass, relative to the total mass of the dispersion medium and the polymer [P].

[0068] The solids concentration of the dispersion composition (i.e., the proportion of the total mass of the components of the dispersion composition other than the dispersion medium to the total mass of the dispersion composition) is appropriately selected taking into consideration the viscosity, volatility of the dispersion medium, etc., but is preferably in the range of 1 to 70 mass %, more preferably in the range of 3 to 50 mass %, and even more preferably in the range of 5 to 40 mass %. The dispersion composition of the present disclosure may be used in a form in which it is applied to the surface of a substrate, and a coating film is formed, preferably by removing the dispersion medium. In this case, if the solids concentration is 1 mass % or more, the coating film thickness will not be too thin, and it will be easy to form a coating film containing the dispersed substance. On the other hand, if the solids concentration is 70 mass % or less, the coating film thickness will not be too large, and it will be easy to form a high-quality coating film. In addition, the viscosity of the dispersion composition will not be too high, and a decrease in coatability will be suppressed.

[0069] The dispersion composition of the present disclosure may contain a dispersant other than the polymer [P] (hereinafter also referred to as "other dispersant") as long as the purpose and effect of the present disclosure are not impaired. The content of the other dispersant is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total amount of dispersants contained in the dispersion composition.

[0070] <Other ingredients> The dispersion composition of the present disclosure may contain other components in addition to (A) the dispersed substance, (B) the dispersion medium, and (C) the dispersant, as long as the components do not impair the objects and effects of the present disclosure. Examples of other components include surfactants, fillers, pigments, antifoaming agents, sensitizers, antioxidants, adhesion aids, antistatic agents, leveling agents, and antibacterial agents. The content ratio of the other components can be appropriately set depending on each compound to be blended, as long as the effects of the present disclosure are not impeded.

[0071] The method for preparing the dispersion composition is not particularly limited, and can be carried out according to a known method. For example, the dispersion composition can be prepared by mixing the substance to be dispersed, the dispersion medium, and the dispersant, and optionally heating, stirring, etc. The temperature when preparing the dispersion composition is preferably 5 to 90°C, more preferably 10 to 65°C. The treatment of mixing the substance to be dispersed, the dispersion medium, and the dispersant may be carried out using, for example, a homogenizer, a bead mill, etc.

[0072] The dispersion composition of the present disclosure uses a polymer [P] as a polymer dispersant to suppress aggregation of the dispersed substance, thereby stably dispersing the dispersed substance in the dispersion medium. The dispersion composition of the present disclosure is applied to a substrate, and then preferably heated to remove the dispersion medium, thereby forming a coating film containing the dispersed substance on the substrate. The dispersion composition of the present disclosure can also be used in liquid form, either as is or by mixing with other dispersions.

[0073] The dispersion composition of the present disclosure can be used for various applications depending on the type of substance to be dispersed, specifically, for transparent conductive films, antistatic films, insulating films, protective films, antireflective films, colored films, field effect transistors (FETs), touch panels, conductive inks, paints, printing inks, inkjet coating inks, etc.

[0074] Second Embodiment Next, a method for producing an anisotropic film according to the present disclosure will be described. This method includes a holding step in which a dispersion composition containing a substance to be dispersed, a dispersion medium, and a compound exhibiting lyotropic liquid crystallinity is held on a support surface while applying shear stress, and a transfer step in which the dispersion composition held on the support surface is transferred onto a substrate. Details of this method will be described below.

[0075] (holding process) For the dispersed substance and dispersion medium contained in the dispersion composition, the explanations of (A) the dispersed substance and (B) the dispersion medium in the first embodiment can be applied. 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 lyotropic liquid crystallinity, but is preferably a polymer, and more preferably at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide. Among these, compound (L) is particularly preferably a polymer having a structural unit U1 derived from a diamine compound [D1] represented by the following formula (1). The description of diamine compound [D1] in the first embodiment can be applied to the description of diamine compound [D1] in the first embodiment. [ka] (In formula (1), n ​​is 0 or 1. When n is 0, R 1 ~R 4 At least one of R is a monovalent group having an ionic functional group, and the rest are each independently a hydrogen atom, a halogen atom, or a monovalent organic group. 1 ~R 8 At least one of the groups is a monovalent group having an ionic functional group, and the remaining groups are each independently a hydrogen atom, a halogen atom, or a monovalent organic group.

[0076] Compound (L) may be a polymer in which all structural units constituting compound (L) are structural units U1, or may be a polymer [P] further having a structural unit U2 different from structural unit U1. When compound (L) further has structural unit U2, the explanation of the structural unit U2 and polymer [P] can be applied to the explanation of the first embodiment. In addition, the explanation of the first embodiment can be applied to the explanation of the tetracarboxylic acid anhydride used in the synthesis of compound (L), the polymerization method, etc.

[0077] The support for holding the dispersion composition is not particularly limited, and examples include rotating bodies made of resin, rubber, metal, etc.; flat plates, etc. The support is preferably a rotating body. In this process, the dispersion composition is supplied to the support while applying shear stress, thereby causing the support to hold the dispersion composition. In a preferred example, a stress generator is placed opposite the surface of the support, and the dispersion composition is supplied so that it passes between the rotating body and the stress generator. In this process, shear stress is applied to the dispersion composition by differentiating the movement speed of the support surface from the movement speed of the stress generator surface. The surface of the stress generator may move in the same direction as the movement direction of the support surface (the rotation direction if the support is a rotating body), or in the opposite direction to the movement direction of the support surface. The stress generator may also be, for example, a housing or a blade, and may be a member whose position is fixed.

[0078] The amount of dispersion composition retained on the surface of the support can be adjusted appropriately depending on the size of the gap between the surface of the support and the surface of the stress generator. The gap is, for example, 0.01 to 5 μm. The stress generator preferably also functions as a retention amount adjuster that adjusts the amount of dispersion composition retained on the surface of the support.

[0079] Alternatively, the dispersion composition may be applied to a flat plate serving as a support by bar coating, slit coating, or the like while applying shear stress to form a coating film, thereby holding the dispersion composition on the support.

