TWI535335B - A structure, a light extraction film, an electronic device, and a structure - Google Patents

Description

Structure, light extraction film, electronic device, and formation method of structure

The present invention relates to a structure, a light extraction film, an electronic device, and a structure for forming a structure having irregularities formed by self-organization of a polyimide or a polyimide precursor on a surface thereof.

In recent years, the light extraction efficiency of an optical device (optical element) has been extensively discussed. In the optical device, for example, a transparent substrate, a transparent electrode, a light-emitting layer, and an electrode are laminated in this order, and a light-emitting diode (LED, Light Emitting Diode) element is taken out from the transparent substrate side, but on a transparent substrate, The light extraction efficiency is lowered due to reflection of light on the surface of the transparent electrode and the light-emitting layer, so that the light extraction efficiency is required to be improved. As a technique for improving the efficiency of light extraction, a method of providing a lens at the forefront of a surface on which light is taken out (light extraction surface) is known in an organic light-emitting diode (OLED) device (refer to Patent Document 1), and a light extraction surface is used. A method of providing a porous light-scattering body by a sol-gel method (refer to Patent Document 2) and a method of disposing a light-scattering layer in which metal fine particles generating a plasmon is dispersed (refer to Patent Document 3).

Also, as between the transparent substrate and the transparent electrode or transparent A technique of providing a light extraction film for improving the light extraction efficiency between the electrode and the light-emitting layer, for example, a technique of providing a low refractive index layer (light extraction film) having a concave-convex portion formed by an imprint method has been reported (refer to the patent) Document 4). Further, recently, it has been reported that aluminum is used to form irregularities on the surface of PDMS (polymethyl siloxane), and a structure having a transfer unevenness (light extraction film) is obtained by transferring unevenness by a nanoimprint method. The light extraction efficiency of the OLED element in which the structure is provided between the transparent substrate and the transparent electrode is improved by about 100% (refer to Non-Patent Document 1).

Therefore, the light extraction efficiency can be improved by removing the film by the light having irregularities on the surface. However, when the unevenness is formed by the above-described imprint method, the manufacturing process is long and there is a problem that it cannot be easily formed.

Here, a technique of self-organizing by thermally annealing a block copolymer of polystyrene and polymethyl methacrylate, and then making fine irregularities by dry etching has been reported (refer to Non-patent) Literature 2). This self-organization has an advantage that it can be processed at a nanometer scale in a simple and inexpensive manner as compared with the photolithography method used in the manufacture of semiconductor devices in the past.

However, it may be because the block copolymer of polystyrene and polymethyl methacrylate of the propylene-based block copolymer is extremely difficult to manufacture, and polystyrene and polymethyl methacrylate are used. The problem of poor reproducibility of the irregularities formed by the self-organization of the block copolymer.

Further, by performing the self-organization of the block copolymer to form irregularities, it is necessary to perform dry etching for unevenness on the surface, firing at 300 ° C, annealing, or operation in a nitrogen atmosphere. , Therefore, the manufacturing process is long and complicated, and it is necessary to invest in high-priced equipment.

Furthermore, it is not only limited to LEDs having a light extraction film having irregularities on the surface, but also various optical devices, or even electronic devices such as semiconductor devices, solar cells, displays, memory media, biochemical wafers, etc., are also expected to be so easy. Moreover, the structure having irregularities on the surface is manufactured with good reproducibility.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-29172

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-238507

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-165284

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2011-44296

[Non-patent literature]

[Non-Patent Document 1] Nature Photonics, USA, 2010, Vol. 4, p. 222-226

[Non-Patent Document 2] Japanese Journal of Applied Physics, Japan, 2002, 41, p. 6112-6118

The present invention has been made in view of the above circumstances, and the object to be solved is to provide a structure having irregularities on the surface, and it is easy to It is an object of a structure, a light extraction film, an electronic device, and a method of forming a structure which are manufactured with good reproducibility.

The inventors of the present invention have conducted intensive studies to solve the above problems, and have found that a polymer containing a polyimine precursor or a polyimine, which is different from the polyimide precursor or polyimine, or At the same time, the composition containing propylene glycol monomethyl ether is applied to a substrate, and is self-organized only when placed and fired, and the knowledge of the structure having irregularities on the surface is reproducible, and the completion is completed. this invention.

That is, the present invention has the following gist.

A structure comprising a first polymer composed of polyimide and having irregularities formed by self-organization of the first polymer on a surface thereof.

2. The structure of 1, wherein the convex portion formed on the surface has an average height of 0.5 nm to 500 nm.

3. The structure according to 1. or 2., comprising the first polymer and a second polymer different from the first polymer, and having a first polymer and a second polymerization layer on a surface thereof The bump formed by the self-organization of the object.

4. The structure according to any one of 1 to 3, wherein the second polymer is composed of a polyimine different from the first polymer.

5. The structure of any one of 1 to 4, wherein at least one of the first polymer and the second polymer is selected from the group consisting of Or a bond forming a hydrogen bond between the molecules, and at least one of a substituent capable of forming a hydrogen bond in or between molecules.

6. The structure according to 5., wherein the bond capable of forming a hydrogen bond in or between molecules is represented by the following formula (1), and the substituent capable of forming a hydrogen bond in or between molecules is A group selected from the group consisting of a hydroxyl group, a thiol group, an amine group, and a carboxyl group.

A light extraction film comprising the structure of any one of 1. to 6.

8. An electronic device characterized by having a light extraction film as in 7.

9. An electronic device as in 8. It is a light emitting diode.

A method of forming a structure, which is a method of forming a structure having irregularities on a surface, and is characterized by the following steps.

The coating step of applying the composition for forming a structure of the following component (A) and the component (B) to the substrate, the standby step of standing after the application step, and the step of standing after the step of baking Into the firing step.

Component (A): a first polymer composed of polyimine or a first polymer precursor composed of a polyimide precursor.

(B) component: the second polymer or the second component different from the component (A) At least one of a polymer precursor, and propylene glycol monomethyl ether.

The structure having irregularities on the surface of the present invention can be applied to a substrate by placing a composition containing a polyimide precursor or a polyimine and a polymer containing another polymer or propylene glycol monomethyl ether. It is manufactured by an easy method of firing to self-organize. For example, complicated operations such as a dry etching step, a high-temperature firing step, and a high-humidity operation are not required, and the number of steps is also small. Moreover, since the reproducibility is good, the structure can be stably produced. Further, the structure having irregularities of the present invention can be applied to various electronic devices such as a light extraction film of an OLED.

11‧‧‧Transparent substrate

12‧‧‧Light removal film

13‧‧‧Transparent electrode

14‧‧‧ hole transport layer

15‧‧‧Lighting layer

16‧‧‧Electrode

[Fig. 1] Outlined schematic cross-sectional view of an OLED

[Fig. 2] AFM image of the surface of the structure of Example 1.

[Fig. 3] AFM image of the surface of the structure of Example 14.

[Fig. 4] AFM image of the surface of the structure of Comparative Example 2

Hereinafter, the present invention will be described in more detail.

The structure of the present invention comprises a first polymer composed of polyimine and has irregularities formed by self-organization of the first polymer on the surface.

In the present specification, self-organizing means that a polymer molecule such as a polyimide or a polyimide precursor coated on a substrate has a pattern structure by causing irregularities such as spontaneous aggregation. Self-organization is not the formation of a specific pattern that has been determined, but the formation of a Fractal pattern. Further, the specific pattern that has been determined refers to an artificially-defined pattern obtained by a human pattern forming method such as photolithography or imprinting, and is based on a technique for continuously obtaining the same pattern. On the other hand, the self-organized fractal pattern refers to a part of the geometry represented by the Mandebo collection, which is difficult to define mathematically, but refers to the pattern that humans can intuitively understand. The self-organization is based on a technique of continuously obtaining a fractal pattern (that is, a pattern composed of a collection of self-similar structures), and is intended to store the physical property values of the obtained self-organized film in specifications.

The basic unit pattern of the fractal pattern formed by self-organization is, for example, a dot shape, a worm shape, a Via shape, or the like. A pattern of fractals formed by a basic unit figure and a similar structure to its basic unit figure. Furthermore, when measured by AFM (atomic force microscope, SEM (scanning electron microscope) or TEM (transmission electron microscope), the basic unit pattern cannot be confirmed in 50 μm square. In addition, it is excluded from the definition of the fractal pattern. The shape of the dot may be a hemispherical shape such as an ellipse or a circle in a plan view. The shape of the crucible may be a shape in which a dot shape and a dot shape are connected to each other. The shape of the hole may be a shape such as an opening at the outermost surface of the structure. The types of such shapes are selected according to the applicable place of the structure of the present invention. Just choose. Further, the type of the basic unit figure may be one or more types, and the plural type may be combined.

The self-organization is caused by the use of (i) the polarity term of the polymer, the difference in dispersion or surface energy, (ii) the difference in solubility of the polymer to the solvent, or (iii) the hygroscopicity of the polymer. The difference in sex, etc., is not particularly limited as long as the fractal pattern can be obtained.

The structure of the present invention has an unevenness such as a convex portion formed by self-organization on the surface, and has an average height of 0.5 nm to 500 nm. Here, the average height of the convex portions means the average surface roughness (R _a ) measured by AFM.

The average height of the preferred projections may be selected depending on the place of application. For example, when the structure of the present invention is applied as a light extraction film provided between a transparent substrate such as glass and a transparent electrode such as ITO (Indium Tin Oxide) in an OLED, the average height of the convex portion is considered in consideration of the short-circuit characteristics. It is preferably 0.5 nm to 50 nm, preferably 0.5 nm to 30 nm. Further, when the structure of the present invention is applied as a light extraction film provided on the front surface of the light-removing surface (light extraction surface) of the OLED, the average height of the convex portions is preferably 40 nm to 500 nm. When the average height of the convex portions is higher than 500 nm, the transparency is lost and the light extraction efficiency is deteriorated.

The structure having irregularities on the surface of the present invention can be applied to a substrate by, for example, a composition for forming a structure (hereinafter also referred to as a varnish) containing the component (A) and the component (B). Coating step, standby placement step after standby after the coating step, waiting After the machine is placed, the method of forming the firing step is performed.

The component (A) is a polyimine (first polymer), or a polyimide precursor which is imidized into a polyimine (first polymer) by firing (first polymer precursor) ()). That is, the component (A) is a component of the polyimine (first polymer) in the structure of the present invention produced. Polyimine precursor refers to polyamic acid (also known as polyamic acid or polyamide acid) or polyamidomate. Further, the polyimine or polyimine precursor of the component (A) has never been discussed as a self-organizing material.

