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WO2014054703A1 - Structure, film d'extraction de lumière, dispositif électronique et procédé pour la formation de la structure - Google Patents

Structure, film d'extraction de lumière, dispositif électronique et procédé pour la formation de la structure Download PDF

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Publication number
WO2014054703A1
WO2014054703A1 PCT/JP2013/076850 JP2013076850W WO2014054703A1 WO 2014054703 A1 WO2014054703 A1 WO 2014054703A1 JP 2013076850 W JP2013076850 W JP 2013076850W WO 2014054703 A1 WO2014054703 A1 WO 2014054703A1
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Prior art keywords
polymer
mass
polyimide
film
group
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Japanese (ja)
Inventor
加藤　拓
夏樹 佐藤
洋介 飯沼
徳俊 三木
宏之 桜井
幸広 見山
正睦 鈴木
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/854—Arrangements for extracting light from the devices comprising scattering means

Definitions

  • the present invention relates to a structure having irregularities formed on the surface by self-organization of polyimide or a polyimide precursor, a light extraction film, an electronic device, and a method for forming the structure.
  • optical devices optical elements
  • the optical device include a light emitting diode (LED, Light Emitting Diode) element in which a transparent substrate, a transparent electrode, a light emitting layer, and an electrode are laminated in this order, and light is extracted from the transparent substrate side.
  • LED Light Emitting Diode
  • the transparent substrate a transparent electrode, a light emitting layer, and an electrode are laminated in this order, and light is extracted from the transparent substrate side.
  • improvement in light extraction efficiency is required.
  • an organic light emitting diode (OLED) element As a technique for improving the light extraction efficiency, in an organic light emitting diode (OLED) element, a method of providing a lens on the front surface of a light extraction surface (light extraction surface) (see Patent Document 1), a sol-gel on the front surface of the light extraction surface There are known a method of providing a porous light scatterer by a method (see Patent Document 2) and a method of providing a light scattering layer in which metal fine particles generating plasmons are dispersed (see Patent Document 3).
  • the light extraction efficiency is improved by providing the light extraction film having the unevenness on the surface, when the unevenness is formed by the imprint method, there is a problem that the manufacturing process is long and cannot be easily formed.
  • Non-Patent Document 2 a technique has been reported in which self-organization is performed by thermally annealing a block copolymer of polystyrene and polymethyl methacrylate, followed by dry etching to produce fine irregularities.
  • This self-organization has an advantage that nano-scale processing can be performed easily and inexpensively as compared with a photolithography method or the like conventionally used in semiconductor device manufacturing.
  • block copolymer of polystyrene and polymethyl methacrylate which is an acrylic block copolymer
  • the block copolymer of polystyrene and polymethyl methacrylate is very difficult to manufacture, or the unevenness formed by the self-assembly of the block copolymer of polystyrene and polymethyl methacrylate.
  • the method of forming irregularities by self-organizing this block copolymer requires dry etching for expressing irregularities on the surface, baking at a high temperature of 300 ° C., annealing, and operation in a nitrogen atmosphere.
  • the manufacturing process is long, complicated and expensive.
  • the structure having unevenness on the surface that can be easily and reproducibly manufactured as described above is not limited to the LED including the light extraction film having the unevenness on the surface, but various optical devices, and further, semiconductor devices, The same applies to electronic devices such as solar cells, displays, storage media, and biochips.
  • the present invention has been made based on the above circumstances, and the problem to be solved is a structure having irregularities on its surface, a structure that can be easily and reproducibly manufactured, a light extraction film, An object is to provide an electronic device and a method for forming a structure.
  • a polyimide precursor or polyimide is contained together with a polymer different from the polyimide precursor or polyimide, or a composition containing propylene glycol monomethyl ether.
  • the present invention has been completed by obtaining the knowledge that a structure having irregularities on its surface can be obtained with good reproducibility by simply applying it to a substrate, leaving it to stand and firing it.
  • the gist of the present invention is as follows. 1. A structure comprising a first polymer made of polyimide and having irregularities formed on the surface by self-organization of the first polymer.
  • the average height of the convex portions formed on the surface is 0.5 nm to 500 nm.
  • the first polymer and a second polymer different from the first polymer are included, and irregularities formed by self-organization of the first polymer and the second polymer are formed on the surface. 1. It is characterized by having Or 2. The structure described in 1.
  • the second polymer is made of polyimide different from the first polymer.
  • ⁇ 3. The structure described in any one of.
  • At least one of the first polymer and the second polymer is selected from a bond capable of forming a hydrogen bond within a molecule or between molecules and a substituent capable of forming a hydrogen bond within a molecule or between molecules. Characterized by having at least one of the following: ⁇ 4. The structure described in any one of.
  • a bond capable of forming a hydrogen bond within the molecule or between the molecules is represented by the following formula (1), and a substituent capable of forming a hydrogen bond within the molecule or between the molecules includes a hydroxyl group, a thiol group, an amino group, and a carboxyl. 4. a group selected from groups; The structure described in 1.
  • a light extraction film comprising the structure described in any of the above.
  • a method for forming a structure having irregularities on the surface which is applied after a coating step of applying a composition for forming a structure containing the following component (A) and the following component (B) on a substrate, and after the coating step:
  • a method for forming a structure comprising: a placing step for placing, and a firing step for firing after the placing step.
  • Component (A) a first polymer made of polyimide or a first polymer precursor made of polyimide precursor.
  • Component (B) At least one of a second polymer or a second polymer precursor different from component (A) and propylene glycol monomethyl ether.
  • the structure having irregularities on the surface of the present invention is self-organized by applying a polyimide precursor or a composition containing polyimide together with another polymer or propylene glycol monomethyl ether to a substrate, leaving and baking the composition. It can be manufactured by an easy method. For example, complicated operations such as a dry etching process, a high-temperature baking process, and an operation in a high-humidity environment are unnecessary, and the number of processes is small. In addition, since the reproducibility is good, the structure can be manufactured stably. And the structure which has the unevenness
  • the structure according to the present invention includes a first polymer made of polyimide, and has irregularities formed on the surface by self-organization of the first polymer.
  • the self-organization means that a polymer structure such as polyimide or polyimide precursor applied on a base material is spontaneously assembled to create a structure with irregularities and a pattern.
  • a fractal pattern is formed instead of forming a specific pattern.
  • the determined specific pattern refers to an artificially determined pattern obtained by an artificial pattern forming method such as photolithography or imprint, and is based on a technique for continuously obtaining the same pattern.
  • the fractal pattern obtained by self-organization is a part of the geometry represented by the Mandelbrot set, which is difficult to define mathematically but is intuitively understood by humans.
  • Self-organization is based on a technique that continuously obtains fractal patterns (that is, patterns composed of sets having a self-similar structure) and attempts to keep the physical property values of the obtained self-assembled film within the standard. .
  • the basic unit figure of the fractal pattern formed by self-organization is, for example, a dot (dot) shape, a worm (worm) shape, a hole (Via) shape, or the like.
  • a basic unit graphic and a similar structure of the basic unit graphic form a fractal pattern.
  • AFM Atomic Force Microscope
  • SEM Sccanning Electron Microscope
  • TEM Transmission Electron Microscope
  • the basic unit figure is confirmed within 50 ⁇ m square. If this is not possible, it is excluded from the definition of a fractal pattern.
  • Examples of the point shape include a hemisphere whose shape in plan view is an ellipse or a circle.
  • the earthworm shape includes a shape in which a point shape and a point shape are connected and connected.
  • Examples of the hole shape include a shape in which a hole is opened on the outermost surface of the structure. These types of shapes may be selected depending on the application location of the structure of the present invention. Further, the number of basic unit graphics may be one or more, and a combination of a plurality of types may be used.
  • Factors that cause self-assembly in the present invention are (i) a difference in the polar term, dispersion term or surface energy of the polymer, (ii) a difference in solubility of the polymer in the solvent, or (iii) moisture absorption of the polymer.
  • a difference in property is utilized, and there is no particular limitation as long as a fractal pattern is obtained.