[0080] (Transfer process) In this step, the dispersion composition held on the support surface is transferred onto a substrate. Examples of the substrate include glass such as float glass and soda glass; and transparent substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly(alicyclic olefin). The dispersion composition can be transferred to the substrate by contacting the dispersion composition on the support surface with the substrate, preferably by moving the substrate relative to the support. When transferring the dispersion composition to the substrate, the transfer may be performed by pressing the support from the opposite side of the support, sandwiching the substrate between them, at a position facing the support.

[0081] The coating film transferred to the substrate is preferably heated to form an anisotropic film on the substrate. The heating temperature is, for example, 30 to 180°C, more preferably 40 to 150°C. The heating time is, for example, 1 to 30 minutes. The thickness of the anisotropic film formed is preferably 0.05 to 5 μm.

[0082] Next, an anisotropic film forming apparatus for forming an anisotropic film on a substrate using the present manufacturing method will be described. The anisotropic film forming apparatus of the present disclosure includes a holding unit that holds a dispersion composition containing a dispersion medium, a compound exhibiting lyotropic liquid crystallinity, and a compound to be dispersed on a support surface while applying shear stress, and a transfer unit that transfers the dispersion composition held on the support surface onto the substrate.

[0083] 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.

[0084] 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 is made of, for example, a rubber layer, and a dispersion composition 20 is applied to its surface.

[0085] The doctor roll 12 is, for example, a metallic rotating body, and is positioned opposite the coating roll 11. In the shear coating device 10, a dispersion composition 20 is supplied into the gap between the coating roll 11 and the doctor roll 12, whereby the dispersion composition 20 is applied to the surface of the coating roll 11 to form a coating film. The doctor roll 12 scrapes off excess dispersion composition on the surface of the coating roll 11, thereby adjusting the amount of dispersion composition applied to the surface of the coating roll 11 (i.e., the film thickness). The amount of dispersion composition applied can be adjusted by 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, etc.

[0086] The rotation directions of the coating roll 11 and the doctor roll 12 may be the same or opposite to each other. In this embodiment, the rotation direction of the coating roll 11 and the rotation direction of the doctor roll 12 are the same. Furthermore, the rotation speed V1 of the coating roll 11 is different from the rotation speed V2 of the doctor roll 12; for example, the rotation speed V2 is faster than the rotation speed V1. At least one of the coating roll 11 and the doctor roll 12 may be reversible. The coating roll 11 corresponds to the "holding body," and the doctor roll 12 corresponds to the "stress generator."

[0087] The backup roll 13 is disposed opposite the coating roll 11 along the transport path of the substrate 30. The arrow in FIG. 1 indicates the direction of movement of the substrate 30. The backup roll 13 presses the substrate 30 from the surface opposite to the coating surface of the substrate 30. As a result, as the substrate 30 moves relative to the coating roll 11, the coating film on the surface of the coating roll 11 is transferred to the surface of the substrate 30 at the contact portion 19 between the coating roll 11 and the substrate 30, and an anisotropic film 21 is formed on the surface of the substrate 30.

[0088] 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 this time, at a contact portion 18 where the coating roll 11 and the doctor roll 12 come into contact with each other via 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 excess dispersion composition 20 on the surface of the coating roll 11 is scraped off. This shear stress causes the compound (L) in the coating film made of the dispersion composition 20 to be uniaxially oriented, and the dispersed substance is aligned along the molecular chains of the compound (L). The rotation directions of the coating roll 11 and the doctor roll 12 are preferably the same, so that sufficient shear stress can be applied to the coating film made of the dispersion composition 20. The coating film formed on the surface of the coating roll 11 is then transferred at a contact portion 19 between the coating roll 11 and the substrate 30, thereby forming an anisotropic film 21 on the substrate 30.

[0089] The shear coating apparatus 10 described above is configured such that a dispersion composition containing compound (L) as a dispersant is applied to a coating roll 11 while applying shear stress to form a coating film, and then the coating film is transferred onto a substrate 30 to form an anisotropic film on the substrate 30. This configuration includes a step of transferring a coating film temporarily formed on the coating roll 11 as a support to the substrate 30, thereby making it possible to obtain an anisotropic film with excellent properties such as electrical conductivity anisotropy, polarization absorption characteristics, heat transfer anisotropy, and degassing resistance, compared to when an anisotropic film is formed directly on a substrate. In particular, using the coating roll 11, which is a rotating body, as a support is advantageous in that it can enhance the effect of improving various properties.

[0090] The contact portion 18 where 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 the "holding portion that holds the dispersion composition on the surface of the support while applying shear stress," and the contact portion 19 of the coating roll 11 with the substrate 30 corresponds to the "transfer portion that transfers the dispersion composition held on the surface of the support onto the substrate."

[0091] 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.

[0092] 2, shear application device 100 is a ballpoint pen-type application device, and includes main body 101 and ball 102. Main body 101 is an elongated cylindrical body, and a storage section 103 for storing dispersion composition 200 is formed inside. In addition, a ball holding section 104 for rotatably holding ball 102 is provided at the axial tip of main body 101. A small gap is formed between ball holding section 104 and the circumferential surface of ball 102, and dispersion composition 200 filled in storage section 103 can enter this gap.

[0093] To form an anisotropic film on the surface of substrate 30 using shear coater 100, ball 102 of shear coater 100 is brought into contact with substrate 30 and then moved relative to substrate 30 (e.g., in the direction A in FIG. 2 ). This causes ball 102 to rotate, and as the ball rotates, dispersion composition 200 filled in storage section 103 adheres to the surface of ball 102. At this time, at contact section 105 where ball 102 and ball holder 104 come into contact with each other via a layer of dispersion composition 20, shear stress is applied to dispersion composition 20 from ball storage section 104 due to the rotation of ball 102. This shear stress causes compound (L) in the dispersion composition to be uniaxially oriented in the coating film formed on the surface of ball 102, and the dispersed substance is aligned along the molecular chains of compound (L). Thereafter, the coating film formed on the surface of ball 102 is transferred at contact portion 106 with substrate 30, thereby forming an anisotropic film 201 on substrate 30. In Fig. 2, arrow B indicates the direction in which dispersion composition 200 in storage portion 103 moves when an anisotropic film 201 is being formed on the surface of substrate 30 by shear coating device 100.