A polyimide precursor such as polyamine or polyphthalamide is obtained by reacting a diamine component with a tetracarboxylic acid component. Polyammonium esters can also be obtained by a method of converting a carboxyl group of polylysine to an ester. Further, the polyimide can be obtained by subjecting the polyimine precursor such as polylysine or polyphthalate to ruthenium imidization. Further, the diamine component may be one type or two or more types, and the tetracarboxylic acid component may be one type or two or more types.

The tetracarboxylic acid component means at least one selected from the group consisting of a tetracarboxylic acid and a tetracarboxylic acid derivative. The tetracarboxylic acid derivative may, for example, be a tetracarboxylic acid dihalide, a tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride or a tetracarboxylic acid diester. For example, polylysine can be obtained by reacting a tetracarboxylic acid dihalide, a tetracarboxylic dianhydride or the like with a diamine component. Further, by reacting a tetracarboxylic acid diester dichloride with a diamine component, or by reacting a tetracarboxylic acid diester with a diamine component in the presence of a suitable condensing agent or a base, a polyfluorene can be obtained. Amine ester.

The tetracarboxylic acid component is exemplified by the following formula (2). Carboxylic dianhydride.

(In the formula (2), Z ₁ is an organic group having a carbon number of 4 to 13 and having a carbon number of 4 to 6 and a non-aromatic cyclic hydrocarbon group.)

In the formula (2), specific examples of Z ₁ include a tetravalent organic group represented by the following formulas (2a) to (2j).

(In the formula (2a), Z ₂ to Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, and in the formula (2g), Z ₆ and Z ₇ are a hydrogen atom or The methyl groups may be the same or different.

In the formula (2), in terms of polymerization reactivity or ease of synthesis, a particularly preferable structure of Z ₁ is a formula (2a), a formula (2c), a formula (2d), a formula (2e), a formula (2f) or a formula. (2g). Among them, the formula (2a), the formula (2e), the formula (2f) or the formula (2g) is also preferred.

In addition, the ratio of the tetracarboxylic dianhydride represented by the formula (2) to the total amount of the tetracarboxylic acid component is not particularly limited, and for example, 5 to 40 mol% of the total amount of the tetracarboxylic acid component is the above formula (2). The tetracarboxylic dianhydride shown is preferred, more preferably 10 to 30 mol%.

Examples of the other tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by the above formula (2) include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5. 6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-nonanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3' , 4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4' - benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl) Propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, Bis(3,4-dicarboxyphenyl)diphenylnonane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3' , 4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10-decanetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid Diacid anhydride.

The tetracarboxylic acid diester is also not particularly limited. Specific examples thereof are given below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester and 1,2-dimethyl-1,2,3,4-. Dialkyl cyclobutane tetracarboxylate, dialkyl 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylate, 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid Dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxyl-1 , 2,3,4-tetrahydro-1-naphthalene succinate dialkyl ester, 1,2,3,4-butane tetracarboxylic acid dialkyl ester, bicyclo[3,3,0]octane- Dialkyl 2,4,6,8-tetracarboxylate, dialkyl 3,3',4,4'-dicyclohexyltetracarboxylate, 2,3,5-tricarboxycyclopentylacetic acid Alkyl ester, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.0 ^2,5 ]壬Alkane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl ester, hexacyclohexane [6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^{10, 13} ] hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl ester, 4-(2,5-dioxotetrahydrofuran-3-yl)-1, 2,3,4-tetrahydronaphthalene-1,2-dixiang celery Alkyl esters.

Examples of the aromatic tetracarboxylic acid dialkyl esters include dialkyl pyromellitic acid, dialkyl 3,3',4,4'-biphenyltetracarboxylate, and 2,2',3. Dialkyl 3'-biphenyltetracarboxylate, dialkyl 2,3,3',4-biphenyltetracarboxylate, 3,3',4,4'-benzophenonetetracarboxylic acid Alkyl ester, 2,3,3',4-dibenzophenone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4-dicarboxyl) Phenyl)decyl dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl ester, and the like.

The diamine component which reacts with the tetracarboxylic acid component is not particularly limited, and a general diamine can be used. Examples of the diamine component include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, and m-benzene. Diamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diamine Phenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-di Aminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl- 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-di Aminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-di Aminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3' - sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis ( 3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thio Diphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diamino Diphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl (3,3'-diamino Diphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl (2 , 3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminodiphenyl Ketone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6- Diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-Diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminobenzene) Ethylene, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane , 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1, 4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)] Aniline, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine, 3, 4'-[1,3-Exophenylbis(methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3'-[ 1,3-phenylphenylbis(methylene)]diphenylamine, 1,4-phenylphenylbis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3- Aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylphenylbis[(3-aminophenyl)methanone] , 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis (4- Amino benzoate), 1,3-benzene Bis(3-aminobenzoic acid ester), bis(4-aminophenyl)paraphthalic acid ester, bis(3-aminophenyl)p-phthalate, bis(4-aminophenyl)iso Phthalate, bis(3-aminophenyl)isodecanoate, N,N'-(1,4-phenylene)bis(4-aminobenzylamine), N,N'-(1 , 3-phenylene) bis(4-aminobenzylbenzylamine), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1 , 3-phenylene) bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)-p-amine, N,N'-bis(3-aminophenyl) ) amidoxime, N,N'-bis(4-aminophenyl)isodecylamine, N,N'-bis(3-aminophenyl)isodecylamine, 9,10-bis ( 4-aminobenzene ,4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 '-Bis[4-(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-amine Phenylphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2 '-Bis(3-Aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 3,5-diaminobenzoic acid, 2,5-diamine Kean acid, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy) Butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy) Pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxyl) Heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxyl) Octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxyl) Decyl, 1,10-(3-amino Phenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-amino group Aromatic diamines such as phenoxy)dodecane and 1,12-(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino-3) An alicyclic diamine such as -methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamine Hexyl, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diamine A general-purpose diamine such as an aliphatic diamine such as a decane or a 1,12-diaminododecane.

The general use of the diamine is preferably from 50 to 95 mol% of the diamine component used in the synthesis of the polyamic acid, more preferably from 70 to 90 mol% of the diamine component.

Further, the diamine component may, for example, be an alkyl group having a long chain in a side chain, a group having a ring structure branching structure in the middle of a long chain alkyl group, a steroid group, or a hydrogen atom of such a group. Or a diamine which is entirely substituted by a fluorine atom. Specifically, for example, diamines represented by the following formulas (3), (4), (5), and (6) are exemplified, but are not limited thereto.

(In the formula (3), l, m and n each independently represent an integer of 0 or 1, and R ³ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or a C 1~3 alkyl-ether group, R ⁴ , R ⁵ and R ⁶ each independently represent a phenyl or cycloalkyl group, and R ⁷ represents a hydrogen atom, and the carbon number is 2-24. An alkyl group or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, or a large cyclic substituent which constitutes one of the valences.

Further, from the viewpoint of easiness of synthesis, R ³ in the above formula (3) is preferably an alkyl-ether group having -O-, -COO-, -CONH- or a carbon number of 1-3.

Further, from the viewpoint of easiness of synthesis, R ⁴ , R ⁵ and R ⁶ in the formula (3) are preferably a combination of l, m, n, R ⁴ , R ⁵ and R ⁶ shown in the following Table 1.

Further, when at least one of l, m, and n is 1, R ⁷ in the formula (3) is preferably a hydrogen atom or an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, more preferably a hydrogen atom or a carbon number. 2~12 alkyl or fluoroalkyl. Further, when l, m, and n are all 0, 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, and a monovalent heterocyclic ring. One of the large cyclic substituents constituting one of them is more preferably an alkyl group having 12 to 20 carbon atoms or a fluorine-containing alkyl group.

(In the formulae (4) and (5), A ₁₀ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or -NH-, A ₁₁ represents a single bond or a phenyl group, and a represents -R ³ -(R ⁴ ) _l -(R ⁵ ) _m -(R ⁶ ) _n -R ⁷ (R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , l, m, n are the same as defined in the above formula (3), and a' represents a divalent group of a structure in which an element such as hydrogen is removed from the same structure as the above a).

(In the formula (6), A ₁₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A ₁₅ is a 1,4-cyclohexyl group or a 1,4-phenylene group, and A ₁₆ is an oxygen atom. Or -COO-* (but, note that the "*" bond is combined with A ₁₅ ), A ₁₇ is an oxygen atom or -COO-* (however, the "*" bond is linked to (CH ₂ ) a _{2 is} combined.) Further, a ₁ is 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is 0 or 1.

The bonding position of the two amine groups (-NH ₂ ) in the formula (3) is not limited. Specifically, for example, the position of 2, 3 on the benzene ring with respect to the side chain (-R ³ -(R ⁴ ) _l -(R ⁵ ) _m -(R ⁶ ) _n -R ⁷ ) , 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position, 3, 5 position. Among them, from the viewpoint of reactivity in synthesizing poly-proline, the position of 2, 4, 2, 5 or 3, 5 is preferred. If the ease of synthesizing the diamine is added, the position of 2, 4 or 3, 5 is more preferable.

The specific structure of the formula (3) is exemplified by the diamines represented by the following formulas [A-1] to [A-24], but are not limited thereto.

(In the formula [A-1] to the formula [A-5], A ₁ is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.)

(In the formula [A-6] and the formula [A-7], A ₂ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and A ₃ is a carbon number. 1 to 22 alkyl, alkoxy, fluoroalkyl or fluoroalkoxy.)

(In the formula [A-8] to the formula [A-10], A ₄ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ - or -CH ₂ -, A ₅ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

(In the formula [A-11] and the formula [A-12], A ₆ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, -CH ₂ -, -O- or -NH-, A ₇ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, a Alkoxy or hydroxy.)

(In the formula [A-13] and the formula [A-14], A ₈ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of the 1,4-cyclohexyl group are each a trans isomer. .)

(In the formula [A-15] and the formula [A-16], A ₉ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of the 1,4-cyclohexyl group are each a trans isomer. )

Specific examples of the diamine represented by the formula (4) include a diamine represented by the following formula [A-25] to the formula [A-30], but are not limited thereto.

(In the formula [A-25] to the formula [A-30], 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.)

Specific examples of the diamine represented by the formula (5) include a diamine represented by the following formula [A-31] to the formula [A-32], but are not limited thereto.

Thus, the alkyl group having a long chain in the side chain, the group having a ring structure or a branched structure on the way of the long chain alkyl group, a steroid group, or a group in which one or all of the hydrogen atoms of the group are substituted by a fluorine atom The diamine is preferably used in an amount of from 0 to 50 mol%, more preferably from 10 to 40 mol%, based on the diamine component used in the synthesis of the polyamic acid.