  • the unevenness formed by self-organization on the surface of the structure of the present invention has, for example, an average height of the protrusions of 0.5 nm to 500 nm.
  • the average height of the convex portion is represented by an average surface roughness (R a ) when measured by AFM.
  • the preferred average height of the protrusions may be selected according to the application location.
  • the average of convex portions is considered in consideration of short-circuit characteristics.
  • the height is preferably 0.5 nm to 50 nm, more preferably 0.5 nm to 30 nm.
  • the average height of the convex portions is preferably 40 nm to 500 nm. This is because if the average height of the protrusions is higher than 500 nm, the transparency may be lost and the light extraction efficiency may deteriorate.
  • the structure having unevenness on the surface of the present invention is, for example, applied on a substrate with a composition for forming a structure (hereinafter also referred to as varnish) containing the component (A) and the component (B). It can be obtained by a forming method including an application step, a leaving step for drawing after the applying step, and a firing step for baking after the drawing step.
  • Component (A) is polyimide (first polymer) or a polyimide precursor (first polymer precursor) that is imidized by firing to become polyimide (first polymer). That is, (A) component is a component which becomes a polyimide (1st polymer) in the structure of this invention manufactured.
  • the polyimide precursor is a polyamic acid (also called polyamic acid), a polyamic acid ester, or the like.
  • the polyimide and polyimide precursor which are (A) components have not been examined as a self-organization material until now.
  • Polyimide precursors such as polyamic acid and polyamic acid ester are obtained by reacting a diamine component with a tetracarboxylic acid component.
  • the polyamic acid ester can also be obtained by a method of converting the carboxyl group of the polyamic acid into an ester.
  • a polyimide is obtained by imidating polyimide precursors, such as these polyamic acids and polyamic acid ester.
  • the diamine component may be one type or two or more types
  • the tetracarboxylic acid component may be one type or two or more types.
  • the tetracarboxylic acid component is at least one selected from tetracarboxylic acids and tetracarboxylic acid derivatives.
  • the tetracarboxylic acid derivative include tetracarboxylic acid dihalide, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, and tetracarboxylic acid diester.
  • a polyamic acid can be obtained by reacting a diamine component with a tetracarboxylic acid dihalide, tetracarboxylic dianhydride, or the like.
  • a polyamic acid ester can be obtained by reacting a tetracarboxylic acid diester dichloride with a diamine component or reacting a tetracarboxylic acid diester with a diamine component in the presence of a suitable condensing agent or base.
  • tetracarboxylic acid component examples include a tetracarboxylic dianhydride represented by the following formula (2).
  • Z 1 is a tetravalent organic group having 4 to 13 carbon atoms containing a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms.
  • Z 1 examples include tetravalent organic groups represented by the following formulas (2a) to (2j).
  • Z 2 to Z 5 are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, which may be the same or different
  • Z 6 and Z 7 is a hydrogen atom or a methyl group, which may be the same or different.
  • Z 1 particularly preferred structure of Z 1 is represented by formula (2a), formula (2c), formula (2d), formula (2e), formula (2f) or formula from the viewpoint of polymerization reactivity and ease of synthesis. (2g).
  • the formula (2a), the formula (2e), the formula (2f), or the formula (2g) is preferable.
  • the ratio of the tetracarboxylic dianhydride represented by the formula (2) to the total amount of the tetracarboxylic acid component is not particularly limited. For example, 5 to 40 mol% of the total amount of the tetracarboxylic acid component is represented by the above formula (2).
  • the tetracarboxylic dianhydride is preferably 10 to 30 mol%.
  • tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the above formula (2) include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6 -Naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic Acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphen
  • Tetracarboxylic acid diesters are not particularly limited. Specific examples are given below. Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1 , 3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2, 3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1 -Cyclohexyl succinic acid dialkyl ester, 3,
  • aromatic tetracarboxylic acid dialkyl ester examples include pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, 2,2 ′, 3,3′-biphenyltetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-biphenyltetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-benzophenone tetracarboxylic acid dialkyl ester, bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3,6,7- Naphthalenetetracarboxylic acid dialkyl
  • the diamine component to be reacted with the tetracarboxylic acid component is not particularly limited, and general diamines can be used.
  • Examples of the diamine component include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, and 2,4-dimethyl-m.
  • Such a general-purpose diamine is preferably used in an amount of 50 to 95 mol% of the diamine component used for the synthesis of the polyamic acid, and more preferably 70 to 90 mol% of the diamine component.
  • a diamine component a long-chain alkyl group, a group having a ring structure or a branched structure in the middle of a long-chain alkyl group, a steroid group, or a group in which some or all of the hydrogen atoms of these groups are replaced with fluorine atoms Can be mentioned as a side chain.
  • diamines represented by the following formulas (3), (4), (5), and (6), but are not limited thereto.
  • l, m and n each independently represents an integer of 0 or 1
  • R 3 represents an alkylene group having 2 to 6 carbon atoms, —O—, —COO—, —OCO—, —NHCO.
  • R 4 , R 5 and R 6 each independently represents a phenylene group or a cycloalkylene group
  • R 7 is a hydrogen atom or carbon number 2
  • R 3 in the above formula (3) is preferably —O—, —COO—, —CONH—, or an alkylene-ether group having 1 to 3 carbon atoms from the viewpoint of ease of synthesis.
  • R 4 , R 5 and R 6 in the formula (3) are preferably combinations of l, m, n, R 4 , R 5 and R 6 shown in the following Table 1 from the viewpoint of ease of synthesis.
  • R 7 in formula (3) is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, more preferably A hydrogen atom, an alkyl group having 2 to 12 carbon atoms, or a fluorine-containing alkyl group.
  • R 7 is preferably an alkyl group having 12 to 22 carbon atoms or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent Heterocycles and monovalent macrocyclic substituents composed of these are preferred, and alkyl groups having 12 to 20 carbon atoms or fluorine-containing alkyl groups are more preferred.
  • a 10 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—.
  • a 11 represents a single bond or a phenylene group, and a represents —R 3 — (R 4 ) 1 — (R 5 ) m — (R 6 ) n —R 7 (R 3 , R 4 , R 5 , R 6 , R 7 , l, m, and n are the same as defined in the above formula (3), and a ′ is a divalent structure in which one element such as hydrogen is removed from the same structure as a. Represents a group of
  • a 14 is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
  • a 15 is a 1,4-cyclohexylene group or 1,4-phenylene.
  • a 16 is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A 15 )
  • a 17 is an oxygen atom or —COO— * (wherein a bond marked with "*” is (CH 2) binds to a 2.) it is.
  • a 1 is 0 or 1
  • a 2 is an integer of 2 ⁇ 10, a 3 0 Or 1.
  • the bonding position of the two amino groups (—NH 2 ) in the formula (3) is not limited. Specifically, with respect to the side chain (—R 3 — (R 4 ) 1 — (R 5 ) m — (R 6 ) n —R 7 ), 2, 3 positions on the benzene ring, 2, 4 Position, 2, 5 position, 2, 6 position, 3, 4 position, 3, 5 position. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.
  • a 1 is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.
  • a 2 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
  • 3 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
  • a 4 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, or —CH 2 —
  • a 5 represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.
  • a 6 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O—, or —NH—
  • a 7 represents fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy Group or hydroxyl group.
  • a 8 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .
  • a 9 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .
  • diamine represented by the formula (4) examples include diamines represented by the following formulas [A-25] to [A-30], but are not limited thereto.
  • a 12 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—
  • a 13 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
  • diamine represented by the formula (5) examples include diamines represented by the following formulas [A-31] to [A-32], but are not limited thereto.
  • Such a long chain alkyl group, a group having a ring structure or a branched structure in the middle of a long chain alkyl group, a steroid group, or a group in which some or all of the hydrogen atoms of these groups are replaced with fluorine atoms is a side chain. It is preferable to use an amount of 0 to 50 mol% of the diamine component used for the synthesis of the polyamic acid, and more preferably 10 to 40 mol% of the diamine component.
  • examples of the diamine component include diamines having a photoreactive group.