[0094] The shear coater 100 described above can easily form an anisotropic film with various excellent properties on the substrate 30. Furthermore, even when forming a narrow anisotropic film such as a wiring, the shear coater 100 is advantageous in that an anisotropic film 201 can be formed on the substrate 30 by a simple operation of moving the shear coater 100 relative to the substrate 30 while the ball 102 is in contact with the substrate 30. The contact portion 105, where the ball 102 and the ball holder 104 come into contact with each other via a layer of the dispersion composition 20, corresponds to a "holding portion that holds the dispersion composition on the holder surface while applying shear stress," and the contact portion 106 of the ball 102 with the substrate 30 corresponds to a "transfer portion that transfers the dispersion composition held on the holder surface to the substrate." The ball 102 corresponds to the "holder," and the ball holder 104 corresponds to a "stress generator."

[0095] Here, a material exhibiting lyotropic liquid crystallinity can be applied to a substrate while applying shear stress using a slit coating method, a bar coating method, or the like, to obtain a coating film in which the material exhibiting lyotropic liquid crystallinity is uniaxially oriented. However, when a coating film is formed on a substrate using a slit coating method or a bar coating method, for example, the orientation on the air-contacting surface side is easily disturbed, for example, due to the influence of highly hydrophobic air on the air-contacting surface side, causing hydrophobic groups to orient at a polar angle, and the anisotropy is reduced, making it difficult to fully obtain the desired properties. Furthermore, with regard to coatability, the slit coating method or the bar coating method may make it difficult to form a coating film on a substrate with insufficient wettability, or to apply the coating to irregularly shaped or curved substrates.

[0096] In contrast, the anisotropic film manufacturing method and anisotropic film forming apparatus disclosed herein combine the shear coating method and the transfer method to obtain an anisotropic film that is excellent in various properties such as conductive anisotropy, polarized light absorption characteristics, heat conduction anisotropy, degassing resistance, etc. Therefore, the anisotropic film obtained by the anisotropic film manufacturing method and anisotropic film forming apparatus disclosed herein can be used as various anisotropic films, such as polarizing films, retardation films, piezoelectric films, anisotropic conductive films, anisotropic thermally conductive films, and anisotropic magnetic films.

[0097] Although it is unclear why a production method including a transfer step can produce an anisotropic film with improved properties such as conductive anisotropy, one possible reason is that the transfer improves the uniaxial orientation of compound (L), thereby improving the dispersibility and orientation of the dispersed substance. In particular, when a rotating body is used as the support, the uniaxial orientation is further improved, which is thought to have further improved various properties. [Example]

[0098] The present disclosure will be explained in more detail below with reference to examples, but the contents of the present disclosure are not limited to these examples.

[0099] In the following examples, the weight average molecular weight Mw and imidization ratio 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 synthesis on a synthesis scale shown in the following synthesis examples as necessary.

[0100] [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: TSKgel GRCXLII, manufactured by Tosoh Corporation Solvent: N,N-dimethylformamide solution containing lithium bromide and phosphoric acid Temperature: 40℃ Pressure: 68kgf / cm 2 [Imidization rate of polymer] A solution containing polyimide was poured into pure water, and the resulting precipitate was thoroughly dried under reduced pressure at room temperature. After that, it was dissolved in deuterated dimethyl sulfoxide and measured at room temperature using tetramethylsilane as a reference substance. 1 H-NMR was measured. 1 The imidization rate was calculated from the H-NMR spectrum using the following formula (EX-1). Imidization rate (%) = (((1-E 1 ) / E 2 )×α)×100 …(EX-1) (In formula (EX-1), E 1 is the peak area due to the proton of the NH group that appears at a chemical shift of around 10 ppm, and E 2 is the peak area due to other protons, and α is the ratio of the number of other protons to one proton of the NH group in the polymer precursor (polyamic acid). In the following, the compound represented by formula (X) may be simply abbreviated as "compound (X)".

[0101] [First Example] 1. Polymer synthesis [Synthesis Example 1: Synthesis of polyamic acid] 36.77 g (95 mol parts) of pyromellitic dianhydride, 6.68 g (20 mol parts) of 2,5-diaminobenzenesulfonic acid, and 31.56 g (80 mol parts) of 2,4-diaminoheptyloxybenzene were dissolved in 425 g of N-methyl-2-pyrrolidone (NMP) and reacted 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, yielding 68 g of polyamic acid (hereinafter referred to as polymer (PAA-1)).

[0102] [Synthesis Example 2: Synthesis of Polyimide] 26.32 g (95 mol parts) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 23.03 g (99 mol parts) of 2,5-diaminobenzenesulfonic acid, and 0.65 g (1 mol part) of cholestanyl 3,5-diaminobenzoate were dissolved in 200 g of N-methyl-2-pyrrolidone (NMP) and reacted at room temperature for 6 hours. A polyamic acid solution with a polymer concentration of 20% by mass was obtained. 250 g of NMP was added to the resulting polyamic acid solution, followed by addition of 46.4 g of pyridine and 36.0 g of acetic anhydride. 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 resulting polymer (PI-1) was 99%.

[0103] [Synthesis Examples 3 to 9] Polyimides (polymers (PI-2) to (PI-6), (PI-1), and (PI-2)) were obtained in the same manner as in Synthesis Example 2, except that the types and amounts of tetracarboxylic dianhydrides and diamine compounds used in the reaction were changed as shown in Table 1 below. The imidization ratios of each polyimide are also shown in Table 1 below. [Synthesis Example 10] Polyamic acid (polymer (paa-1)) was obtained in the same manner as in Synthesis Example 1, except that the types and amounts of tetracarboxylic dianhydride and diamine compound used in the reaction were changed as shown in Table 1 below.