Further, the diamine component may be a diamine having a photoreactive group. A diamine having a photoreactive group is exemplified by having a vinyl group and a propylene group. a photoreactive group such as an alkylene group, a methacryloyl group, an allyl group, a styryl group, a cinnamyl group, a ketone group, a coumarin group or a maleimine group as a side chain diamine, for example The diamine represented by the following general formula (7) is mentioned, but it is not limited by these.

(In the formula (7), R ⁸ represents a single bond, or -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, - Any of N(CH ₃ )-, -CON(CH ₃ )-, -N(CH ₃ )CO-; R ⁹ represents a single bond, or a carbon number of 1 to 20 which is unsubstituted or substituted by a fluorine atom The alkyl group and the alkyl group -CH ₂ - may be optionally substituted with -CF ₂ - or -CH=CH-, and any of the following groups may be used when they are not adjacent to each other. Substituting for the group; or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, a divalent heterocyclic ring. R ¹⁰ represents a vinyl group, a propylene group A mercapto group, a methacryl fluorenyl group, an allyl group, a styryl group, -N(CH ₂ CHCH ₂ ) ₂ , or a structure represented by the following formula.)

Further, the R ⁸ in the above formula (7) can be formed by a usual organic synthesis method, but from the viewpoint of easiness of synthesis, -CH ₂ -, -O-, -COO-, -NHCO-, -NH-, -CH ₂ O- is preferred.

Further, as a carbon ring or a heterocyclic ring in which a divalent carbocyclic ring or a divalent heterocyclic ring of any -CH ₂ - in R ⁹ is substituted, specifically, the following structures are mentioned, but are not limited thereto. By.

R ¹⁰ is a structure represented by a vinyl group, an acrylonitrile group, a methacryl fluorenyl group, an allyl group, a styryl group, -N(CH ₂ CHCH ₂ ) ₂ or a formula represented by the following formula from the viewpoint of photoreactivity. good.

Further, -R ⁸ -R ⁹ -R ^{10 of the} above formula (7) is preferably the structure described below.

The bonding position of the two amine groups (-NH ₂ ) in the formula (7) is not limited. Specifically, with respect to the side chain (-R ⁸ -R ⁹ -R ¹⁰ ), the position of 2, 3 on the benzene ring, the position of 2, 4, the position of 2, 5, 2, 6 Position, 3, 4 position, 3, 5 position. Among them, from the viewpoint of reactivity in synthesizing poly-proline, the position of 2, 4, the position of 2, 5, or the position of 3, 5 is preferred. If the ease of synthesizing the diamine is added, it is preferably at the position of 2, 4 or 3, 5.

The diamine having a photoreactive group may specifically be a compound as described below, but is not limited thereto.

(wherein X is a single bond, or a bond selected from -O-, -COO-, -NHCO-, -NH-, and Y represents a single bond, or a carbon number substituted by a fluorine atom or substituted by a fluorine atom ~20 alkyl group.)

Further, the diamine having a photoreactive group is preferably used in an amount of from 0 to 70 mol%, more preferably from 0 to 60 mol%, of the diamine component used in the synthesis of polyamic acid.

The polymerization of the diamine component and the tetracarboxylic dianhydride component is usually carried out in an organic solvent. The organic solvent to be used at this time is not particularly limited as long as it is a polyimine precursor such as a soluble polyamine. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, and dimethyl Azulene, tetramethylurea, pyridine, dimethyl hydrazine, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl decyl ketone, Methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, Butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol Monomethyl ether, propylene glycol-tert-butyl ether, propylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, propylene glycol monoacetate monomethyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoacetate monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxy Butyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, Diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate Ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, Cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate , 3-methoxypropionic acid methyl ester, 3-ethoxypropionic acid methyl ethyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3 - propyl methoxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination. Further, even if it is a solvent in which the polyimide precursor is not dissolved, it may be used in the above solvent as long as it does not precipitate the formed polyimide precursor. Further, since the water in the organic solvent hinders the polymerization reaction and causes the produced polyimide precursor to be hydrolyzed, it is preferred that the organic solvent be dried by dehydration.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, a solution in which a diamine component is dispersed or dissolved in an organic solution, and a tetracarboxylic acid component is directly added to the solution, or a method in which a carboxylic acid component is dispersed or dissolved in an organic solvent, and a method of adding a carboxylic acid component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent is added, and a tetracarboxylic acid component and a diamine are alternately added. Any of these methods can be used as the method of the component or the like. Further, when a plurality of kinds of diamine components or tetracarboxylic acid components are used for the reaction, the reaction can be carried out in a state of being mixed beforehand, and the reaction can be carried out in an individual order, or the individual reacted low molecular weight bodies can be mixed. reaction. The polymerization temperature at this time may be selected from any of -20 ° C to 150 ° C, but preferably in the range of -5 ° C to 100 ° C. Again, the reaction It can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a high molecular weight polyimine precursor (or even a polyimide), and if the concentration is too high, the viscosity of the reaction liquid changes. It is too high to stir evenly. Therefore, the concentration of the total amount of the diamine component and the tetracarboxylic acid component is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the total amount of the reaction solution. The initial stage of the reaction is carried out at a high concentration, and thereafter an organic solvent can be added.

In the polymerization reaction of the polyimine precursor such as polylysine, 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. As with the usual polycondensation reaction, the molecular weight of the polyimine precursor formed when the molar ratio approaches 1.0 becomes large.

Further, the polyglycolate may be reacted by a tetracarboxylic acid diester dichloride with a diamine component, or a tetracarboxylic acid diester and a diamine component in the presence of a suitable condensing agent or a base, as described above. Get the reaction. Alternatively, the polyamic acid can be synthesized in advance by the above method, and the carboxyl group of the polylysine can be esterified by a polymer reaction.

Specifically, for example, by reacting the tetracarboxylic acid diester dichloride and the diamine component in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, the reaction 30 The polyphthalate is synthesized by reacting for ~24 hours, preferably for 1 hour to 4 hours.

As the base, pyridine, triethylamine or 4-dimethylaminopyridine can be used, but in order to carry out the reaction stably, pyridine is preferred. From the viewpoint of being easily removable and easily obtaining a high molecular weight body, the amount of the base added is preferably 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride system.

Further, the tetracarboxylic acid diester and the diamine component are present in the condensing agent When the condensation polymerization is carried out, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide can be used as the base. Amine hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium salt, O-(benzotriazol-1-yl)-N, N,N',N'-tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate , (2,3-dihydro-2-thioketo-3-benzoxazole)phosphonic acid diphenyl, 4-(4,6-dimethoxy-1,3,5-triazine chloride -2-yl) 4-methoxymorpholine n-hydrate and the like.

Further, in the above method using a condensing agent, the reaction can be efficiently carried out by adding Lewis acid as an additive. The Lewis acid is preferably lithium halide such as lithium chloride or lithium bromide. The addition amount of Lewis acid is preferably 0.1 to 1.0 times the molar amount of the diamine or tetracarboxylic acid diester which is reacted.

The solvent used in the above reaction may be carried out in the same solvent as the above-exemplified solvent for synthesizing polyamic acid, but the solubility from the monomer and the polymer is N-methyl-2-pyrrolidine. The ketone and γ-butyrolactone are preferred, and one type of these may be used or two or more types may be used in combination. The concentration at the time of the synthesis is preferably from 1 to 30% by mass in terms of the total concentration of the tetracarboxylic acid component and the diamine component in the reaction solution from the viewpoint that the precipitation of the polymer is less likely to occur and the high molecular weight body is easily obtained. 20% by mass is preferred. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for synthesizing the polyphthalate is preferably dehydrated as much as possible, and it is preferable to prevent the incorporation of outside air in a nitrogen atmosphere.

The polyimine precursor precursor which is thereby polymerized is, for example, a A polymer having a repeating unit represented by the following formula [a].

(In the formula [a], R ₁₁ is a tetravalent organic group derived from a tetracarboxylic acid component of a raw material, R ₁₂ is a divalent organic group derived from a diamine component of a raw material, and A ₁₁ and A ₁₂ are a hydrogen atom or carbon. Alkyl groups of 1 to 4, each of which may be the same or different, and j represents a positive integer.)

In the above formula [a], R ₁₁ and R ₁₂ are each a single type and may also be a polymer having the same repeating unit, and R ₁₁ or R ₁₂ may be a plural type and may also be a repeating unit having a different structure. The polymer.

In the above formula [a], R ₁₁ is a group derived from a tetracarboxylic acid component represented by the following formula [c] or the like which is derived from a raw material. Further, R ₁₂ is a group derived from a diamine component represented by the following formula [b] or the like which is derived from a raw material.

Further, the polyimine can be obtained by dehydrating and ring-closing the polyimide precursor.

The method for carrying out the hydrazine imidization of the polyimine precursor may be, for example, directly heating the solution of the polyimide precursor to thermally imidize the solution, or adding a contact to the solution of the polyimide precursor The medium causes the catalyst to be imidized.

The temperature at which the polyimine precursor is thermally imidated in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water formed by the imidization reaction is excluded. It is better to carry out the system at the same time.

The ruthenium imidization of the polyimide precursor is carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor, at -20 to 250 ° C, preferably at 0 to 180 ° C. Stir and carry out. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine has a moderate alkalinity in the reaction. Examples of the acid anhydride include anhydrous acetic acid, anhydrous trimellitic acid or anhydrous pyromellitic acid. Among them, when anhydrous acetic acid is used, purification after completion of the reaction becomes easy. The imidization ratio of the ruthenium imidization is controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

Further, when recovering the polyamidiamine precursor of polylysine, polyphthalamide or the like, or recovering the produced polyimine precursor or polyimine from the reaction solution of polyimine, The reaction solution is put into a solvent to make It can be precipitated. The solvent used for the precipitation may, for example, be methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene or water. After the solvent is introduced, the precipitated polyimine precursor or polyimine is recovered by filtration, and then dried at room temperature or under reduced pressure at normal temperature or under reduced pressure. Further, the precipitated polyimine precursor or polyimine is redissolved in an organic solvent, and the reprecipitation is repeated 2 to 10 times to reduce the polyimine precursor or polyimine. Impurities. In the case of the solvent, for example, an alcohol, a ketone or a hydrocarbon may be used. When a solvent selected from three or more types selected from the above is used, the efficiency of purification can be further improved.

The dehydration ring closure ratio of the amidino group of the polyimine is not necessarily 100%, and may be arbitrarily selected in the range of 0% to 100% depending on the purpose or purpose, but 50% to 100%. It is better.