  • examples of the diamine having a photoreactive group include a diamine having a photoreactive group such as a vinyl group, an acrylic group, a methacryl group, an allyl group, a styryl group, a cinnamoyl group, a chalconeyl group, a coumarin group, and a maleimide group as a side chain.
  • the diamine represented by following General formula (7) can be mentioned, it is not limited to this.
  • R 8 is a single bond or —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, — Represents any one of N (CH 3 ) —, —CON (CH 3 ) —, —N (CH 3 ) CO—, and R 9 represents a single bond, or an unsubstituted or substituted carbon atom.
  • 10 vinyl group, an acryl group, a methacryl group, an allyl group, a styryl group, N (CH 2 CHCH 2) represents a 2, or represented by the following formula structure.
  • R 8 in the above formula (7) can be formed by a usual organic synthetic method, but from the viewpoint of ease of synthesis, —CH 2 —, —O—, —COO—, —NHCO —, —NH— and —CH 2 O— are preferred.
  • divalent carbocycle or divalent heterocycle carbocycle or heterocycle for replacing any —CH 2 — in R 9 include the following structures, but are not limited thereto. Is not to be done.
  • R 10 is preferably a vinyl group, an acrylic group, a methacryl group, an allyl group, a styryl group, —N (CH 2 CHCH 2 ) 2 or a structure represented by the following formula from the viewpoint of photoreactivity.
  • —R 8 —R 9 —R 10 in the above formula (7) is more preferably the following structure.
  • the bonding position of the two amino groups (—NH 2 ) in the formula (7) is not limited. Specifically, with respect to the side chain (-R 8 -R 9 -R 10 ), 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position on the benzene ring, Examples include positions 3, 4 and 3, 5. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.
  • diamine having a photoreactive group examples include, but are not limited to, the following compounds.
  • X is a single bond or a linking group selected from —O—, —COO—, —NHCO—, —NH—, Y is a single bond, or carbon that is unsubstituted or substituted by a fluorine atom. Represents an alkylene group of 1 to 20.
  • the diamine having such a photoreactive group is preferably used in an amount of 0 to 70 mol%, more preferably 0 to 60 mol% of the diamine component used for the synthesis of the polyamic acid.
  • the polymerization reaction between the diamine component and the tetracarboxylic dianhydride component is usually performed in an organic solvent.
  • the organic solvent used at that time is not particularly limited as long as the generated polyimide precursor such as polyamic acid dissolves. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, ⁇ -butyrolactone, isopropyl alcohol.
  • the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid component is dispersed or dissolved in the organic solvent as it is.
  • a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent a method of alternately adding a tetracarboxylic acid component and a diamine component, and the like. Any of these methods may be used.
  • the polymerization temperature can be selected from -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polyimide precursor (and thus polyimide), and if the concentration is too high, the viscosity of the reaction solution becomes too high. Uniform stirring becomes difficult.
  • the concentration of the total amount of the diamine component and the tetracarboxylic acid component is preferably 1 to 50% by mass, more preferably 5 to 30% by mass in the reaction solution.
  • the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
  • the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
  • the polyamic acid ester can be obtained by reacting the tetracarboxylic acid diester dichloride with the diamine component as described above, or reacting the tetracarboxylic acid diester with the diamine component in the presence of an appropriate condensing agent or base. it can. Alternatively, it can also be obtained by previously synthesizing a polyamic acid by the above method and esterifying the carboxyl group of the polyamic acid using a polymer reaction.
  • tetracarboxylic acid diester dichloride and a diamine component in the presence of a base and an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1
  • a polyamic acid ester By reacting for 4 to 4 hours, a polyamic acid ester can be synthesized.
  • pyridine triethylamine, 4-dimethylaminopyridine can be used, but pyridine is preferable because the reaction proceeds gently.
  • the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
  • the reaction proceeds efficiently by adding Lewis acid as an additive.
  • Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the addition amount of the Lewis acid is preferably 0.1 to 1.0 times the molar amount of the diamine or tetracarboxylic acid diester to be reacted.
  • the solvent used in the above reaction can be the same solvent as that used in the synthesis of the polyamic acid shown above.
  • N-methyl-2-pyrrolidone, ⁇ -Butyrolactone is preferred, and these may be used alone or in combination of two or more.
  • the concentration at the time of synthesis is preferably 1 to 30% by mass of the total concentration of the tetracarboxylic acid component and the diamine component in the reaction solution from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained. More preferable is 20% by mass.
  • the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.
  • the polyimide precursor thus polymerized is, for example, a polymer having a repeating unit represented by the following formula [a].
  • R 11 is a tetravalent organic group derived from the raw material tetracarboxylic acid component
  • R 12 is a divalent organic group derived from the raw material diamine component
  • a 11 and A 12 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different
  • j represents a positive integer.
  • each of R 11 and R 12 may be one type and a polymer having the same repeating unit, or R 11 and R 12 may be a plurality of types and a polymer having a repeating unit having a different structure. But you can.
  • R 11 is a group derived from a tetracarboxylic acid component represented by the following formula [c] or the like which is a raw material.
  • R 12 is a group derived from a diamine component represented by the following formula [b] as a raw material.
  • polyimide is obtained by dehydrating and ring-closing such a polyimide precursor.
  • Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalytic imidization in which a catalyst is added to the polyimide precursor solution.
  • the temperature is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
  • the catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has a basicity appropriate for advancing the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the polyimide precursor or polyimide that has been deposited in a solvent and collected can be collected by filtration, and then dried at normal temperature or under reduced pressure at room temperature or by heating. Further, by repeating the steps of re-dissolving and recovering the precipitated and recovered polyimide precursor and polyimide in an organic solvent 2 to 10 times, impurities in the polyimide precursor and polyimide can be reduced.
  • the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further increased.
  • the dehydration cyclization rate (imidation rate) of the amic acid group of the polyimide does not necessarily need to be 100%, and can be arbitrarily selected in the range of 0% to 100% depending on the application and purpose. % Is preferred.
  • the molecular weight of the polyimide precursor or polyimide is preferably 5,000 to 1,000,000, more preferably a weight average molecular weight measured by GPC (Gel Permeation Chromatography) method. Is 10,000 to 150,000.
  • GPC Gel Permeation Chromatography
  • the weight average molecular weight is lower than 5,000, the solubility may increase and it may be difficult to obtain the structure.
  • the weight average molecular weight is higher than 1,000,000, the solubility in a solvent is lowered, and a polymer solution may not be obtained.
  • the component (B) is at least one of a second polymer or a second polymer precursor different from the component (A) and propylene glycol monomethyl ether.
  • a 2nd polymer precursor the polyimide precursor which is imidized by baking and becomes a polyimide (2nd polymer) is mentioned.
  • the molecular weight of the second polymer or the second polymer precursor is preferably 5,000 to 1,000,000 in terms of weight average molecular weight measured by GPC method in consideration of solubility in a solvent. More preferably, it is 10,000 to 150,000. In consideration of resistance such as sputtering, polyimide and a polyimide precursor are preferable.
  • a polyimide and polyimide precursor of a component the same polyimide and polyimide precursor as what was illustrated by the said 1st polymer and 1st polymer precursor are mentioned. Of course, it is necessary to be a polyimide or a polyimide precursor different from the component (A).
  • the component (B) includes the second polymer or the second polymer precursor, the first polymer or the first polymer precursor, and the second polymer or the second polymer
  • At least one of the polymer precursors preferably has at least one selected from a bond capable of forming a hydrogen bond within a molecule or between molecules and a substituent capable of forming a hydrogen bond within a molecule or between molecules. . This is because self-organization tends to occur. In this way, at least one of the first polymer or the first polymer precursor and the second polymer or the second polymer precursor forms a hydrogen bond in the molecule or between the molecules.
  • the resulting structure of the present invention comprises the first polymer and the second polymer. And at least one of the first polymer and the second polymer is a bond capable of forming a hydrogen bond within a molecule or between molecules, and a substituent capable of forming a hydrogen bond within a molecule or between molecules. You will have at least one selected.
  • Examples of the bond capable of forming a hydrogen bond within a molecule or between molecules include a divalent group represented by the above formula (1).