[0104] [Table 1]

[0105] The numerical values ​​in Table 1 indicate the proportion (mol %) of tetracarboxylic dianhydrides used relative to the total amount of tetracarboxylic dianhydrides used in the reaction, and the numerical values ​​in Table 1 indicate the proportion (mol %) of diamine compounds used relative to the total amount of diamine compounds used in the reaction. The abbreviations for tetracarboxylic dianhydrides and diamine compounds in Table 1 are as follows: (Tetracarboxylic acid dianhydride) AN-1; 2,3,5-tricarboxycyclopentylacetic dianhydride AN-2; Pyromellitic dianhydride AN-3; 1,3-propylene glycol bis(anhydrotrimellitate) (diamine compounds) DA-1; 2,5-diaminobenzenesulfonic acid DA-2; 2,5-diaminobenzoic acid DA-3; cholestanyl 3,5-diaminobenzoate DA-4; Cholestanyloxy-2,4-diaminobenzene DA-5: A compound represented by the following formula (DA-5): DA-6; 2,4-diamino-heptyloxybenzene DA-7; Paraphenylenediamine [ka]

[0106] 2. Preparation and evaluation of CNT-containing dispersion composition [Example 1] (1) Preparation of Dispersion Composition 400 parts by mass of distilled water was added as a solvent to a container containing 5 parts by mass of multi-walled carbon nanotubes (MWNTs) and 95 parts by mass of the polymer (PI-1) obtained in Synthesis Example 2. Next, ultrasonic dispersion was carried out for 10 minutes to prepare a dispersion composition (S-1).

[0107] (2) Evaluation of CNT dispersibility (water-based) The dispersion composition (S-1) obtained in (1) above was left to stand on a flat surface for one day. The evaluation was "good (○)" if the initial dispersion state was maintained, and "poor (×)" 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 distilled water as the solvent. The resulting dispersion composition was left to stand on a flat surface, and the dispersion state was observed over time. The evaluation was as follows: if the initial dispersion state was maintained after one week, it was rated "excellent (◎◎)"; if the initial dispersion state was maintained after three days, it was rated "excellent (◎)"; if the initial dispersion state was maintained after one day, it was rated "good (○)"; if the initial dispersion state was maintained after three hours, it was rated "fair (△)"; and if sedimentation or aggregation was observed after three hours, it was rated "poor (×)." As a result, the CNT dispersibility (organic solvent system) of this dispersion composition was rated "fair (△)."

[0108] (4) Evaluation of CNT coatability The dispersion composition (S-1) obtained in (1) above was applied to a glass substrate using a blade and dried on a hot plate at 80°C for 10 minutes to form a coating film with an average thickness of 1 μm. This coating film was observed under a microscope at 50x magnification to check for unevenness in thickness and the presence of pinholes. The coating was evaluated as "good (○)" when neither unevenness in thickness nor pinholes were observed, and as "poor (×)" when at least one of unevenness in thickness and pinholes was clearly observed. As a result, neither unevenness in thickness nor pinholes were observed, and the coating was evaluated as "good (○)."

[0109] (5) Evaluation of volume resistivity The dispersion composition (S-1) was applied to a glass substrate and dried in the same manner as in (4) above, except that the blade gap was changed, to obtain a film-like test piece (thickness: approximately 20 μm). Next, the volume resistivity of the obtained test piece was measured by a four-terminal method. The volume resistivity was calculated from the surface resistivity and film thickness using the following mathematical formula (5). In addition, the measurement was performed five 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 using this dispersion composition (S-1) was 1000 μΩ·m (0.1 Ω·cm). Note that the lower the volume resistivity, the higher the conductivity.

[0110] (6) Finger pressure test The dispersion composition (S-1) obtained in (1) above was applied to a glass substrate using a blade and dried on a hot plate at 80°C for 10 minutes to form a coating film with an average thickness of 10 μm. The resulting coating film was pressed with a finger to confirm its resistance to cracking (external force resistance). Evaluation was based on the following criteria: if no cracks were observed under a microscope (magnification: 10x), it was rated "good (○)"; if no cracks were observed visually but cracks were observed under a microscope, it was rated "fair (△)"; and if cracks were observed visually, it was rated "poor." As a result, the external force resistance of the coating film formed using this dispersion composition (S-1) was evaluated as "fair (△)" because no cracks were observed visually but cracks were observed under a microscope.

[0111] (7) Evaluation of substrate adhesion A substrate with carbon nanotubes was prepared by applying the dispersion composition (S-1) to a glass substrate and drying it in the same manner as in (4) above, except that the dispersion composition was applied by spray coating. A 0.5 μm-thick coating film was formed on the glass substrate. A solvent prepared so that the mixture was distilled water / isopropyl alcohol / propylene glycol monomethyl ether acetate = 5 / 25 / 70 (mass ratio) was then poured onto the substrate with carbon nanotubes, and the substrate was then dried on a hot plate at 80°C for 10 minutes. The resulting substrate (hereinafter referred to as the "adhesion evaluation specimen") was observed under a microscope (magnification: 10x) and its volume resistivity was evaluated to evaluate its substrate adhesion. The evaluation was as follows: if all of the following criteria 1, 2, and 3 were met, the product was rated as "best quality (◎◎)"; if criteria 1 and 2 were met but criterion 3 was not met, the product was rated as "excellent (◎)"; if criteria 1 was met but criterion 2 was not met, the product was rated as "good (○)"; if criteria 2 was met but criterion 1 was not met, the product was rated as "fair (△)"; and if neither criteria 1 nor 2 were met, the product was rated as "poor (×)". Criterion 1: No cracks are observed when the test piece for adhesion evaluation is observed under a microscope. Criterion 2: The volume resistivity of the test piece for adhesion evaluation, determined according to the method in (5) above, is 0.05 Ω·cm or less (500 μΩ·m or less). Criterion 3: The volume resistivity of the test piece for adhesion evaluation, determined according to the method in (5) above, is equal to or less than the volume resistivity value in (5) above. As a result, the substrate adhesion of this dispersion composition (S-1) was rated as "fair (Δ)".

[0112] [Examples 2 to 7, Comparative Examples 1 to 3] Dispersion compositions (S-2) to (S-7) and (sr-1) to (sr-3) were prepared in the same manner as dispersion composition (S-1) in Example 1, except that the composition of the dispersion composition was changed as shown in Table 2 below. Various evaluations were performed in the same manner as in Example 1, except that dispersion compositions (S-2) to (S-7) and (sr-1) to (sr-3) were used instead of dispersion composition (S-1). Evaluation of CNT dispersibility (organic solvent system) was performed using dispersion compositions prepared using cyclopentanone instead of distilled water as the solvent, as in (3) above in Example 1. The evaluation results for Examples 1 to 7 and Comparative Examples 1 to 3 are summarized in Table 2 below.