The molecular weight of the polyimine precursor or the polyimine, when considering the solubility in a solvent, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, preferably. It is 10,000~150,000. When the weight average molecular weight is less than 5,000, the solubility may become high and it may become difficult to obtain a structure. Further, when the weight average molecular weight is more than 1,000,000, the solubility in a solvent may be lowered, and the polymer solution may not be obtained.

Further, the component (B) is at least one of a second polymer, a second polymer precursor, and a propylene glycol monomethyl ether which are different from the component (A).

The second polymer may, for example, be a polyimine different from the component (A), or a polysiloxane, a polyacrylic acid, a triethyl fluorenyl cellulose, a polyethylene terephthalate or a cycloolefin (total). Polymer, polyvinyl alcohol, polycarbonate, polystyrene, polyamine, polyolefin, polypropylene, polyethylene, polyethylene naphthalate, polyether oxime, and the like. The second polymer precursor may be a polyimine precursor which is a polyimine (second polymer) by imidization by firing. When the molecular weight of the second polymer or the second polymer precursor is considered to be solubility in a solvent, the weight average molecular weight measured by the GPC method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000. Further, in consideration of resistance such as sputtering, a polyimide or a polyimide precursor is preferred. The polyimine or polyimine precursor of the component (B) may, for example, be the same as the polyimine or polyimine which is exemplified in the first polymer and the first polymer precursor. Precursor. Of course, it is necessary to use a polyimine or a polyimide precursor which is different from the component (A).

Here, when the component (B) includes the second polymer or the second polymer precursor, at least one of the first polymer or the first polymer precursor and the second polymer or the second polymer precursor It is preferred to have at least one selected from the group consisting of a bond capable of forming a hydrogen bond in or between molecules, and a substituent capable of forming a hydrogen bond in or between molecules. It is because it is easier to self-organize. Further, at least one of the first polymer or the first polymer precursor and the second polymer or the second polymer precursor has a bond selected from a group capable of forming a hydrogen bond in or between molecules. And at least one of the substituents capable of forming a hydrogen bond in the molecule or in the molecule, the obtained structure of the present invention has the first polymer and the second polymer, and At least one of the first polymer and the second polymer has at least one selected from the group consisting of a bond capable of forming a hydrogen bond in a molecule or a molecule, and a substituent capable of forming a hydrogen bond in or between molecules.

The bond system capable of forming a hydrogen bond in a molecule or a molecule may be a divalent group represented by the above formula (1). Further, examples of the substituent capable of forming a hydrogen bond in the molecule or in the molecule include a hydroxyl group, a thiol group, an amine group, and a carboxyl group.

Thus, a bond capable of forming a hydrogen bond in a molecule or a molecule, or a substituent capable of forming a hydrogen bond in or between molecules can be, for example, a diamine component or a tetra group having such a bond or substituent The carboxylic acid component is used as a raw material and 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 it can be self-organized. For example, when the component (B) is the second polymer or the second polymer precursor, the component (A): (B) Component = 40 to 60: 60 to 40 (mass ratio) is preferred, and particularly preferred is (A) component: (B) component = 45 to 55: 55 to 45 (mass ratio). In addition, when the component (B) is propylene glycol monomethyl ether, it is selected in the range of not depositing a polymer in the structure for forming a structure (varnish), that is, it is not particularly limited, but the component (A): (B) Composition = 99~70: 1~30 (mass ratio) is better.

The structure-forming composition may contain a polymer other than the first polymer, the first polymer precursor, the second polymer, or the second polymer precursor. Hereinafter, the first polymer, the first polymer precursor, the second polymer, the second polymer precursor, and other polymers are collectively described as a polymer component. Examples of the other polymer include a first polymer and a first polymer. a polymer precursor, a second polymer or a second polymer precursor other than a polyimide precursor, a polyimine, a polyoxyalkylene, a polyacrylic acid, a triethylenesulfonyl cellulose, a polyparaphthalic acid Diester, cycloolefin (co)polymer, polyvinyl alcohol, polycarbonate, polystyrene, polyamine, polyolefin, polypropylene, polyethylene, polyethylene naphthalate, polyether oxime, and the like.

When the composition for forming a structure contains another polymer, 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 structure for forming a structure is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, particularly preferably 3% by mass to 10% by mass.

The solvent contained in the structure for forming a structure is an organic solvent capable of dissolving a polymer component such as a first polymer, a first polymer precursor, a second polymer or a second polymer precursor, that is, Specially limited. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, and 2 - pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylene fluorene, γ-butyrolactone, 3- Methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1 ,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate , propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 2-butoxyethanol, propylene glycol monomethyl ether acetate, and the like. These can be used separately and mixed use.

The structure for forming a structure may contain a crosslinking agent in order to increase the physical strength of the structure. The crosslinking agent may, for example, be a compound having an amine group alkylated with an alkoxy group, a polyfunctional (meth) acrylate compound, an epoxy group or a propylene oxide compound, a hydroxymethyl-substituted phenol compound, and a capping group. Compounds of isocyanate and the like. These crosslinking agents may be used singly or in combination of two or more.

Examples of the compound having an amine group alkylated with an alkoxy group include (poly)methylolated melamine, (poly)methylolated acetylene urea, and (poly)methylolated benzoguanamine. (poly)methylolated urea or the like having at least one hydrogen atom of a plurality of active methylol groups in one molecule and having at least one hydrogen atom of a hydroxyl group of a methylol group substituted with an alkyl group such as a methyl group or a butyl group Compound.

A compound having an amine group alkylated with an alkoxy group is a mixture of a plurality of substituted compounds, and a mixture containing a part of self-condensed oligomer components may be used. mixture. More specifically, hexamethoxymethyl melamine (made by Cytec Industries Co., Ltd., CYMEL (registered trademark) 303), tetrabutoxymethyl acetylene urea (made by Cytec Industries, Japan), CYMEL (registered trademark) 1170), tetramethoxymethyl benzoguanamine (made by Cytec Industries Co., Ltd., CYMEL (registered trademark) 1123), etc., CYMEL series of products, methylated melamine resin ((share) three And chemical system, NIKALAC (registered trademark) MW-30HM, same MW-390, same MW-100LM, same MX-750LM), A product of the NIKALAC series of methylated urea resin ((3) and Chemical, NIKALAC (registered trademark) MX-270, MX-280, and MX-290).

Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri(meth) acrylate, trimethylolpropane tetra(meth) acrylate, and pentaerythritol tri(meth) acrylate. , pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, ginseng (2-hydroxyethyl) Cyanurate tri(meth)acrylate, ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(methyl) Acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(methyl) Acrylate, propylene glycol di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, and the like. More specifically, for example, NK ester 701A, the same A-DCP, the same A-DON-N, the same A-HD-N, the same A-NOD-N, the same DCP, the same DOD-N, the same HD- N, same as NOD-N, same NPG, same A-TMM-3, same A-TMM-3L, same A-TMM-3LMN, same A-TMPT, same TMPT, same A-TMMT, same AD-TMP, same A-DPH, the same as A-9550, the same A-9530, the same ADP-51EH, the same ATM-31EH, UA-7100 (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) T-1420, the same D-330, the same D-320, the same D-310, the same DPCA-20, the same DPCA-30, the same DPCA-60, the same DPCA-120, the same TMPTA, the same PET- 30. Same as DPHA, DPHA-2C (above, manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, UA-510H (above, Kyoeisha Chemical Co., Ltd.).

Examples of the epoxy group or the propylene oxide compound include 1,4-butanediol diepoxypropyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, and C. Triol triepoxypropyl ether, diethylene glycol diepoxypropyl ether, 2,6-diepoxypropyl phenylepoxypropyl ether, 1,1,3-parade [p-(2, 3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diepoxypropyl ester, 4,4'-methylenebis(N,N-diepoxypropyl Aniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triepoxypropyl ether, bisphenol-A-diepoxy Propyl ether, pentaerythritol polyepoxypropyl ether, and the like. More specifically, for example, YH-434, YH434L (manufactured by Tohto Kasei Co., Ltd.), Epolide GT-401 having an epoxycyclohexane structure, GT-403, and GT-301, Same as GT-302, Ceroxide 2021, Ceroxide 3000 (manufactured by Dell Chemical Industry Co., Ltd.), Epikote (now, jER) 1001 of bisphenol A type epoxy resin, same as 1002, same 1003, same 1004, same 1007, same 1009 , with the same 1010, the same as 828 (above, Japanese epoxy resin (stock)), bisphenol F-type epoxy resin Epikote (now, jER) 807 (made by Japan Epoxy Resin Co., Ltd.), phenol novolac type epoxy Epikote (now, jER) 152 of resin, 154 (above, manufactured by Nippon Epoxy Resin Co., Ltd.), EPPN201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.), EOCN of cresol novolac type epoxy resin -102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, Nippon Kayaku Co., Ltd.), Epikote (now, jER) 180S75 (made by Nippon Epoxy Resin Co., Ltd.), Denacol EX-252 (made by Nagase ChemteX Co., Ltd.), CY175, CY177, CY179 (above, CIBA-GEIGY AG) System), Araldite CY-182, CY-192, CY-184 (above, CIBA-GEIGY AG), Epiclon 200, 400 (above, Dainippon Ink Industry Co., Ltd.), Epikote (now, jER) 871, the same as 872 (above, manufactured by Nippon Epoxy Co., Ltd.), ED-5661, ED-5662 (above, manufactured by Celanese Coating), Denacol EX-611 of aliphatic polyepoxypropyl ether, Same as EX-612, same EX-614, same EX-622, same EX-411, same EX-512, same EX-522, same EX-421, same EX-313, same EX-314, same EX-321 ( Nagase ChemteX (share) system, etc.

Examples of the hydroxymethyl-substituted phenol compound include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, and 3,5-dihydroxymethyl-4-methyl. Oxytoluene [2,6-bis(hydroxymethyl)-p-cresol] and the like.

The compound containing blocked isocyanate is a compound in which an isocyanate group (-N=C=O) is blocked by a suitable protecting group. Examples of the blocking agent include methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol, and a ring. Alcohols such as hexanol, phenol, o-nitrophenol, p-chlorophenol, o-cresol, m-cresol, P-cresol, etc., decylamine such as ε-caprolactam Anthraquinones such as acetone, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, pyrazole, 3,5-dimethyl a pyrazole such as pyrazole or 3-methylpyrazole, a mercaptan such as dodecanethiol or benzenethiol. More specific For example, VESTANAT (registered trademark) T, the same as HB, the same HT, the same B, the same DS (above, Evonik), Takenate (registered trademark) B-830, B-815N, B-842N , B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, B-5010 (above, manufactured by Mitsui Chemical Polyurethane Co., Ltd.).