  • Examples of the substituent capable of forming a hydrogen bond within a molecule or between molecules include a hydroxyl group, a thiol group, an amino group, and a carboxyl group.
  • Such a bond capable of forming a hydrogen bond within or between molecules or a substituent capable of forming a hydrogen bond within or between molecules includes, for example, a diamine component having these bonds or substituents, tetracarboxylic
  • an acid component as a raw material, it can be introduced into a polyimide or a polyimide precursor.
  • the mixing ratio of the component (A) and the component (B) is not particularly limited as long as self-assembly can be caused.
  • the component (B) is the second polymer or the second polymer precursor.
  • component (B) is propylene glycol monomethyl ether
  • component (A): (B) Component 99 to 70: 1 to 30 (mass ratio) is preferable.
  • the composition-forming composition may contain a first polymer, a first polymer precursor, another polymer other than the second polymer or the second polymer precursor.
  • a polymer component the first polymer, the first polymer precursor, the second polymer, the second polymer precursor, and other polymers are collectively referred to as a polymer component.
  • first polymer first polymer precursor, polyimide precursor other than second polymer and second polymer precursor, polyimide, polysiloxane, polyacrylic acid, triacetyl cellulose, polyethylene terephthalate , Cycloolefin (co) polymer, polyvinyl alcohol, polycarbonate, polystyrene, polyamide, polyolefin, polypropylene, polyethylene, polyethylene naphthalate, polyethersulfone and the like.
  • the content of the other polymer in the total amount of the polymer component is 0.5% by mass to 50% by mass, preferably 1% by mass to 30% by mass. .
  • the polymer component contained in the composition for forming a structure is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
  • the solvent contained in the structure-forming composition is an organic solvent that dissolves polymer components such as the first polymer, the first polymer precursor, the second polymer, and the second polymer precursor. If it is, it will not specifically limit. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetra Methylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropane Amides, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl
  • the composition-forming composition can contain a crosslinking agent in order to improve the physical strength of the structure.
  • a crosslinking agent examples include a compound having an alkoxyalkylated amino group, a polyfunctional (meth) acrylate compound, an epoxy or oxetane compound, a hydroxymethyl group-substituted phenol compound, and a compound containing a blocked isocyanate. These crosslinking agents can be used alone or in combination of two or more.
  • Examples of compounds having an alkoxyalkylated amino group include (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, and (poly) methylolated urea in one molecule.
  • the compound having an alkoxyalkylated amino group may be a mixture in which a plurality of substituted compounds are mixed, and there is also a mixture containing an oligomer component partially self-condensed, and such a mixture should also be used.
  • Can do More specifically, for example, hexamethoxymethyl melamine (manufactured by Nippon Cytec Industries, Ltd., CYMEL (registered trademark) 303), tetrabutoxymethyl glycoluril (manufactured by Nippon Cytec Industries, Ltd., CYMEL (registered trademark) 1170).
  • CYMEL series products such as tetramethoxymethyl benzoguanamine (CYCEL (registered trademark) 1123 manufactured by Nippon Cytec Industries, Ltd.), methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd., Nicalac (registered trademark) MW-30HM, MW-390, MW-100LM, MX-750LM), methylated urea resin (manufactured by Sanwa Chemical Co., Ltd., Nicalac (registered trademark) MX-270, MX-280, MX-290), etc. List the products of the Nicarak series It can be.
  • CYCEL registered trademark
  • methylated melamine resin manufactured by Sanwa Chemical Co., Ltd., Nicalac (registered trademark) MW-30HM, MW-390, MW-100LM, MX-750LM
  • methylated urea resin manufactured by Sanwa Chemical Co., Ltd., Nicalac (registered trademark) MX
  • polyfunctional (meth) acrylate compound examples include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta.
  • NK ester 701A A-DCP, A-DON-N, A-HD-N, A-NOD-N, DCP, DOD-N, HD-N NOD-N, NPG, A-TMM-3, A-TMM-3L, A-TMM-3LMN, A-TMPT, TMPT, A-TMMT, AD-TMP, A -DPH, A-9550, A-9530, ADP-51EH, ATM-31EH, UA-7100 (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) T-1420, D- 330, D-320, D-310, DPCA-20, DPCA-30, DPCA-60, DPCA-120, TMPTA, PET-30, DPHA, DPHA-2C (and above) Nippon Kayaku Co., Ltd. Ltd.), UA-306H, UA-306T, UA-306I, UA-510H
  • epoxy or oxetane compound examples include 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, and 2,6-diglycidylphenyl glycidyl.
  • Ether 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis (N, N-diglycidylaniline) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl Ether and the like.
  • YH-434, YH434L manufactured by Tohto Kasei Co., Ltd.
  • epoxy resins having a cyclohexene oxide structure Epolide GT-401, GT-403, GT-301, GT- 302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.), bisphenol A type epoxy resin, Epicoat (currently jER) 1001, 1002, 1003, 1004, 1007, 1009, 1010 828 (above, manufactured by Japan Epoxy Resins Co., Ltd.), Epicoat (currently jER) 807 (produced by Japan Epoxy Resins Co., Ltd.), which is a bisphenol F type epoxy resin, Epicoat (which is a phenol novolac type epoxy resin) (Currently jER) 152, 154 (above, Japan) Epoxy Resin Co., Ltd.), EPPN 201, 202 (manufactured by Nippon Kayaku Co., Ltd.),
  • hydroxymethyl group-substituted phenol compound examples include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl-4-methoxytoluene [2,6- Bis (hydroxymethyl) -p-cresol] and the like.
  • the compound containing a blocked isocyanate is a compound in which an isocyanate group (—N ⁇ C ⁇ O) is blocked with an appropriate protecting group.
  • the blocking agent include methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol and other alcohols, phenol, o-nitrophenol.
  • Phenols such as p-chlorophenol, o-cresol, m-cresol, p-cresol, lactams such as ⁇ -caprolactam, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, etc.
  • Oximes, pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole, and thiols such as dodecanethiol and benzenethiol. .
  • VESTANAT registered trademark
  • T HB
  • HT HT
  • B DS
  • Takenate registered trademark
  • a compound containing an epoxy group or a block isocyanate is preferable from the viewpoint of heat resistance and storage stability.
  • the composition-forming composition can contain an adhesion promoter in order to improve the adhesion between the structure and the substrate.
  • adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-ureidopropyltriethoxysilane, N-methylaminopropyltrimethoxysilane, N, N-dimethylaminopropyltrime
  • composition for forming a structure can contain a surfactant.
  • Surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol Polyoxyethylene alkyl allyl ethers such as ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as nopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorb
  • compositions for forming a structure When such a composition for forming a structure is used, self-organization of polyimide, a polyimide precursor, or the like occurs through a subsequent coating process, a placing process, and a baking process, and irregularities can be formed in the structure. Specifically, when a composition for forming a structure containing a polyimide or a polyimide precursor and a polymer different from the polyimide or the polyimide precursor is used, the molecules of the polyimide or the polyimide precursor and different polymers are gathered. As a result, self-organization occurs and irregularities are formed.
  • compositions for forming a structure containing polyimide or a polyimide precursor and propylene glycol monomethyl ether molecules of the polyimide or polyimide precursor are aggregated to cause self-organization to form irregularities.
  • Propylene glycol monomethyl ether is a poor solvent in which the solubility of the polyimide or polyimide precursor as the component (A) is extremely low, and it is estimated that self-organization of the polyimide or polyimide precursor occurs.
  • the presence or absence and degree of self-organization by polyimide, polyimide precursor, etc. are the type and mixing ratio of (A) component and (B) component, solid content concentration, coating method, firing temperature, pulling. Since it depends on manufacturing conditions such as placing time (leaving time), it is necessary to appropriately set these manufacturing conditions that affect self-organization.
  • Such a structure-forming composition is applied onto a substrate (application process).
  • the substrate is not particularly limited as long as the composition forming composition can be applied, but indium tin oxide (ITO), indium zinc oxide (IZO), indium gallium zinc oxide (IGZO), glass, silicon, silicone And a substrate made of silicon nitride, cobalt, aluminum, zirconium, chromium, nickel, zinc, iron, ruthenium, and alloys thereof.