[0113] [Table 2]

[0114] In Table 2, the numerical values ​​for "blended amount" indicate parts by mass. The abbreviations for the compounds are as follows. <cnt> MWNT; multi-walled carbon nanotubes DWNT; double-walled carbon nanotubes SWNT; Single-wall carbon nanotube

[0115] The results in Table 2 show that Examples 1 to 7 had better dispersibility of carbon nanotubes in both aqueous and organic solvent systems than Comparative Examples 1 to 3. Furthermore, Examples 1 to 7 had better resistance to external forces, conductivity, and adhesion to substrates than Comparative Examples 1 to 3. These results are thought to be due to the fact that introducing CNTs (guests) into the lyotropic liquid crystal field (host) created by the polymer [P] orients the CNTs along the molecular chains of the polymer [P], thereby improving the dispersibility of the CNTs.

[0116] 3. Preparation and evaluation of metal particle-containing dispersion composition [Example 8] (1) Preparation of Dispersion Composition 53 parts by mass of distilled water as a solvent was added 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. The mixture was then shaken for 10 minutes using a paint shaker to prepare a dispersion composition (S-8).

[0117] (2) Evaluation of dispersibility (aqueous system) The dispersion composition (S-8) obtained in (1) above was left to stand on a flat surface 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). The resulting dispersion composition was left standing on a flat surface, and the dispersion state was observed over time. 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 evaluated as "fair (△)."

[0118] (4) Evaluation of particle coating properties The coating properties were 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 unevenness in film thickness nor pinholes were observed, and the coating properties were evaluated as "good (◯)." (5) Finger pressure test A finger pressure test was carried out in the same manner as in Example 1 (6), except that the dispersion composition (S-8) obtained in (1) above was used, to confirm the resistance to cracking (also referred to as external force resistance or finger pressure resistance). As a result, although no cracks were observed visually in the coating film formed using this dispersion composition (S-8), cracks were observed under a microscope, and therefore the finger pressure resistance was judged to be "fair (△)".

[0119] [Examples 9 to 19, Comparative Example 4] Dispersion compositions (S-9) to (S-19) and (sr-4) were prepared in the same manner as dispersion composition (S-8) in Example 8, except that the composition of the dispersion composition was changed as shown in Table 3 below. Furthermore, various evaluations were carried out in the same manner as in Example 8, except that dispersion compositions (S-9) to (S-19) and (sr-4) were used instead of dispersion composition (S-8). The evaluation of particle dispersibility (organic solvent system) was carried out using a dispersion composition prepared using cyclopentanone instead of distilled water as the solvent, as in (3) above in Example 8. The evaluation results for Examples 9 to 19 and Comparative Example 4 are summarized in Table 3 below.

[0120] [Table 3]

[0121] In Table 3, the numerical values ​​for "amount blended" indicate parts by mass. The abbreviations for the compounds are as follows: <Dispersant> BYK180; BYK-Chemie DISPERBYK-180 (polyacrylic dispersant)

[0122] The results in Table 3 show that Examples 8 to 19 had better dispersibility of metal particles even in an organic solvent system than Comparative Example 4. Furthermore, Examples 8 to 19 had better resistance to external forces than Comparative Example 4.

[0123] [Second Example] 1. Polymer synthesis [Synthesis Example 11: Synthesis of polyamic acid] A three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube was charged with 85.5 mol parts of 2,5-diaminobenzenesulfonic acid, 9.5 mol parts of paraphenylenediamine, and 218 mol parts of triethylamine dissolved in m-cresol, followed by stirring under nitrogen. After dissolving the diamine, 100 mol parts of pyromellitic dianhydride was added and stirred at 80°C for 3 hours. The reaction was carried out so that the solids content was 30%. After the reaction was completed, the reaction solution was diluted with m-cresol to a solids concentration of 15% and added dropwise to acetone to coagulate. The resulting coagulated material was filtered, washed in 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 resulting Polymer (PAA-2) was 151,000.

[0124] [Synthesis Example 12: Synthesis of Polyimide] 95 mol parts of 2,3,5-tricarboxycyclopentylacetic dianhydride, 20 mol parts of cholestanyl 3,5-diaminobenzoate, 60 mol parts of 4,4'-diaminodiphenyl ether, and 20 mol parts of 2,5-diaminobenzenesulfonic acid were dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a polyamic acid solution with a polymer concentration of 15% by mass. NMP was added to the resulting polyamic acid solution to dilute it to a polymer concentration of 10% by mass. After that, 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 resulting Polymer (PI-7) had a weight-average molecular weight of 202,000 and an imidization rate of 99%.

[0125] [Synthesis Example 13: Synthesis of polyimide] A polyimide polymer (PI-8) was obtained in the same manner as in Synthesis Example 1, except that the types and amounts of the tetracarboxylic dianhydride and diamine compound used in the reaction were changed as shown in Table 4 below, and the amount of catalyst was also changed. The imidization rate of each polyimide is also shown in Table 4 below.

[0126] [Table 4]

[0127] The numerical values ​​in Table 4 show the proportion (mol %) of tetracarboxylic dianhydrides used relative to the total amount of tetracarboxylic dianhydrides used in the reaction, and the numerical values ​​in Table 4 show the proportion (mol %) of diamine compounds used relative to the total amount of diamine compounds used in the reaction. The abbreviations for tetracarboxylic dianhydrides and diamine compounds in Table 4 are as follows: (Tetracarboxylic acid dianhydride) AN-1; 2,3,5-tricarboxycyclopentylacetic dianhydride AN-2; Pyromellitic dianhydride AN-4; Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride (diamine compounds) DA-1; 2,5-diaminobenzenesulfonic acid DA-3; cholestanyl 3,5-diaminobenzoate DA-7; Paraphenylenediamine DA-8; 4,4'-diaminodiphenyl ether [ka]

[0128] 2. Preparation of CNT-containing dispersion composition [Preparation Example 1] 10,000 parts by mass of distilled water was added as a solvent to a container containing 5 parts by mass of single-walled carbon nanotubes (SWNTs) and 25 parts by mass of the polymer (PAA-2) obtained in Synthesis Example 11. Next, ultrasonic dispersion was carried out for 60 minutes to prepare a dispersion composition (S-20). [Preparation Examples 2-5] Each dispersion composition was prepared in the same manner as in Preparation Example 1, except that the formulation of the dispersion composition was changed as shown in Table 5 below.