Among the above crosslinking agents, a compound containing an epoxy group or a blocked isocyanate is preferred from the viewpoint of heat resistance or storage stability.

The composition for forming a structure may contain an adhesion promoter in order to improve the adhesion between the structure and the substrate. Examples of the adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, and 3-glycol propylene. Oxypropyl propyl dimethoxy decane, p-styryl trimethoxy decane, 3-methyl propylene methoxy propyl methyl dimethoxy decane, 3- propylene methoxy propyl trimethoxy Baseline, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane , 3-ureidopropyltriethoxydecane, N-methylaminopropyltrimethoxydecane, N,N-dimethylaminopropyltrimethoxydecane, 3-2-(imidazoline- 1-yl)-propyltriethoxydecane, and the like.

Further, the composition for forming a structure may contain a surfactant. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oleyl ether. Polyoxyethylene alkyl allylate ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl allyl ether, polyoxyethylene. Polyoxypropylene block copolymers, saponin monolaurate, saponin monopalmitate Ester, saponin monostearate, saponin monooleate, saponin trioleate, saponin tristearate, etc. Monolaurate, polyoxyethylene calendron monopalmitate, polyoxyethylene calendan monostearate, polyoxyethylene calendron trioleate, polyoxyethylene calendron tristearate Other nonionic surfactants such as polyoxyethylene calendan fatty acid esters, trade names Eftop EF301, EF303, EF352 (manufactured by Tohkem Products), trade names Megaafac F-553, F-554, F171, F173, R-08, R-30, R-30-N (made by Dainippon Ink Chemical Industry Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade name Asahiguide AG710, Surflon S-382, A fluorine-based surfactant such as SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.), and an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used singly or in combination of two or more.

When the composition for forming a structure is used, the self-organization of the polyimide or the polyimide precursor is generated by the coating step, the standby step, and the baking step in the subsequent stage, and the structure is further formed. Bumps are formed on the upper surface. Specifically, when a composition for forming a structure containing a polyimide or a polyimide precursor and a polymer different from the polyimide or polyimide precursor, a polyimide composition is used. Or the molecules of the polyimine precursor and the dissimilar polymer are self-organized by aggregation or the like to form irregularities. Further, when a composition for forming a structure comprising a polyimine or a polyimide intermediate and a propylene glycol monomethyl ether is used, the molecules of the polyimide or the polyimide precursor are self-organized by aggregation or the like. And the bumps are formed. Propylene glycol monomethyl ether Since the solubility of the polyimine or polyimine precursor of the component (A) is extremely low, it is presumed that self-organization of the polyimide or polyimide precursor is produced. Further, although detailed later, the presence or degree of self-organization of the polyimide or polyimine precursors depends on the type or mixture ratio of the components (A) and (B), and the solid form. Since the production conditions such as the concentration, the coating method, the firing temperature, and the standby time (placement time) are set, it is necessary to appropriately set such manufacturing conditions that affect the self-organization.

This composition for forming a structure is applied onto a substrate (coating step). The substrate is not particularly limited as long as it can be coated with a composition for forming a structure, and examples thereof include indium tin oxide (ITO), indium zinc oxide (IZO), indium gallium zinc oxide (IGZO), and glass. A substrate composed of ruthenium, polyfluorene oxide, tantalum nitride, cobalt, aluminum, zirconium, chromium, nickel, zinc, iron, niobium, and the like.

Examples of the coating method include a spin coating method, a slit coating method, a dip coating method, a casting method, an inkjet method, a spray method, a bar coating method, a gravure coating method, a roll coating method, and a lithography method. Transfer printing method, brush coating method, blade coating method, air knife coating method, and the like. Among them, a spin coating method is preferred. For example, the spin coating condition is set to a number of revolutions of 10 to 10,000 rpm, and 3 to 60 seconds.

The film thickness of the coating film formed by the coating step can be set, for example, in the range of 5 nm to 1 μm, and the average height of the convex portions formed on the surface of the obtained structure is 0.5 nm to 500 nm by coating. The film thickness of the coating film formed in the step is preferably in the range of 5 nm to 500 nm.

After the coating step, it is placed in standby, that is, the coating film formed on the substrate by the coating step is directly placed (standby placement step). The standby standing time (placement time) may be suitably selected, for example, from 10 seconds to 72 hours, but the placement time is directly related to the takt time of the manufacturing process actually performed, and the shorter the manufacturing time, the shorter the manufacturing time becomes. It is ideal, so it is better to divide from 10 seconds to 10, and more preferably 10 seconds to 5 minutes.

The baking is performed after the standby standing step (sintering step). The firing machine is not particularly limited, and examples thereof include a hot plate, an oven, and a hot furnace. Further, the environment in which the firing step is carried out is not particularly limited, and for example, it may be calcined in an inert gas atmosphere such as the atmosphere or nitrogen or under a vacuum. Among them, in order to increase the average height of the convex portions of the irregularities formed by the self-organization, it is preferable to perform the burning in the atmosphere.

The firing temperature is not particularly limited, and it is preferably carried out at 40 ° C to 250 ° C at which the solvent contained in the composition for forming a structure can be volatilized. Further, in order to stabilize the shape of the obtained structure, the firing temperature is preferably 70 ° C to 120 ° C. Therefore, since the firing can be performed at a relatively large temperature, it is possible to create a design corresponding to the type of the apparatus to which the structure of the present invention is applied, and to enlarge the process boundary, and the structure of the present invention can be suitably used for, for example, optical. Device, etc.

The firing time is not particularly limited, and may be, for example, 5 to 40 minutes. It can also be changed according to the imidization rate of the target. As a specific example, when the baking temperature is 230 ° C, it is preferably 20 minutes or longer. Further, in the firing step, both low-temperature firing at a temperature of about 40 ° C to 120 ° C and high-temperature firing at a temperature of about 180 ° C to 250 ° C may be sequentially performed.

Further, the coating step, the standby placing step, and the firing step may be carried out in an environment of normal temperature and normal humidity.

Therefore, by applying a composition for forming a structure containing the specific component of the component (A) and the component (B) to a substrate and allowing it to stand, a simple method of forming the composition can be obtained, and the composition can be obtained. A structure in which a ruthenium imine or a polyimide precursor is self-organized to have irregularities on the surface. For example, a structure can be formed without complicated operations such as a dry etching step, a high-temperature firing step, or a high-humidity environment. Further, since the number of steps is small, the manufacturing steps are short, and expensive equipment for complicated operations is not required, it can be manufactured at a low price.

In the above formation method, the structure can be formed remarkably and reproducibly compared to the case of using a block copolymer of polystyrene and polymethyl methacrylate. Therefore, the difference in the number of days and the like is suppressed, and the structure having the fractal pattern of the uneven shape can be stably manufactured.

Further, 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, and the like, for example, the average of the convex portions can be obtained. Highly made to the desired value.

Further, the structure of the present invention is not a structure which is manufactured by photolithography or embossing, but is a structure having a patterned surface shape, and is a structure having a fractal surface shape, so that optical interference fringes are less likely to occur.

Moreover, since the structure of the present invention contains polyimine, it has the chemistry of high transparency, alkali resistance, chemical resistance, high refractive index, dry etching resistance, ITO sputtering resistance, etc. of polyimine. Physically Useful properties, and high reliability as a permanent film.

The structure of the present invention can be used as a member constituting various electronic devices. The electronic device to be applied is not particularly limited, and examples thereof include an optical device (optical device), a semiconductor device, a solar cell, a display, a memory medium, and a biochemical wafer. Hereinafter, an organic light emitting diode (OLED) of an optical device will be described as an example.

1 is a schematic cross-sectional view showing an OLED in outline. As shown in FIG. 1( a ), the OLED is a structure in which the transparent substrate 11 , the transparent electrode 13 , the hole transport layer 14 , the light emitting layer 15 , and the electrode 16 are sequentially laminated. In the present invention, the transparent substrate 11 and the transparent electrode 13 are The light extraction film 12 composed of the structure of the present invention is disposed between.

The light extraction film 12 is formed on the transparent substrate 11 by the above-described formation method, and contains polyimide. In FIG. 1(a), the surface on the side of the transparent electrode 13 has irregularities formed by self-organization. The size of the concavities and convexities is, for example, an average height of the convex portions of 0.5 nm to 50 nm.

Other than the light extraction film 12 composed of the structure of the present invention, the other systems are the same as the conventional OLED, and specific examples thereof are as follows.

Examples of the transparent substrate 11 include a glass substrate, triethyl fluorenyl cellulose, polyethylene terephthalate, polymethyl methacrylate, cycloolefin (co)polymer, polyvinyl alcohol, polycarbonate, and poly. A plastic substrate such as a copolymer of styrene, polyimine, polyamine, polyolefin, polypropylene, polyethylene, polyethylene naphthalate, polyether oxime, or a combination polymer.

Examples of the transparent electrode (anode) 13 include ITO, IZO, IGZO, and the like.

Examples of the electrode (cathode) 16 include aluminum, indium, gold, silver, and the like, or alloys thereof.

The light-emitting material constituting the light-emitting layer 15 may be a low-molecular light-emitting material such as an aluminum complex or a polymer light-emitting material such as a π-conjugated polymer, or a dopant may be added to the light-emitting material. A material for colored pigments.

The OLED thus injects electrons and holes by applying a voltage to the transparent electrodes 13 and the electrodes 16, and bonds them in the light-emitting layer 15. Further, by the bonding energy in the light-emitting layer 15, the light-emitting material of the light-emitting layer 15 is excited, and light (fluorescence) is generated when returning from the excited state to the substrate state. This light is taken out from the side of the transparent substrate 11.

The light generated by the light-emitting layer 15 is reflected at the respective interfaces of the light-emitting layer 15, the hole transport layer 14, the transparent electrode 13, and the transparent substrate 11, and the intensity of light taken out from the side of the transparent substrate 11 is usually greatly reduced. In the OLED, since the structure of the present invention is provided as the light extraction film 12, the light extraction efficiency is extremely high.

Further, the transparent electrode 13 such as ITO is usually provided by a sputtering method, but the structure of the present invention is strong because it contains a polyimide, and the sputtering resistance is also excellent, and it is still possible after sputtering. Fully maintain the concave and convex shape. Further, when a light extraction film composed of a self-assembled film of a block copolymer of polystyrene and polymethyl methacrylate is used, if the transparent electrode 13 is provided by sputtering, the uneven shape collapses. And light extraction Efficiency has also been greatly reduced. Further, since the structure of the present invention contains a polyimine (refractive index of about 1.65) and has a high refractive index, for example, ITO (refractive index of about 2.1) of the transparent electrode 13 and glass of the transparent substrate 11 (refractive index) can be used. The refractive index between about 1.4).