  • Coating methods include, for example, spin coating method, slit coating method, dip method, flow coating method, ink jet method, spray method, bar coating method, gravure coating method, roll coating method, offset printing method, transfer printing method, brush coating, Examples thereof include a blade coating method and an air knife coating method.
  • the spin coating method is preferred.
  • the spin coating conditions may be set at 3 to 60 seconds at a rotational speed of 10 to 10,000 rpm.
  • the film thickness of the coating film formed by the coating process can be, for example, in the range of 5 nm to 1 ⁇ m, but the average height of the uneven portions formed on the surface of the resulting structure is 0.5 nm.
  • the thickness of the coating film formed by the coating process is preferably in the range of 5 nm to 500 nm.
  • the holding time may be selected, for example, from 10 seconds to 72 hours, but the leaving time is directly related to the tact time of the actual manufacturing process, and if it is short, it is preferable because the manufacturing time is shortened.
  • the time is preferably from 10 seconds to 10 minutes, more preferably from 10 seconds to 5 minutes.
  • a baking apparatus is not specifically limited, For example, a hotplate, oven, and furnace are mentioned.
  • the atmosphere in which the firing step is performed is not particularly limited, and for example, the firing may be performed in the atmosphere, an inert gas atmosphere such as nitrogen, or in a vacuum. Among them, firing in the air is preferable in order to increase the average height of the unevenness formed by self-organization.
  • the firing temperature is not particularly limited, but for example, it is preferably performed at 40 ° C. to 250 ° C. where the solvent contained in the structure forming composition can be volatilized.
  • the firing temperature is preferably 70 ° C. to 120 ° C. Since firing at a relatively wide temperature is possible in this way, design corresponding to the device type to which the structure of the present invention is applied is possible, the process margin can be expanded, and the structure of the present invention is, for example, an opto device or the like. Can be suitably used.
  • the firing time is not particularly limited, and can be, for example, about 5 to 40 minutes. You may change with the target imidation ratio. As a specific example, when the firing temperature is 230 ° C., it is preferably 20 minutes or more. In the baking step, both low temperature baking at about 40 ° C. to 120 ° C. and high temperature baking at about 180 ° C. to 250 ° C. may be sequentially performed.
  • coating process, a leaving process, and a baking process can be performed in normal temperature and a normal humidity environment.
  • the composition for forming a structure containing the specific component (A) and the component (B) is applied onto a substrate, left to stand, and then baked to form a polyimide.
  • a polyimide precursor or the like can be self-organized to obtain a structure having irregularities on the surface.
  • the structure can be formed without complicated operations such as a dry etching process, a high-temperature baking process, and an operation in a high-humidity environment.
  • the manufacturing process is short, and expensive equipment for performing complicated operations is not necessary, so that it can be manufactured at low cost.
  • the structure can be formed with significantly good reproducibility as compared with the case where a block copolymer of polystyrene and polymethyl methacrylate is used. Therefore, the difference in day and the like can be suppressed, and the structure having the unevenness of the target fractal pattern can be stably manufactured.
  • the structure of the present invention can control the shape of the obtained fractal pattern by adjusting the composition for forming a structure, the coating method, the standing time after coating, the firing temperature, etc.
  • the thickness can be set to a desired value.
  • the structure of the present invention is not a structure in which a standardized pattern such as photolithography or imprint is produced and transferred, but a structure having a fractal surface shape, so that optical interference fringes are generated. Hard to do.
  • the structure of the present invention contains polyimide, it has chemically and physically useful characteristics such as high transparency, alkali resistance, chemical resistance, high refractive index, dry etching resistance, and ITO sputtering resistance. Combined and highly reliable as a permanent film.
  • the structure of the present invention can be used as a member constituting various electronic devices.
  • the applicable electronic device is not particularly limited, and examples thereof include an optical device (optical element), a semiconductor device, a solar cell, a display, a storage medium, and a biochip.
  • an organic light emitting diode (OLED) which is an opto device will be described as an example.
  • FIG. 1 is a schematic cross-sectional view schematically showing an OLED.
  • the OLED has a structure in which a transparent substrate 11, a transparent electrode 13, a hole transport layer 14, a light emitting layer 15 and an electrode 16 are laminated in this order.
  • a light extraction film 12 made of the structure of the present invention is provided between the transparent electrode 13 and the transparent electrode 13.
  • the light extraction film 12 is formed on the transparent substrate 11 by the above-described formation method, and includes polyimide.
  • FIG. Have Regarding the size of the unevenness, for example, the average height of the protrusions is 0.5 nm to 50 nm.
  • transparent substrate 11 glass substrate, triacetyl cellulose, polyethylene terephthalate, polymethyl methacrylate, cycloolefin (co) polymer, polyvinyl alcohol, polycarbonate, polystyrene, polyimide, polyamide, polyolefin, polypropylene, polyethylene, polyethylene naphthalate, poly Examples include ether sulfone and plastic substrates such as copolymers obtained by combining these polymers.
  • Examples of the transparent electrode (anode) 13 include ITO, IZO and IGZO.
  • Examples of the electrode (cathode) 16 include aluminum, indium, gold, silver, and alloys thereof.
  • Examples of the light emitting material constituting the light emitting layer 15 include a low molecular light emitting material such as an aluminum complex, a high molecular light emitting material such as a ⁇ -conjugated polymer, and a material obtained by adding a colored dye to these light emitting materials as a dopant.
  • a low molecular light emitting material such as an aluminum complex
  • a high molecular light emitting material such as a ⁇ -conjugated polymer
  • a material obtained by adding a colored dye to these light emitting materials as a dopant.
  • electrons and holes are injected by applying a voltage to the transparent electrode 13 and the electrode 16, and are combined by the light emitting layer 15.
  • the light emitting material of the light emitting layer 15 is excited by the binding energy in the light emitting layer 15, and light (fluorescence) is generated when returning from the excited state to the ground state. This light is extracted from the transparent substrate 11 side.
  • the intensity of light extracted from the transparent substrate 11 side is usually greatly reduced.
  • the structure of the present invention is provided as the light extraction film 12, the light extraction efficiency is very high.
  • the transparent electrode 13 such as ITO is usually provided by a sputtering method
  • the structure of the present invention is durable because it contains polyimide, has excellent sputtering resistance, and can maintain a sufficiently uneven shape after sputtering. it can.
  • membrane which consists of a self-organization film
  • the transparent electrode 13 is provided on it by the sputtering method, the uneven
  • the structure of the present invention contains polyimide (refractive index of about 1.65) and has a relatively high refractive index, for example, ITO (refractive index of about 2.1) as the transparent electrode 13 and glass as the transparent substrate 11.
  • the refractive index can be between (refractive index of about 1.4).
  • the position at which the light extraction film 12 made of the structure of the present invention is provided is not limited between the transparent substrate 11 and the transparent electrode 13, and the front surface of the light extraction surface, for example, as shown in FIG. You may make it provide in the surface on the opposite side to the transparent electrode 13 of the board
  • FIG. The light extraction film 12 is formed on the transparent substrate 11 by the above-described forming method, includes polyimide, and is formed by self-assembly on the surface opposite to the transparent electrode 13 in FIG. 1B. Have unevenness. Regarding the size of the unevenness, for example, the average height of the protrusions is 40 nm to 500 nm.
  • the position where the light extraction film 12 made of the structure of the present invention is provided may be between the transparent electrode 13 and the hole transport layer 14 or the light emitting layer 15.
  • AFM atomic force microscope
  • SI-DF40 back surface AL coat
  • the scanning range was 5 ⁇ m ⁇ 5 ⁇ m, and the scanning frequency was 1.0 Hz.
  • the spin coater used Brewer Science Inc. Cee200X.
  • the film thickness was measured using a multi-incident angle spectroscopic ellipsometer VASE manufactured by JA Woollam Japan.