[0129] [Table 5]

[0130] In Table 5, the numerical values ​​for "blended amount" indicate parts by mass. The abbreviations for CNT are as follows: <cnt> MWNT; multi-walled carbon nanotubes DWNT; double-walled carbon nanotubes SWNT; Single-wall carbon nanotube SWNT-D; Single-walled carbon nanotubes with many defects <Dispersant> SDBS; Sodium dodecylbenzenesulfonate

[0131] 3. Evaluation of CNT-containing dispersion composition [Example 20] (1) Evaluation of coating properties on glass substrates The coating properties on glass substrates were evaluated using a shear coating device (see Figure 1) equipped with a coating roll and a doctor roll. First, the coating roll and doctor roll were rotated in the same direction (forward rotation), and the dispersion composition (S-20) obtained in Preparation Example 1 above was transferred onto a 150 mm x 150 mm glass substrate to form a coating film. Note that the coating method of forward rotation of the coating roll and doctor roll differs from conventional printing methods (offset printing, etc., in which the rolls are rotated in reverse to apply the coating). The coating was then dried on a hot plate at 80 °C for 10 minutes to form a coating film with a thickness of 0.5 μm. The evaluation was performed visually: if there were no pinholes or repelling, it was judged as "good (○)"; if there were pinholes or repelling, it was judged as "poor (×)." As a result, no pinholes or repelling were observed in the coating film on the glass substrate, and the coating properties on the glass substrate were judged as "good (○)."

[0132] (2) Evaluation of friction and wear resistance Using a shear coater similar to that described in (1) above, the dispersion composition (S-20) obtained in Preparation Example 1 above was shear-transfer coated onto a glass substrate, and the coating was dried at 80 ° C for 10 minutes to form a coating with an average thickness of 0.5 μm at the center of the substrate. This coating was subjected to a rubbing treatment with an indentation length of 0.3 mm, and the frictional wear resistance was evaluated by measuring the change in film thickness before and after the rubbing treatment. The evaluation was as follows: if the film thickness change was less than 20 nm, the frictional wear resistance was "good (○)", if the film thickness change was 20 nm or more but less than 35 nm, the frictional wear resistance was "fair (△)", and if the film thickness change was 35 nm or more, the frictional wear resistance was "poor (×)". In this example, the change in film thickness due to rubbing was 5 nm, so the frictional wear resistance was "good (○)".

[0133] (3) Evaluation of conductive anisotropy Using a shear coater similar to that described in (1) above, the dispersion composition (S-20) obtained in Preparation Example 1 was shear-transfer coated onto a glass substrate, and the coating was dried at 80°C for 10 minutes to obtain a test specimen. If necessary, multiple coatings were applied, adjusting the number of coatings to achieve a film thickness of approximately 20 μm. The volume resistivity (μΩ·m) of the resulting test specimen was measured using a two-terminal method. The electrical conductivity anisotropy of the test specimen was measured by changing the arrangement of the two terminals relative to the shear coating direction. The parallel volume resistivity was measured when the two terminals were arranged parallel to the shear coating direction, and the perpendicular volume resistivity was measured when the two terminals were arranged perpendicular to the shear coating direction. The volume resistivity was calculated from the surface resistivity and film thickness using the following formula (EX-2). Five measurements were performed at different locations, and the average value was estimated as the volume resistivity. Volume resistivity (μΩ m) = surface resistivity (Ω) x film thickness (μm) …(EX-2) The evaluation was as follows: when the ratio of parallel volume resistivity to perpendicular volume resistivity (parallel volume resistivity / perpendicular volume resistivity) was 100 or more, the conductive anisotropy was "good (○)"; when the parallel volume resistivity / perpendicular volume resistivity was 10 or more and less than 100, the conductive anisotropy was "fair (△)"; and when the parallel volume resistivity / perpendicular volume resistivity was less than 10, the conductive anisotropy was "poor (×)". As a result, the parallel volume resistivity / perpendicular volume resistivity ratio of the test piece obtained by shear transfer coating of the dispersion composition (S-20) was 508, and was judged to be "good (○)." Note that the larger the value of the parallel volume resistivity / perpendicular volume resistivity ratio, the greater the conductive anisotropy.

[0134] (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 above was coated onto a glass substrate and dried at 80°C for 10 minutes to obtain a film-like test piece. If necessary, the number of coatings was adjusted so that the film thickness was approximately 20 μm by coating multiple times. The coating was then washed by immersion in distilled water for 30 seconds. The volume resistivity (μΩ·m) of the resulting test piece was measured in the same manner as in (3) above. The evaluation was as follows: if the parallel volume resistivity / perpendicular volume resistivity ratio was 100 or greater, the electrical conductivity anisotropy after washing was deemed "good (○)." If the parallel volume resistivity / perpendicular volume resistivity ratio was 10 or greater but less than 100, the electrical conductivity anisotropy after washing was deemed "fair (△)." If the parallel volume resistivity / perpendicular volume resistivity ratio was less than 10, the electrical conductivity anisotropy after washing was deemed "poor (×)." As a result, the ratio of the parallel volume resistivity to the perpendicular volume resistivity of the test piece obtained by shear transfer coating with the dispersion composition (S-20) was 1818, which was deemed "good (○)."

[0135] (5) Polarized light absorption characteristics Using the same shear coating device as described in (1) above, the dispersion composition (S-20) obtained in Preparation Example 1 above was applied to a glass substrate and dried at 80°C for 10 minutes to form a coating film with an average thickness of 10 μm. The substrates were arranged so that the polarization axis (polarized light transmission axis) of a single Nicol lens and the shear coating direction of the coating film were parallel and perpendicular (approximately 90°), and the difference in transmittance between the horizontal and perpendicular orientations was measured when omnidirectional light was incident. The polarized light absorption properties were evaluated by measuring the difference in transmittance between the horizontal and perpendicular orientations when the difference in transmittance between the horizontal and perpendicular orientations was 40% or more, "good (○)," "fair (△)" when the difference was 25% or more but less than 40%, and "poor (×)" when the difference was less than 25%. As a result, the difference in transmittance between the horizontal and perpendicular orientations of the substrate was 48%, and the polarized light absorption properties were determined to be "good (○)."