The position at which the light extraction film 12 composed of the structure of the present invention is provided is not limited to the space between the transparent substrate 11 and the transparent electrode 13, and may be provided at the forefront of the light extraction surface, for example, as shown in Fig. 1(b). It may be provided on the surface of the transparent substrate 11 opposite to 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. In FIG. 1(b), the surface on the opposite side to the side of the transparent electrode 13 has self-organization. The unevenness formed. The size of the concavities and convexities is, for example, an average height of the convex portions of 40 nm to 500 nm. The other matters are the same as those of Fig. 1(a) described above, and thus the description thereof is omitted. Further, the position at which the light extraction film 12 composed 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.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited by the examples. Further, each measuring device used in the examples is as follows. Further, the measurement of the molecular weight and the measurement method of the ruthenium imidization ratio are also shown below.

AFM (Atomic Force Microscopy) was measured using a Nano Navi L-trace manufactured by SII Nanotechnology Co., Ltd. The cantilever system uses SI-DF40 (back AL number). In the scanning range The measurement was performed at 5 μm × 5 μm and the scanning frequency was 1.0 Hz.

The spin coater was used by Brewer Science Co., Ltd. Cee 200X.

The film thickness was measured using a multi-incidence angle spectroscopic ellipsometer VASE manufactured by J.A. Woollam JAPAN.

The fluorescence spectrum system was a spectrophotometer F-7000 manufactured by Hitachi High-Tech Co., Ltd.

<Measurement of molecular weight>

The molecular weight of polyaminic acid and polyimine is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and the polyamine or polyimine is measured in terms of polyethylene glycol and polyethylene oxide. The number average molecular weight (Mn) and the weight average molecular weight (Mw).

GPC device: manufactured by Shodex (GPC-101)

Pipe column: made by Shodex company (inline of KD803, KD805)

Column temperature: 50 ° C

Dissolution: N,N-dimethylformamide (additive is lithium bromide-hydrate (LiBr.H ₂ O) 30 mM/L, phosphoric acid. Anhydrous crystal (o-phosphoric acid) 30 mmol/L, Tetrahydrofuran (THF) 10ml/L)

Flow rate: 1.0ml/min

Standard sample for the production of calibration lines: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight of about 12,000, 4000, 1000) manufactured by Polymer Laboratories .

<Measurement of yttrium imidation rate>

The ruthenium imidization ratio of the polyimine was measured as follows.

20 mg of polyimine powder was placed in an NMR sample tube, and 0.53 ml of dimethyl hydrazine hydride (DMSO-d ₆ , 0.05% TMS (tetramethyl decane) mixture) was added to completely dissolve it. A proton NMR of 500 MHz of this solution was measured in a NMR measuring instrument (JNM-ECA500) manufactured by Nippon Denshi Co., Ltd. The ruthenium imidization ratio is determined by using a proton derived from a structure which has not changed before and after imidization as a reference proton and a peak accumulating value of the proton, and a guanamine derived from 9.5 ppm to 10.0 ppm. The proton peak accumulating value of the NH group of acid, and is obtained by the following formula.

醯 imidization rate (%) = (1-α.x/y) × 100

In the above formula, x is the proton peak accumulating value of the NH group derived from proline, y is the peak accumulating value of the reference proton, and α is the reference proton pair polylysine (the imidization ratio is 0%) A ratio of the number of NH protons of the proline.

<abbreviation>

NBoc3TBS: a diamine represented by the following formula (wherein Boc represents tert-butoxycarbonyl and t-Bu represents tert-butyl.)

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: γ-butyrolactone

[Synthesis of Polymers] <Synthesis Example 1>

To a 200 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, 14.03 g (48.0 mmol) of 1,3-bis(4-aminophenoxy)benzene and 141.3 g of NMP were added, and nitrogen was supplied and stirred at the same time. Dissolved. The diamine solution was stirred and 10.05 g (46.0 mmol) of pyromellitic dianhydride was added thereto, and NMP was added to have a solid content concentration of 12% by mass, and stirred in a water bath at 23 ° C for 20 hours to obtain polyglycine. Solution (abbreviated as P1). Further, the molecular weight of the polyamic acid was Mn = 15466 and Mw = 41,241. The varnish having a solid content concentration of 6 mass% and 1 mass% was prepared by diluting P1 with NMP.

<Synthesis Example 2>

Add 4,4'-diaminodiphenylmethane 4.02g (20.3mmol), 1,3-bis(4-aminophenethyl) to a 100ml four-necked flask equipped with a stirring device and a nitrogen inlet tube. 2.60 g (8.7 mmol) of urea and 70.8 g of NMP. The nitrogen is delivered while stirring to dissolve it. The diamine solution was stirred while adding 5.61 g (28.5 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and NMP was added to have a solid content concentration of 12% by mass in a water bath at 23 ° C. The mixture was stirred for 5 hours to obtain a solution of polylysine (abbreviated as P2). Further, the molecular weight of the polyamic acid was Mn = 10,120 and Mw = 22,465. The varnish having a solid content concentration of 6 mass% and 1 mass% was prepared by diluting P2 with NMP.

<Synthesis Example 3>

4,4'-diaminodiphenylmethane 4.59 g (23.1 mmol), p-phenylenediamine 1.07 g (9.9 mmol), NMP 70.6 were placed in a 100 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube. g, transporting nitrogen while stirring to dissolve it. The diamine solution was stirred while adding 6.26 g (32.4 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and NMP was added to have a solid concentration of 12% by mass in a water bath at 23 ° C. The mixture was stirred for 5 hours to obtain a solution of polylysine (abbreviated as P3). Further, the molecular weight of the polyamic acid was Mn = 13899 and Mw = 30,991. The varnish having a solid content concentration of 6 mass% was prepared by diluting P3 with NMP.

<Synthesis Example 4>

4,4'-diaminodiphenylmethane 2.66 g (13.4 mmol) and 4,4'-diaminobenzilide aniline 1.31 g were placed in a 50 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube. (5.8 mmol), NMP 34.1 g, nitrogen was supplied while stirring to dissolve. Stir this diamine solution and add at the same time 3.54 g (1.8 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and addition of NMP so that the solid content concentration thereof was 12% by mass, and the mixture was stirred for 5 hours in a water bath of 23 ° C to obtain a polyfluorene. A solution of the amine acid (abbreviated as P4). Further, the molecular weight of the polyamic acid was Mn = 12,254 and Mw = 27,234. The varnish having a solid content concentration of 6 mass% was prepared by diluting P4 with NMP.

<Synthesis Example 5>

A 300 mL four-necked flask equipped with a stirring apparatus was placed in a nitrogen atmosphere, and 2.81 g (26.0 mmol) of p-phenylenediamine, 1.10 g (2.89 mmol) of NBoc3TBS, 51.99 g of NMP, 155.97 g of GBL, and pyridine 5.16 as a base were added. g (65.18 mmol) was stirred to dissolve. Next, the diamine solution was stirred and 8.83 g (27.2 mmol) of dimethyl1,3-bis(chlorocarbonyl)cyclobutane-2,4-dicarboxylate was added thereto, and the mixture was reacted for 4 hours under water cooling. After 4 hours, 0.75 g (8.3 mmol) of acrylonitrile chloride was added, and the mixture was reacted for 30 minutes under water cooling. The obtained polyamidate solution was placed and stirred in 905 g of 2-propanol, and the precipitate was precipitated by filtration, and then washed with 448 g of 2-propanol for 5 times, and dried to obtain a polyfluorene. Amine acid powder. The molecular weight of this polyphthalate was Mn = 15623 and Mw = 30510. The polyphthalate powder was diluted with GBL to prepare a varnish having a solid content concentration of 10% by mass, 6% by mass, and 1% by mass (abbreviated as P5).

<Synthesis Example 6>

100ml four-necked flask with a stirring device and a nitrogen inlet tube DADPA 3.99 g (20.0 mmol), DDM 0.99 g (5.0 mmol), and NMP 72.4 g were transported with nitrogen while stirring to dissolve. The diamine solution was stirred while 3.57 g (18.3 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and after stirring for 2 hours in a water bath of 23 ° C, TDA 1.50 g (5.0 mmol) was added. N58.58 g of NMP was stirred in a water bath of 23 ° C for 3 hours to obtain a solution of polyamic acid having a solid content of 10.5% by mass (abbreviated as P6). Further, the molecular weight of the polyproline was Mn = 14375 and Mw = 34,127. P6 was diluted with NMP to prepare a varnish having a solid content concentration of 10% by mass, 6% by mass, and 1% by mass.

<Synthesis Example 7>

48.67 g (0.45 mol) of p-phenylenediamine and 18.83 g of 4-(octadecyloxy)-1,3-phenylenediamine were added to a 2000 ml separable flask equipped with a stirring device and a nitrogen introduction tube. 0.05 mol), NMP 1233 g, and nitrogen was supplied while stirring to dissolve. The diamine solution was stirred while adding 150.14 g (0.5 mmol) of TDA and NMP, and the mixture was stirred at 50 ° C for 24 hours to obtain a solution of poly-proline. The polyaminic acid solution was diluted to 5 mass%, and 237.9 g of pyridine of ruthenium catalyzed catalyst and 510.6 g of anhydrous acetic acid were further added thereto, and the mixture was reacted at 40 ° C for 3 hours. This solution was poured into 17.4 L of methanol, and the obtained precipitate was separated by filtration and dried to obtain a white polyimine powder. The obtained polyamidiamine was Mn=9273 and Mw=18815. The yield of hydrazine was 84%. The polyimine powder was dissolved in NMP to prepare a varnish having a solid content concentration of 6 mass% (abbreviated as P7).

<Synthesis Example 8>

A mixed solvent of 4,4'-diaminodiphenylmethane 198.27 g (1.0 mol) and NMP and GBL was added to a 2000 ml separable flask equipped with a stirring device and a nitrogen introduction tube (NMP: GBL = 25.3: 74.7 (volume ratio) of 1111 g, nitrogen was supplied while stirring to dissolve. The diamine solution was stirred while 98.05 g (0.5 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 98.98 g (0.44 mol) of pyromellitic dianhydride were added, and the reaction was carried out at room temperature. A solution of polylysine was obtained in an hour (abbreviated as P8). The polyglycolic acid was Mn=11067 and Mw=26270. The varnish having a solid content concentration of 6 mass% was prepared by diluting P8 with NMP.