  • GPC device manufactured by Shodex (GPC-101) Column: manufactured by Shodex (series of KD803 and KD805) Column temperature: 50 ° C Eluent: N, N-dimethylformamide (as additive, lithium bromide-hydrate (LiBr ⁇ H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L , Tetrahydrofuran (THF) at 10 ml / L) Flow rate: 1.0 ml / min Standard sample for preparation of calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight: about 12000, 4000, 1000) manufactured by Polymer Laboratory .
  • TSK standard polyethylene oxide molecular weight: about 900,000, 150,000, 100,000, 30000
  • polyethylene glycol molecular weight: about 12000, 4000, 1000
  • the imidation ratio of polyimide was measured as follows. 20 mg of polyimide powder was placed in an NMR sample tube, and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS (tetramethylsilane) mixture) was added and completely dissolved. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNM-ECA500) manufactured by JEOL Datum.
  • DMSO-d 6 deuterated dimethyl sulfoxide
  • TMS tetramethylsilane
  • the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 ppm to 10.0 ppm. It calculated
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is the proton peak integrated value derived from the NH group of the amic acid
  • y is the peak integrated value of the reference proton
  • ⁇ is one NH group proton of the amic acid in the case of polyamic acid (imidation rate is 0%).
  • NBoc3TBS diamine represented by the following formula
  • DADPA 4,4′-diaminodiphenylamine represented by the following formula
  • DDM 4,4-diaminodiphenylmethane represented by the following formula
  • PCH7AB 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene represented by the following formula
  • TDA 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • P6 polyamic acid solution
  • P6 was diluted with NMP to prepare varnishes having solid content concentrations of 10 mass%, 6 mass%, and 1 mass%.
  • This polyamic acid solution was diluted to 5% by mass, and 237.9 g of pyridine and 510.6 g of acetic anhydride were further added as an imidization catalyst, followed by reaction at 40 ° C. for 3 hours.
  • This solution was put into 17.4 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder.
  • the polyimide powder was dissolved in NMP to prepare a varnish (abbreviated as P7) having a solid content concentration of 6% by mass.
  • Example 1 To a 20 mL one-necked eggplant-shaped flask, 5.0 g of P1 (6 mass%) obtained in Synthesis Example 1 and 5.0 g of P2 (6 mass%) obtained in Synthesis Example 2 were added, and a magnetic stirrer was used. And stirred to obtain a uniform varnish (composition forming composition).
  • This varnish is a glass surface (that is, a surface on which ITO is formed) of 1.1 mm-thick glass (hereinafter also referred to as a glass substrate) on which ITO having a thickness of 3 cm ⁇ 4 cm and a thickness of 150 nm is laminated.
  • a glass substrate 1.1 mm-thick glass
  • the film was left for 10 seconds, then baked on a hot plate at 80 ° C. for 5 minutes, and then baked on a hot plate at 230 ° C. for 30 minutes to obtain a film (structure) having a thickness of 100 nm.
  • Example 2 The same operation as in Example 1 was performed except that 5.0 g of P3 (6% by mass) obtained in Synthesis Example 3 was used instead of 5.0 g of P2 (6% by mass) obtained in Synthesis Example 2. Thus, a uniform varnish was obtained, and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 3 The same operation as in Example 1 was performed except that 5.0 g of P4 (6% by mass) obtained in Synthesis Example 4 was used instead of 5.0 g of P2 (6% by mass) obtained in Synthesis Example 2. Thus, a uniform varnish was obtained, and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 4> Instead of 5.0 g of P1 (6% by mass) obtained in Synthesis Example 1 and 5.0 g of P2 (6% by mass) obtained in Synthesis Example 2, 5.0 g of P7 (6%) obtained in Synthesis Example 7 was obtained. Mass%) and 5.0 g of P8 (6 mass%) obtained in Synthesis Example 8 were used, and the same operation as in Example 1 was performed to obtain a uniform varnish, and on the glass substrate. A film with a thickness of 100 nm was obtained.
  • Example 5> Instead of 5.0 g of P1 (6% by mass) obtained in Synthesis Example 1 and 5.0 g of P2 (6% by mass) obtained in Synthesis Example 2, 5.0 g of P5 (6 Mass%) and 5.0 g of P7 (6 mass%) obtained in Synthesis Example 7 were used, and the same operation as in Example 1 was performed to obtain a uniform varnish, and on the glass substrate. A film with a thickness of 100 nm was obtained.
  • Example 6 The same operation as in Example 1 was performed except that 5.0 g of P6 (6% by mass) obtained in Synthesis Example 6 was used instead of 5.0 g of P2 (6% by mass) obtained in Synthesis Example 2. Thus, a uniform varnish was obtained, and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 7 Instead of 5.0 g of P1 (6 mass%) obtained in Synthesis Example 1 and 5.0 g of P2 (6 mass%) obtained in Synthesis Example 2, 5.0 g of P6 (6 Mass%) and 5.0 g of P7 (6 mass%) obtained in Synthesis Example 7 were used, the same operation as in Example 1 was performed to obtain a uniform varnish, and on the glass substrate. A film with a thickness of 100 nm was obtained.
  • Example 8> Instead of 5.0 g of P1 (6% by mass) obtained in Synthesis Example 1 and 5.0 g of P2 (6% by mass) obtained in Synthesis Example 2, 5.0 g of P2 (6%) obtained in Synthesis Example 2 was obtained. Mass%) and 5.0 g of P9 obtained in Synthesis Example 9 (6 mass%) were used in the same manner as in Example 1 to obtain a uniform varnish. A film with a thickness of 100 nm was obtained.
  • Example 9 Instead of 5.0 g of P1 (6 mass%) obtained in Synthesis Example 1 and 5.0 g of P2 (6 mass%) obtained in Synthesis Example 2, P2 (6 mass%) obtained in Synthesis Example 2 and Except for using P10 (6% by mass) obtained in Synthesis Example 10, the same operation as in Example 1 was performed to obtain a uniform varnish, and a film having a thickness of 100 nm was obtained on a glass substrate. .
  • Example 10 Instead of 5.0 g of P1 (6% by mass) obtained in Synthesis Example 1 and 5.0 g of P2 (6% by mass) obtained in Synthesis Example 2, 5.0 g of P7 (6%) obtained in Synthesis Example 7 was obtained. Mass%) and 5.0 g of P10 (6 mass%) obtained in Synthesis Example 10 were used, and the same operation as in Example 1 was performed to obtain a uniform varnish, and on the glass substrate. A film with a thickness of 100 nm was obtained.
  • Example 12 A uniform varnish was obtained by performing the same operation as in Example 1 except that 0.5 g of propylene glycol monomethyl ether (PGME) was used instead of 5.0 g of P2 (6% by mass) obtained in Synthesis Example 2. In addition, a film having a thickness of 100 nm was obtained on a glass substrate.
  • PGME propylene glycol monomethyl ether
  • Example 13 A uniform varnish is obtained by performing the same operation as in Example 1 except that spin coating, leaving and baking are performed in a glove box having a nitrogen atmosphere with an oxygen concentration of 20 ppm, and a film is formed on a glass substrate. A film with a thickness of 100 nm was obtained.
  • Example 14 Instead of 5.0 g of P1 (6% by mass) obtained in Synthesis Example 1 and 5.0 g of P2 (6% by mass) obtained in Synthesis Example 2, 5.0 g of P5 (6 % Mass) and 5.0 g of P6 (6 mass%) obtained in Synthesis Example 6 were used to obtain a uniform varnish by performing the same operation as in Example 1, and a film on a glass substrate. A film with a thickness of 100 nm was obtained.
  • Example 15 A uniform varnish is obtained by performing the same operation as in Example 14 except that spin coating, standing and baking are performed in a glove box having an oxygen concentration of 20 ppm, and a film having a thickness of 100 nm is formed on a glass substrate.
  • Example 16> A film having a thickness of 120 nm was obtained on a glass substrate by performing the same operation as in Example 1 except that the operation for baking for 30 minutes on a 230 ° C. hot plate was not performed.
  • Example 17 A film having a thickness of 120 nm was obtained on a glass substrate by performing the same operation as in Example 14 except that the operation for baking for 30 minutes on a 230 ° C. hot plate was not performed.