[0136] (6) Evaluation of heat transfer anisotropy Using the same shear coating device as described in (1) above, the dispersion composition (S-20) obtained in Preparation Example 1 above was applied to a glass substrate and dried at 80°C for 10 minutes to form a 10 μm-thick coating film on a 120 mm × 120 mm glass substrate. Measurements were performed by heating the center of the substrate with a laser and measuring the heat propagation time using thermography. Evaluation was based on the time required for a point 50 mm from the center in the x-axis direction and a point 50 mm from the center in the y-axis direction to reach the same temperature as the center (heat-up time), measured based on the time difference. A time difference of 3 seconds or more was evaluated as "good (○)," a time difference of 1 second or more but less than 3 seconds was evaluated as "fair (△)," and a time difference of less than 1 second was evaluated as "poor (×)." As a result, the heat-up time difference in this example was 3.4 seconds, and was evaluated as "good (○)." Note that the larger the heat-up time difference, the greater the electrothermal anisotropy.

[0137] (7) Evaluation of heat transfer anisotropy after cleaning Using the same shear coating device as described in (1) above, the dispersion composition (S-20) obtained in Preparation Example 1 above was applied to a glass substrate and dried at 80°C for 10 minutes to form a 10 μm-thick coating film on a 120 mm × 120 mm glass substrate. The substrate on which the coating film was formed was then immersed in distilled water for 30 seconds to clean the coating film. The heat transfer anisotropy of the obtained test piece was measured in the same manner as described in (6) above. Evaluation was based on the time required for a point 50 mm from the center in the x-axis direction and a point 50 mm from the center in the y-axis direction to reach the same temperature as the center (heat-up time). A time difference of 3 seconds or more was rated "good," a time difference of 1 second or more but less than 3 seconds was rated "fair," and a time difference of less than 1 second was rated "poor." As a result, the heat-up time difference in this example was 3.2 seconds, which was judged to be "good."

[0138] (8) Evaluation of degassing resistance Using the same shear coating device as in (1) above, the dispersion composition (S-20) obtained in Preparation Example 1 above was applied to an 8-inch silicon substrate and dried at 80°C for 10 minutes to form a coating film with a thickness of 10 μm on the silicon substrate. The silicon substrate was cut into 1 cm x 5 cm pieces, and four of the cut silicon substrates were heated to 230°C at a rate of 10°C / min using a silicon wafer analyzer (a thermal desorption device JTD-505 manufactured by Japan Analytical Industry Co., Ltd., and a gas chromatograph mass spectrometer GCMS-QP2010Plus manufactured by Shimadzu Corporation), and the amount of outgassing (ng / cm) was measured when the temperature was increased to 230°C at a rate of 10°C / min and maintained at the same temperature for 15 minutes. 2 The evaluation was carried out at an outgassing rate of 200 ng / cm 2 If it was less than 200ng / cm, it was considered "good (○)" 2 More than 600ng / cm 2 If the temperature rise time difference was less than 150 ng / cm², it was rated as "Fair (△)", and if it was 600 ng / cm² or more, it was rated as "Poor (×)". 2 and was judged to be "good."

[0139] [Examples 21 to 23, 25, and 26, and Comparative Examples 5 to 7] Various evaluations were carried out in the same manner as in Example 20, except that the type of dispersion composition and the method of applying it to the substrate were changed as shown in Table 6 below. The evaluation results are shown in Table 6 below. [Example 24] The ink in a ballpoint pen with a ballpoint diameter of 1.2 mm was sucked out of the ink reservoir with a syringe, and the ink reservoir was washed and dried by injecting acetone into the empty ink reservoir. The dispersion composition (S-20) was then injected into the empty ink reservoir, and a drawing was performed to shear-transfer coating the ink onto a glass substrate (see Figure 2). The applicability to the glass substrate and the polarized light absorption properties were evaluated. The drawn lines were visually inspected for pinholes and repelling, as in Example 20, to evaluate the applicability. The polarized light absorption properties were evaluated as "good (○)" if the drawn lines were observed to turn black by rotating the polarizer, and as "poor (×)" if no blackening was observed. The evaluation results are shown in Table 6 below.

[0140] [Table 6]

[0141] In Table 6, the details of the application method are as follows: Transfer coating A: Shear coating was performed using a shear coating device by rotating the coating roll and doctor roll in the same direction. Transfer coating B: Shear coating was performed using a ballpoint pen type method. Transfer coating C: This was carried out in the same manner as transfer coating A, except that shear coating was carried out using a shear coating device with the coating roll and doctor roll rotating in opposite directions. Transfer coating D: Instead of using a shear coating device equipped with a coating roll and a doctor roll, the dispersion composition was shear coated onto a glass substrate using a bar coater, and the resulting coating film was transferred to another substrate to obtain a coating film.

[0142] As shown in Table 6, anisotropic films excellent in various properties such as electrical conductivity anisotropy, polarized light absorption characteristics, heat transfer anisotropy, and degassing resistance were obtained by forming anisotropic films by shear transfer coating using a dispersion composition containing a compound exhibiting lyotropic liquid crystallinity (Examples 20 to 26). The anisotropic films of Examples 20 to 26 also had excellent coatability to glass substrates and friction and abrasion resistance. In particular, Examples 20 to 25, which were subjected to shear transfer coating using a rotating body, were all evaluated as "Good" or "Good," and among these, Examples 20 to 22 were all evaluated as "Good."< / cnt> < / cnt>