<Synthesis Example 9>

Mixing cyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride (2.50 g, 10.00 mmol), 3,5-diaminobenzoic acid in NMP (34.05 g) (1.07 g, 7.03 mmol), PCH7AB (4.95 g, 13.01 mmol), and reacted at 80 ° C for 1 hour, then 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.93 g, 9.84) was added. Methyl) was reacted with NMP (7.73 g) at 40 ° C for 6 hours to obtain a solution of polyamic acid having a solid content concentration of 20% by mass (abbreviated as P9). The polyamine acid had Mn = 13400 and Mw = 58,000. The varnish having a solid content concentration of 6 mass% was prepared by diluting P9 with NMP.

<Synthesis Example 10>

NMP (38.14g) mixed with cyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride (3.94g, 15.75mmol), 3,5-diaminobenzoic acid ( 1.60 g, 10.52 mmol), PCHAB7 (4.00 g, 10.51 mmol), after reacting at 80 ° C for 1 hour, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.01 g, 5.15 mmol) was added. The reaction was carried out with NMP (4.04 g) at 40 ° C for 6 hours to obtain a polyaminic acid solution.

After adding NMP to the polyamic acid solution (20.0 g) and diluting the solid content concentration to 6 mass%, anhydrous acetic acid (4.17 g) and pyridine (1.29 g) of a ruthenium catalyst were added at 50 ° C. It was allowed to react for 2 hours. This reaction solution was poured into methanol (250 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimide pigment. The polyimide imidization ratio of this polyimine was 49%, Mn was 17,200, and Mw was 63,000. The polyimine powder was dissolved in NMP to prepare a varnish having a solid content concentration of 6 mass% (abbreviated as P10).

[Preparation of Composition for Structure Formation and Fabrication of Structure]

The film forming and firing steps were carried out in a clean room at a temperature of 23 ° C and a relative humidity of 55% RH of class 1000.

<Example 1>

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 to a 20 mL single neck pear type flask, and the mixture was stirred using a magnetic stirrer to obtain uniformity. Varnish Forming composition). The varnish was applied by spin coating to a glass surface (hereinafter, also referred to as a glass substrate) having a thickness of 1.1 mm of ITO having a thickness of 3 cm × 4 cm and a thickness of 150 nm (that is, with ITO formed). The surface is the opposite side to form a coating film. After completion of the spin coating, the film was allowed to stand for 10 seconds, and then fired on a hot plate at 80 ° C for 5 minutes, and then fired on a hot plate at 230 ° C for 30 minutes to obtain a film (structure) having a film thickness of 100 nm.

<Example 2>

The same operation as in Example 1 was carried out except that 5.0 g of P2 (6 mass%) obtained in Synthesis Example 2 was used instead of 5.0 g of P3 (6 mass%) obtained in Synthesis Example 3, and uniformity was obtained. A varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 3>

The same operation as in Example 1 was carried out except that 5.0 g of P2 (6 mass%) obtained in Synthesis Example 2 was used instead of 5.0 g of P4 (6 mass%) obtained in Synthesis Example 4, and uniformity was obtained. A varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 4>

In place 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 P7 obtained in Synthesis Example 7 was used (6 mass%). ) and 5.0g obtained in Synthesis Example 8 Other than the P8 (6 mass%), the same operation as in Example 1 was carried out to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 5>

In place 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 P5 obtained in Synthesis Example 5 was used (6 mass%). In the same manner as in Example 1, except that 5.0 g of P7 (6 mass%) obtained in Synthesis Example 7 was used, a uniform varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 6>

The same operation as in Example 1 was carried out except that 5.0 g of P2 (6 mass%) obtained in Synthesis Example 2 was used instead of 5.0 g of P6 (6 mass%) obtained in Synthesis Example 6, and uniformity was obtained. A varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 7>

In place 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 obtained in Synthesis Example 6 was used (6 mass%). In the same manner as in Example 1, except that 5.0 g of P7 (6 mass%) obtained in Synthesis Example 7 was used, a uniform varnish was obtained, and a film thickness of 100 nm was obtained on a glass substrate. The film.

<Example 8>

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 used, and 5.0 g of P2 obtained in Synthesis Example 2 was used instead (6 mass%). In the same manner as in Example 1, except that 5.0 g of P9 (6 mass%) obtained in Synthesis Example 9 was used, a uniform varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 9>

In place 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 was used instead of synthesis. Other than the P10 (6 mass%) obtained in Example 10, the same operation as in Example 1 was carried out to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 10>

In place 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 P7 obtained in Synthesis Example 7 was used (6 mass%). In the same manner as in Example 1, except that 5.0 g of P10 (6 mass%) obtained in Synthesis Example 10 was obtained, a uniform varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 11>

In place 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, 3.0 g of P5 obtained in Synthesis Example 5 was used (6 mass%). In the same manner as in Example 1, except that 3.0 g of P7 (6 mass%) obtained in Synthesis Example 7 and 3.0 g of P9 (6 mass%) obtained in Synthesis Example 9 were used, a uniform varnish was obtained. Further, a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 12>

The same procedure as in Example 1 was carried out, except that 5.0 g of P2 (6 mass%) obtained in Synthesis Example 2 was used instead of 0.5 g of propylene glycol monomethyl ether (PGME), and a uniform varnish was obtained. A film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 13>

The same procedure as in Example 1 was carried out except that spin coating, placing and baking were carried out in a glove box having a nitrogen atmosphere of 20 ppm in oxygen atmosphere, and a uniform varnish was obtained, which was obtained on a glass substrate. A film having a film thickness of 100 nm.

<Example 14>

In the synthesis example 5, the substitution 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 was used. The same procedure as in Example 1 was carried out except that 5.0 g of P5 (6% by mass) obtained in 5.0 g and 5.0 g of P6 (6 mass%) obtained in Synthesis Example 6 were obtained, and a uniform varnish was obtained. A film having a film thickness of 100 nm was obtained.

<Example 15>

The same procedure as in Example 14 was carried out except that spin coating, standing and firing were carried out in a glove box having an oxygen concentration of 20 ppm, and a uniform varnish was obtained, and a film thickness of 100 nm was obtained on the glass substrate. The film.

<Example 16>

A film having a film thickness of 120 nm was obtained on a glass substrate in the same manner as in Example 1 except that the operation was carried out for 30 minutes on a hot plate at 230 ° C.

<Example 17>

A film having a film thickness of 120 nm was obtained on a glass substrate in the same manner as in Example 14 except that the operation was carried out for 30 minutes on a hot plate at 230 ° C.

<Example 18>

The synthesis example 1 was used 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. In the same manner as in Example 1, except that 5.0 g of P1 (1% by mass) and 5.0 g of P2 (1% by mass) obtained in Synthesis Example 2 were obtained, a uniform varnish was obtained, and the glass substrate was further obtained. A film having a film thickness of 20 nm was obtained.

<Example 19>

In place 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 P5 obtained in Synthesis Example 5 was used instead (1 mass%). In the same manner as in Example 1, except that 5.0 g of P6 (1% by mass) obtained in Synthesis Example 6 was used, a uniform varnish was obtained, and a film having a film thickness of 20 nm was obtained on a glass substrate.

<Example 20>

In place 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 P5 obtained in Synthesis Example 5 was used (10% by mass). In the same manner as in Example 1, except that 5.0 g of P6 (10% by mass) obtained in Synthesis Example 6 was obtained, a uniform varnish was obtained, and a film having a film thickness of 200 nm was obtained on the glass substrate.

<Example 21>

A uniform varnish was obtained in the same manner as in Example 1 except that the temperature at which the hot plate was baked for 5 minutes was changed to 40 ° C. Further, a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 22>

The same procedure as in Example 1 was carried out except that the temperature was baked at 70 ° C for 5 minutes on a hot plate to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 23>

The same procedure as in Example 1 was carried out except that the temperature was baked at 90 ° C for 5 minutes on the hot plate to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on the glass substrate.

<Example 24>

The same procedure as in Example 1 was carried out except that the temperature was baked at 120 ° C for 5 minutes on a hot plate to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 25>

A uniform varnish was obtained in the same manner as in Example 14 except that the temperature was baked at 40 ° C for 5 minutes on the hot plate, and a film having a film thickness of 100 nm was obtained on the glass substrate.

<Example 26>

The firing temperature was changed to 70 ° C by firing on a hot plate for 5 minutes. The same procedure as in Example 14 was carried out to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 27>

A uniform varnish was obtained in the same manner as in Example 14 except that the firing temperature was 5 minutes on the hot plate, and a film having a thickness of 100 nm was obtained on the glass substrate.

<Example 28>

A uniform varnish was obtained in the same manner as in Example 14 except that the firing temperature was 5 minutes on the hot plate, and a film having a thickness of 100 nm was obtained on the glass substrate.

<Example 29>

A uniform varnish was obtained in the same manner as in Example 1 except that the standing time after the completion of the spin coating was changed to 1 minute, and a film having a film thickness of 100 nm was obtained on the glass substrate.

<Example 30>

A uniform varnish was obtained in the same manner as in Example 1 except that the standing time after the completion of the spin coating was changed to 5 minutes, and a film having a film thickness of 100 nm was obtained on the glass substrate.

<Example 31>

A uniform varnish was obtained in the same manner as in Example 1 except that the standing time after the completion of the spin coating was changed to 10 minutes, and a film having a film thickness of 100 nm was obtained on the glass substrate.

<Example 32>

A uniform varnish was obtained in the same manner as in Example 1 except that the standing time after the completion of the spin coating was changed to 72 hours, and a film having a film thickness of 100 nm was obtained on the glass substrate.

<Example 33>

A uniform varnish was obtained in the same manner as in Example 14 except that the standing time after the completion of the spin coating was changed to 1 minute, and a film having a film thickness of 100 nm was obtained on the glass substrate.

<Example 34>

A uniform varnish was obtained in the same manner as in Example 14 except that the standing time after the completion of the spin coating was changed to 5 minutes, and a film having a film thickness of 100 nm was obtained on the glass substrate.

<Example 35>

A uniform varnish was obtained in the same manner as in Example 14 except that the standing time after the completion of the spin coating was changed to 10 minutes, and a film having a film thickness of 100 nm was obtained on the glass substrate.

<Example 36>

A uniform varnish was obtained in the same manner as in Example 14 except that the standing time after the completion of the spin coating was changed to 72 hours, and a film having a film thickness of 100 nm was obtained on the glass substrate.