  • Example 18 Instead of 5.0 g of P1 (6% by mass) obtained in Synthesis Example 1 and 5.0 g of P2 (6% by mass) obtained in Synthesis Example 2, 5.0 g of P1 (1) obtained in Synthesis Example 1 Mass%) and 5.0 g of P2 (1 mass%) obtained in Synthesis Example 2 were used to obtain a uniform varnish by performing the same operation as in Example 1, and on the glass substrate. A film with a thickness of 20 nm was obtained.
  • Example 20> Instead of 5.0 g of P1 (6% by mass) obtained in Synthesis Example 1 and 5.0 g of P2 (6% by mass) obtained in Synthesis Example 2, 5.0 g of P5 (10%) obtained in Synthesis Example 5 was used. Mass%) and 5.0 g of P6 (10 mass%) obtained in Synthesis Example 6 were used, and the same operation as in Example 1 was performed to obtain a uniform varnish. A film with a thickness of 200 nm was obtained.
  • Example 21 A uniform varnish was obtained by performing the same operation as in Example 1 except that the temperature for baking for 5 minutes on the hot plate was changed to 40 ° C., and a film having a thickness of 100 nm was obtained on the glass substrate.
  • Example 22 A uniform varnish was obtained by performing the same operation as in Example 1 except that the temperature for baking for 5 minutes on the hot plate was changed to 70 ° C., and a film having a thickness of 100 nm was obtained on the glass substrate.
  • Example 23 A uniform varnish was obtained by performing the same operation as in Example 1 except that the temperature for baking for 5 minutes on the hot plate was changed to 90 ° C., and a film having a thickness of 100 nm was obtained on the glass substrate.
  • Example 24 A uniform varnish was obtained by performing the same operation as in Example 1 except that the temperature for baking for 5 minutes on a hot plate was changed to 120 ° C., and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 25 A uniform varnish was obtained by performing the same operation as in Example 14 except that the temperature for baking for 5 minutes on the hot plate was changed to 40 ° C., and a film having a thickness of 100 nm was obtained on the glass substrate.
  • Example 26 A uniform varnish was obtained by performing the same operation as in Example 14 except that the firing temperature after firing for 5 minutes on a hot plate was changed to 70 ° C., and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 27 A uniform varnish was obtained by performing the same operation as in Example 14 except that the firing temperature after firing for 5 minutes on a hot plate was changed to 90 ° C., and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 28 A uniform varnish was obtained by performing the same operation as in Example 14 except that the firing temperature after firing for 5 minutes on a hot plate was changed to 120 ° C., and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 29> A uniform varnish was obtained by performing the same operation as in Example 1 except that the standing time after completion of spin coating was changed to 1 minute, and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 30 A uniform varnish was obtained by performing the same operation as in Example 1 except that the standing time after completion of the spin coating was changed to 5 minutes, and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 31 A uniform varnish was obtained by performing the same operation as in Example 1 except that the standing time after completion of spin coating was changed to 10 minutes, and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 32> A uniform varnish was obtained by performing the same operation as in Example 1 except that the standing time after completion of the spin coating was changed to 72 hours, and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 33 A uniform varnish was obtained by performing the same operation as in Example 14 except that the standing time after completion of spin coating was changed to 1 minute, and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 34 A uniform varnish was obtained by performing the same operation as in Example 14 except that the standing time after completion of spin coating was changed to 5 minutes, and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 35 A uniform varnish was obtained by performing the same operation as in Example 14 except that the standing time after completion of spin coating was changed to 10 minutes, and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 36 A uniform varnish was obtained by performing the same operation as in Example 14 except that the standing time after completion of spin coating was changed to 72 hours, and a film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 37 A uniform varnish was obtained by performing the same operation as in Example 1 except that P1 (6% by mass) obtained in Synthesis Example 1 was 4.0 g and P2 (6% by mass) obtained in Synthesis Example 2 was 6.0 g. Moreover, the film
  • Example 38 A uniform varnish was obtained by performing the same operation as in Example 1 except that P1 (6% by mass) obtained in Synthesis Example 1 was 6.0 g and P2 (6% by mass) obtained in Synthesis Example 2 was 4.0 g. Moreover, the film
  • Example 39 A uniform varnish was obtained by performing the same operation as in Example 14, except that P5 (6% by mass) obtained in Synthesis Example 5 was 1.0 g and P6 (6% by mass) obtained in Synthesis Example 6 was 9.0 g. Moreover, the film
  • Example 40> A uniform varnish was obtained by performing the same operation as in Example 14, except that P5 (6% by mass) obtained in Synthesis Example 5 was 2.0 g and P6 (6% by mass) obtained in Synthesis Example 6 was 8.0 g. Moreover, the film
  • Example 41 A uniform varnish was obtained by performing the same operation as in Example 14, except that P5 (6% by mass) obtained in Synthesis Example 5 was 3.0 g, and P6 (6% by mass) obtained in Synthesis Example 6 was 7.0 g. Moreover, the film
  • Example 42 A uniform varnish was obtained by performing the same operation as in Example 14 except that P5 (6% by mass) obtained in Synthesis Example 5 was set to 4.0 g and P6 (6% by mass) obtained in Synthesis Example 6 was changed to 6.0 g. Moreover, the film
  • Example 43 A uniform varnish was obtained by performing the same operation as in Example 14 except that P5 (6% by mass) obtained in Synthesis Example 5 was 6.0 g and P6 (6% by mass) obtained in Synthesis Example 6 was 4.0 g. Moreover, the film
  • Example 44 A uniform varnish was obtained by performing the same operation as in Example 14 except that P5 (6% by mass) obtained in Synthesis Example 5 was 7.0 g and P6 (6% by mass) obtained in Synthesis Example 6 was 3.0 g. Moreover, the film
  • Example 45 A uniform varnish was obtained by performing the same operation as in Example 14 except that P5 (6% by mass) obtained in Synthesis Example 5 was 8.0 g and P6 (6% by mass) obtained in Synthesis Example 6 was 2.0 g. Moreover, the film
  • Example 46 A uniform varnish was obtained by performing the same operation as in Example 14 except that P5 (6% by mass) obtained in Synthesis Example 5 was 9.0 g, and P6 (6% by mass) obtained in Synthesis Example 6 was 1.0 g. Moreover, the film
  • Example 11 A uniform varnish was obtained by performing the same operation as in Example 1 except that baking for 5 minutes on a hot plate at 80 ° C. and baking for 30 minutes on a hot plate at 230 ° C. were not performed. A film having a thickness of 100 nm was obtained on a glass substrate.
  • Example 13 In Comparative Example 13 without the light extraction film, the surface of the glass surface (that is, the surface opposite to the surface on which ITO was formed) was observed by AFM and the convex portion in the same manner as in Example 1 above. The average height was measured. The results are shown in Table 2-1 and Table 2-2. As an example of the observation result, the AFM image of Example 1 is shown in FIG. 2, the AFM image of Example 14 is shown in FIG. 3, and the AFM image of Comparative Example 2 is shown in FIG.
  • This varnish (standard solution) was spin-coated on the ITO surface side of the glass substrate on which each structure produced in Examples 1 to 46 and Comparative Examples 1 to 12 was formed, and then heated on a hot plate at 80 ° C. for 10 seconds. Baking was performed to prepare a standard film having a thickness of 100 nm.
  • the measurement conditions of the fluorescence spectrum are as follows: excitation wavelength is 341.0 nm, fluorescence start wavelength is 450 nm, fluorescence end wavelength is 700 nm, scan speed is 240 nm / min, excitation light is irradiated from the standard film side, and light is emitted from the structure side.
  • the fluorescence intensity was determined by reading the maximum fluorescence peak appearing at 531.0 nm.
  • the fluorescence intensity was measured by relative comparison, and the fluorescence intensity measured for the structure obtained in Comparative Example 1 was normalized to 1.00.
  • the relative fluorescence intensities of Examples 1 to 46 and Comparative Examples 1 to 13 are shown in Tables 2-1 and 2-2.
  • Examples of the combination of polymers include polyamic acid and polyamic acid in Examples 1 to 3, 6 and 8, polyamic acid and polyimide in Examples 4, 7 and 9, and polyimide and polyimide in Example 10.