Claims

1. A dispersed material; A dispersion medium; a polymer [P] which is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, and which has a structural unit U1 derived from a diamine compound [D1] represented by the following formula (1) and a structural unit U2 derived from a diamine compound [D2] different from the diamine compound represented by the following formula (1); Contains the dispersed substance is at least one selected from the group consisting of carbon nanotubes and simple metal particles, The diamine compound [D2] is a dispersion composition represented by the following formula (3): 【Chemical 1】 (In formula (1), n ​​is 0 or 1. When n is 0, R １ ~R ４ At least one of R is a monovalent group having an ionic functional group, and the remaining R are each independently a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group. １ ~R ８ At least one of the groups is a monovalent group having an ionic functional group, and the remaining groups are each independently a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group. 【Chemistry 3】 (In formula (3), L ２１ represents a single bond, -O-, -CO-, -COO-* １ , -OCO-* １ , -NR ２５ -, -NR ２５ -CO-* １ , —CO—NR ２５ -* １ , an alkanediyl group having 1 to 6 carbon atoms, —O—R ２６ -* １ , or -R ２６ -O-* １ (However, R ２５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ２６ is an alkanediyl group having 1 to 3 carbon atoms. １ " is R ２１ It indicates that it is a bond with . ２１ and R ２３ are each independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted cycloalkylene group, and R ２２ represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted cycloalkylene group, or -R ２７ -B １ -R ２８ - (However, R ２７ and R ２８ are each independently a substituted or unsubstituted phenylene group or 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 R ２８ It indicates that it is a bond with . ２１ , R ２２ , R ２３ The substituents of the substituted phenylene group and substituted cycloalkylene group in R are 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. ２４ represents a hydrogen atom, a fluorine atom, a cyano group, or a CH ３ COO-* ３ ("* ３ " is R ２３ ), 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, a hydrocarbon group having 17 to 51 carbon atoms and a steroid skeleton, or a monovalent group in which at least one hydrogen atom of an alkyl group having 1 to 18 carbon atoms has been substituted with a cyano group. ２１ , R ２２ and R ２３ When all of R are single bonds, ２４ R 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, a fluoroalkoxy group having 6 to 18 carbon atoms, a hydrocarbon group having 17 to 51 carbon atoms and a steroid skeleton, or a monovalent group in which at least one hydrogen atom of an alkyl group having 6 to 18 carbon atoms has been substituted with a cyano group. ２１ , R ２２ and R ２３ When the total number of substituted or unsubstituted phenylene groups and substituted or unsubstituted cycloalkylene groups contained in R ２４ represents an alkyl group having 4 to 18 carbon atoms, a fluoroalkyl group having 4 to 18 carbon atoms, an alkoxy group having 4 to 18 carbon atoms, a fluoroalkoxy group having 4 to 18 carbon atoms, or a monovalent group in which at least one hydrogen atom of an alkyl group having 4 to 18 carbon atoms has been substituted with a cyano group.

2. The dispersion composition according to claim 1, wherein the content 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.

3. the polymer [P] is a reaction product of at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic acid dianhydrides, tetracarboxylic acid diester compounds, and tetracarboxylic acid diester dihalides, with a diamine compound; The dispersion composition according to claim 1 or 2, wherein the tetracarboxylic acid derivative is an aromatic tetracarboxylic acid derivative.

4. A dispersant for dispersing at least one substance to be dispersed selected from the group consisting of carbon nanotubes and simple metal particles in a dispersion medium, The polymer [P] contains at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, and has a structural unit U1 derived from a diamine compound [D1] represented by the following formula (1) and a structural unit U2 derived from a diamine compound [D2] different from the diamine compound represented by the following formula (1): The diamine compound [D2] is a dispersant represented by the following formula (3): 【Chemistry 2】 (In formula (1), n ​​is 0 or 1. When n is 0, R １ ~R ４ At least one of R is a monovalent group having an ionic functional group, and the remaining R are each independently a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group. １ ~R ８ At least one of the groups is a monovalent group having an ionic functional group, and the remaining groups are each independently a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group. 【Chemistry 4】 (In formula (3), L ２１ represents a single bond, -O-, -CO-, -COO-* １ , -OCO-* １ , -NR ２５ -, -NR ２５ -CO-* １ , —CO—NR ２５ -* １ , an alkanediyl group having 1 to 6 carbon atoms, —O—R ２６ -* １ , or -R ２６ -O-* １ (However, R ２５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ２６ is an alkanediyl group having 1 to 3 carbon atoms. １ " is R ２１ It indicates that it is a bond with . ２１ and R ２３ are each independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted cycloalkylene group, and R ２２ represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted cycloalkylene group, or -R ２７ -B １ -R ２８ - (However, R ２７ and R ２８ are each independently a substituted or unsubstituted phenylene group or 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 R ２８ It indicates that it is a bond with . ２１ , R ２２ , R ２３ The substituents of the substituted phenylene group and substituted cycloalkylene group in R are 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. ２４ represents a hydrogen atom, a fluorine atom, a cyano group, or a CH ３ COO-* ３ ("* ３ " is R ２３ ), 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, a hydrocarbon group having 17 to 51 carbon atoms and a steroid skeleton, or a monovalent group in which at least one hydrogen atom of an alkyl group having 1 to 18 carbon atoms has been substituted with a cyano group. ２１ , R ２２ and R ２３ When all of R are single bonds, ２４ R 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, a fluoroalkoxy group having 6 to 18 carbon atoms, a hydrocarbon group having 17 to 51 carbon atoms and a steroid skeleton, or a monovalent group in which at least one hydrogen atom of an alkyl group having 6 to 18 carbon atoms has been substituted with a cyano group. ２１ , R ２２ and R ２３ When the total number of substituted or unsubstituted phenylene groups and substituted or unsubstituted cycloalkylene groups contained in R ２４ represents an alkyl group having 4 to 18 carbon atoms, a fluoroalkyl group having 4 to 18 carbon atoms, an alkoxy group having 4 to 18 carbon atoms, a fluoroalkoxy group having 4 to 18 carbon atoms, or a monovalent group in which at least one hydrogen atom of an alkyl group having 4 to 18 carbon atoms has been substituted with a cyano group.

5. A step of retaining the dispersion composition according to any one of claims 1 to 3 on a support surface while applying shear stress; transferring the dispersion composition held on the surface of the support onto a substrate; A method for producing an anisotropic film, comprising:

6. A holding part that holds the dispersion composition according to any one of claims 1 to 3 on a support surface while applying shear stress; a transfer unit that transfers the dispersion composition held on the surface of the support onto a substrate; An anisotropic film forming apparatus comprising:

Images