  • Example 14 is an example in which a polyamic acid and a polyamic acid ester are mixed
  • Example 5 is an example in which a polyimide and a polyamic acid ester are mixed. In any mixing, a structure having irregularities formed by self-organization on the surface. The body was formed.
  • Example 11 is an example in which three types of polymers of polyamic acid, polyimide and polyamic acid ester are mixed. In this case as well, a structure having irregularities formed by self-assembly on the surface was formed.
  • Example 12 uses a single polymer and is a system in which different polymers are not mixed, but it is a poor solvent having extremely low solubility in the polymer in the varnish containing the polymer. Since a certain PGME was added, it was found that a self-organized structure having a surface with irregularities formed by self-organization was formed.
  • the basic figure unit of the fractal pattern was an earthworm shape as shown in FIG. .
  • the basic figure unit of the fractal pattern was hemispherical as shown in FIG.
  • the basic figure unit of the fractal pattern was a hole shape.
  • Example 2 When the relative fluorescence intensities of Examples 1 to 11 are compared, only in Example 2 the relative fluorescence intensity is less than 1.30, and the relative fluorescence intensity is a monomer (diamine component or tetracarboxylic acid component) constituting the polymer. The tendency depending on the skeleton was confirmed.
  • Example 2 a bond capable of forming a hydrogen bond within a molecule or between molecules and a hydrogen bond within a molecule or between molecules are formed in the monomer skeleton constituting the polymer contained in the structure forming composition used. It is considered that the relative strength was relatively low in Example 2 because it did not have any of the possible substituents and was not included in any one of the two kinds of mixed polymers.
  • Examples 1 and 13 to 15 are examples in which atmospheres for spin coating, standing after spin coating, and firing are different. Whether the atmosphere is air or nitrogen having an oxygen concentration of 20 ppm, a structure having irregularities due to self-organization is formed on the surface, and whether or not self-organization occurs depends on the atmosphere of these processes. It turns out that it does not depend. In addition, in a nitrogen atmosphere, it has been found that the average height of the convex portions tends to decrease and the relative fluorescence intensity tends to decrease.
  • Examples 1 and 16, Examples 14 and 17, and Comparative Example 11 are examples in which the firing process is different.
  • Example 1 and Example 14 which were baked at 230 ° C. for 30 minutes and baked at 80 ° C. for 5 minutes
  • Example 16 and Example which were baked at 230 ° C. for 30 minutes but were baked at 80 ° C. for 5 minutes
  • Example 17 irregularities were formed by self-organization, but in Comparative Example 11 in which no firing was performed, no self-organization occurred, and thus a structure having irregularities formed by self-organization was formed.
  • the firing step was essential.
  • Examples 1 and 21 to 24, and Examples 14 and 25 to 28 are examples having different firing temperatures. It was found that a structure having irregularities formed by self-assembly was formed at any temperature of 40 ° C. to 120 ° C. after the spin coating. Moreover, since the relative fluorescence intensity was stabilized when the firing temperature was 70 ° C. or higher, it was found that the firing temperature was preferably 70 ° C. or higher.
  • Examples 1 and 18, Examples 14, 19 and 20 are examples in which the solid content concentration of the structure-forming composition, that is, the polymer concentration is different. It was found that a structure having irregularities on the surface due to self-organization was formed without depending on an increase in film thickness due to an increase in solid content concentration. In addition, the relative fluorescence intensity is strong in Example 20 where the solid content concentration is the highest and the average height of the convex portion is the highest, and when the structure is installed on the forefront where light is extracted, the solid content concentration is high and the film thickness is high. It has been found that a larger is advantageous.
  • Examples 1 and 29 to 32, and Examples 14 and 33 to 36 are examples in which the standing time after the end of spin coating is different. It was found that a structure having irregularities formed by self-organization was formed at any standing time after the spin coating was 10 seconds to 72 hours.
  • the standing time is directly related to the tact time of the actual manufacturing process, and is preferably 10 seconds to 10 minutes, more preferably 10 seconds to 5 minutes, since the manufacturing time is preferably shortened if it is short.
  • Example 4 and Comparative Example 12 are also examples in which the mixing ratio of the polymers is different.
  • the mixing ratio of the polymers is different.
  • Comparative Examples 1 to 12 had a lower relative fluorescence intensity and a lower light extraction efficiency than the examples having a structure in which irregularities due to self-organization were formed on the surface. Note that some of the comparative examples 1 to 12 have irregularities with a relatively high average height of the convex portions, but as shown in FIG. 4, the irregularities formed in the comparative example 2 etc. It is not unevenness formed by self-organization. That is, the basic unit figure was not observed in a 50 ⁇ m square, and was unevenness caused by uniform film roughness in the surface of the film surface.
  • Comparative Example 13 shows the relative fluorescence intensity when no light extraction film was provided, but the extraction light extraction efficiency was the worst. From this, it can be seen that the light extraction efficiency is improved when polyimide and polyimide precursor are used as the light extraction film, but the light extraction efficiency is further increased when the structure has irregularities formed by self-organization on the surface. It was.

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06313055A (ja) * 1993-04-27 1994-11-08 Ube Ind Ltd 粗面化ポリイミドフィルムの製造法
JPH0820721A (ja) * 1994-07-05 1996-01-23 Shin Etsu Chem Co Ltd ポリイミドフィルム及びその製造方法
JP2005041936A (ja) * 2003-07-24 2005-02-17 Toray Ind Inc 熱硬化性樹脂組成物およびそれを用いた電子部品
JP2009013384A (ja) * 2007-07-09 2009-01-22 Nippon Paint Co Ltd 易滑性アンチブロッキング光硬化性樹脂組成物、それを基材上に被覆硬化したアンチブロッキング性構造体およびその製法
WO2009096204A1 (fr) * 2008-01-29 2009-08-06 Konica Minolta Opto, Inc. Element electroluminescent organique, dispositif d'affichage et equipement d'eclairage
WO2009119889A1 (fr) * 2008-03-28 2009-10-01 住友化学株式会社 Dispositif organique électroluminescent
WO2013099937A1 (fr) * 2011-12-28 2013-07-04 日産化学工業株式会社 Agent d'alignement de cristaux liquides, membrane d'alignement de cristaux liquides, élément d'écran à cristaux liquides, et procédé de fabrication d'élément d'écran à cristaux liquides
WO2013111836A1 (fr) * 2012-01-26 2013-08-01 日産化学工業株式会社 Procédé de préparation de vernis polyimide et agent d'alignement de cristaux liquides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012103506A (ja) * 2010-11-10 2012-05-31 Tokyo Univ Of Science パターン形成方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06313055A (ja) * 1993-04-27 1994-11-08 Ube Ind Ltd 粗面化ポリイミドフィルムの製造法
JPH0820721A (ja) * 1994-07-05 1996-01-23 Shin Etsu Chem Co Ltd ポリイミドフィルム及びその製造方法
JP2005041936A (ja) * 2003-07-24 2005-02-17 Toray Ind Inc 熱硬化性樹脂組成物およびそれを用いた電子部品
JP2009013384A (ja) * 2007-07-09 2009-01-22 Nippon Paint Co Ltd 易滑性アンチブロッキング光硬化性樹脂組成物、それを基材上に被覆硬化したアンチブロッキング性構造体およびその製法
WO2009096204A1 (fr) * 2008-01-29 2009-08-06 Konica Minolta Opto, Inc. Element electroluminescent organique, dispositif d'affichage et equipement d'eclairage
WO2009119889A1 (fr) * 2008-03-28 2009-10-01 住友化学株式会社 Dispositif organique électroluminescent
WO2013099937A1 (fr) * 2011-12-28 2013-07-04 日産化学工業株式会社 Agent d'alignement de cristaux liquides, membrane d'alignement de cristaux liquides, élément d'écran à cristaux liquides, et procédé de fabrication d'élément d'écran à cristaux liquides
WO2013111836A1 (fr) * 2012-01-26 2013-08-01 日産化学工業株式会社 Procédé de préparation de vernis polyimide et agent d'alignement de cristaux liquides

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