<Example 37>

The same operation as in Example 1 was carried out to obtain uniformity except that P1 (6 mass%) obtained in Synthesis Example 1 was changed to 4.0 g and P2 (6 mass%) obtained in Synthesis Example 2 was changed to 6.0 g. A varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 38>

The same operation as in Example 1 was carried out except that P1 (6 mass%) obtained in Synthesis Example 1 was 6.0 g and the P2 (6 mass%) obtained in Synthesis Example 2 was changed to 4.0 g. A varnish, a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 39>

The same operation as in Example 14 was carried out to obtain uniformity except that P5 (6 mass%) obtained in Synthesis Example 5 was changed to 1.0 g and P6 (6 mass%) obtained in Synthesis Example 6 was changed to 9.0 g. A varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 40>

The same operation as in Example 14 was carried out to obtain uniformity except that P5 (6 mass%) obtained in Synthesis Example 5 was changed to 2.0 g and P6 (6 mass%) obtained in Synthesis Example 6 was changed to 8.0 g. A varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 41>

The same operation as in Example 14 was carried out to obtain uniformity except that P5 (6 mass%) obtained in Synthesis Example 5 was changed to 3.0 g and P6 (6 mass%) obtained in Synthesis Example 6 was changed to 7.0 g. A varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 42>

The same operation as in Example 14 was carried out to obtain uniformity except that P5 (6 mass%) obtained in Synthesis Example 5 was changed to 4.0 g and P6 (6 mass%) obtained in Synthesis Example 6 was changed to 6.0 g. A varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 43>

The same operation as in Example 14 was carried out to obtain uniformity except that P5 (6 mass%) obtained in Synthesis Example 5 was changed to 6.0 g and P6 (6 mass%) obtained in Synthesis Example 6 was changed to 4.0 g. A varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 44>

The same operation as in Example 14 was carried out to obtain uniformity except that P5 (6 mass%) obtained in Synthesis Example 5 was changed to 7.0 g and P6 (6 mass%) obtained in Synthesis Example 6 was changed to 3.0 g. A varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 45>

The same operation as in Example 14 was carried out to obtain uniformity except that P5 (6 mass%) obtained in Synthesis Example 5 was changed to 8.0 g and P6 (6 mass%) obtained in Synthesis Example 6 was changed to 2.0 g. A varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Example 46>

The same operation as in Example 14 was carried out to obtain uniformity except that P5 (6 mass%) obtained in Synthesis Example 5 was changed to 9.0 g and P6 (6 mass%) obtained in Synthesis Example 6 was changed to 1.0 g. A varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Comparative Example 1>

In place 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, 10.0 g of P1 obtained in Synthesis Example 1 was used instead (6 mass%). Other than the above, the same operation as in Example 1 was carried out to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Comparative Example 2>

In place 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, 10.0 g of P2 obtained in Synthesis Example 2 was used instead (6 mass%). Other than the above, the same operation as in Example 1 was carried out to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Comparative Example 3>

In place 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, 10.0 g of P3 obtained in Synthesis Example 3 was used (6 mass%). Other than the above, the same operation as in Example 1 was carried out to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Comparative Example 4>

In place 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, 10.0 g of P4 obtained in Synthesis Example 4 was used instead (6 mass%). Other than the above, the test was carried out in the same manner as in Comparative Example 1, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Comparative Example 5>

In place 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, 10.0 g of P5 obtained in Synthesis Example 5 was used instead (6 mass%). Other than the other embodiments and examples 1 In the same operation, a uniform varnish was obtained, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Comparative Example 6>

In place 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, 10.0 g of P6 obtained in Synthesis Example 6 was used instead (6 mass%). Other than the above, the same operation as in Example 1 was carried out to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Comparative Example 7>

In place 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, 10.0 g of P7 obtained in Synthesis Example 7 was used (6 mass%). Other than the above, the same operation as in Example 1 was carried out to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Comparative Example 8>

In place 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, 10.0 g of P8 obtained in Synthesis Example 8 was used (6 mass%). Other than the above, the same operation as in Example 1 was carried out to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Comparative Example 9>

In place 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, 10.0 g of P9 obtained in Synthesis Example 9 was used (6 mass%). Other than the above, the same operation as in Example 1 was carried out to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Comparative Example 10>

In place 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, 10.0 g of P10 obtained in Synthesis Example 10 was used (6 mass%). Other than the above, the same operation as in Example 1 was carried out to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Comparative Example 11>

The same procedure as in Example 1 was carried out except that firing was performed on a hot plate at 80 ° C for 5 minutes and on a hot plate at 230 ° C for 30 minutes, and a uniform varnish was obtained on the glass substrate. A film having a film thickness of 100 nm was obtained.

<Comparative Example 12>

In place 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, 2.0 g of P7 (6 mass%) obtained in Synthesis Example 7 was used instead. ) and 8.0 g obtained in Synthesis Example 8. Other than the P8 (6 mass%), the same operation as in Example 1 was carried out to obtain a uniform varnish, and a film having a film thickness of 100 nm was obtained on a glass substrate.

<Comparative Example 13>

A glass substrate similar to that of Example 1 was prepared as an example in which a light extraction film was not provided on a glass substrate.

[Surface observation by AFM]

The surface of the film (structure) on each of the glass substrates obtained in Examples 1 to 46 and Comparative Examples 1 to 12 was scanned by AFM at a size of 5 μm × 5 μm, and evaluated for self-organization. Concavity and convexity, and the average height (surface roughness Ra) of the convex portion is obtained. Further, when the unevenness due to self-organization is formed on the film (that is, when it is formed into a shape of a fractal), it is evaluated as ○, and when the unevenness due to self-organization is not formed (that is, the shape of the fractal is not formed) The case) is rated as ×. Further, in Comparative Example 13 in which the film was taken out without light, the same operation as in the above-described Example 1 was carried out on the surface of the glass surface (that is, the surface on the side opposite to the surface on which the ITO was formed), and the observation by AFM was carried out. Measurement of the average height of the projections. The results are shown in Table 2-1 and Table 2-2. Further, 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. 4.

[Measurement of Relative Fluorescence Intensity]

To a 100 mL single neck pear type flask, 9.0 g of polymethyl methacrylate (weight average molecular weight; 15,000, manufactured by Aldrich Co., Ltd.), 0.18 g of 3-hydroxyflavone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 82.62 g were added. Propylene glycol monomethyl ether acetate (PGMEA) was stirred using a magnetic stirrer to obtain a uniform varnish. The varnish obtained here is used as a standard solution for measuring the fluorescence intensity.

The varnish (standard solution) was spin-coated on the ITO surface side of the glass substrate on which each structure was formed in Examples 1 to 46 and Comparative Examples 1 to 12, and fired on a hot plate at 80 ° C. In seconds, a standard film having a film thickness of 100 nm was formed. Further, the measurement conditions of the fluorescence spectrum were set such that the excitation wavelength was 341.0 nm, the fluorescence onset wavelength was 450 nm, the fluorescence end wavelength was 700 nm, and the scanning speed was 240 nm/min, and the excitation light was irradiated from the standard film side, and the structure was irradiated. Light was taken out from the object side, and the fluorescence was obtained by reading the maximum fluorescence peak appearing at 531.0 nm.

Further, in Comparative Example 13, the varnish (standard solution) was spin-coated on the ITO surface side of the glass substrate and fired on a hot plate at 80 ° C for 10 seconds to obtain a standard film having a film thickness of 100 nm. Further, the fluorescence intensity was determined in the same manner as in the above Example 1.

The fluorescence intensity was measured under a relative comparison, and the fluorescence intensity obtained by measuring 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 Table 2-1 and Table 2-2.

As shown in Table 2-1 and Table 2-2, each of Examples 1 to 46 is a structure having irregularities formed by self-organization on the surface, that is, a structure formed on the surface having a pattern of irregularities on the surface. . On the other hand, in Comparative Examples 1 to 12, irregularities due to self-organization were not formed. And real In Examples 1 to 46, the relative fluorescence intensity was higher than that of Comparative Examples 1 to 12, and when used as a light extraction film, it was confirmed that the light extraction efficiency was improved. Therefore, the structure of the present invention can be suitably used as a light extraction film or the like as an optical device such as an LED element. The results of these are more detailed below.

As a combination of polymers, Examples 1 to 3, 6 and 8 are examples of a mixture of polyacrylic acid and polyaminic acid, and Examples 4, 7 and 9 are examples of a mixture of polyamic acid and polyimine. Example 10 is a mixed example of polyimine and polyimine, and Example 14 is a mixed example of polylysine and polyphthalate, and Example 5 is a polyimine and a polyamidolate. In the case of mixing, in any mixing, a structure having irregularities formed by self-organization is formed on the surface. Further, Example 11 is an example in which three types of polymers of polyglycolic acid, polyimine, and polyglycolate are mixed. However, in this case, it may be formed on the surface by self-organization. Concave structure. Further, in the embodiment 12, a system in which a single polymer is used without mixing a dissimilar polymer is used, but in the varnish containing the polymer, PGME is added with a poor solvent having a very low solubility to the polymer, so A structure that is self-organized and formed on the surface with irregularities formed by self-organization. Further, in the examples 1 to 6, 12, 13, 15, 16, 18 to 24, 29 to 32, and 37 to 39, the basic pattern unit of the fractal pattern is as shown in FIG. Further, in the examples 7 to 11, 14, 17, 25 to 28, 33, and 43 to 46, the basic pattern unit of the fractal pattern is a hemispherical shape as shown in Fig. 4 . Further, in Examples 34 to 36 and 40 to 42, the basic pattern unit of the fractal pattern was a hole shape.

Moreover, when comparing the relative fluorescence intensities of Examples 1 to 11, Only the relative fluorescence intensity of Example 2 was less than 1.30, and it was found that the relative fluorescence intensity tends to adhere to the skeleton of the monomer (diamine component or tetracarboxylic acid component) constituting the polymer. In the second embodiment, the monomer skeleton constituting the polymer contained in the composition for forming a structure to be used does not have a bond capable of forming a hydrogen bond in or between molecules and can be intramolecular or molecular. Either of the substituents forming a hydrogen bond, and also containing neither of the two polymers which have been mixed, the relative strength in Example 2 is low.

Examples 1 and 13 to 15 are examples in which the environment after spin coating, spin coating, and firing is different. Any one of the nitrogen in the atmosphere and having an oxygen concentration of 20 ppm is formed on a structure having irregularities formed by self-organization on the surface. Therefore, it is not determined by such a process whether or not self-organization is generated. The environment. Further, in the nitrogen atmosphere, since the average height of the convex portions is lowered and the relative fluorescence intensity tends to decrease, it is preferable to perform the combustion in the atmosphere.

Examples 1 and 16, Examples 14 and 17, and Comparative Example 11 are examples in which the firing steps differ. Example 16 and Example 14 were carried out by firing at 230 ° C for 30 minutes and at 80 ° C for 5 minutes, or by firing at 30 ° C for 30 minutes but at 80 ° C for 5 minutes. In the case of the comparative example 11 in which the self-organization was formed by the self-organization, the self-organization was not produced, and it was found that the structure was formed when the structure having the irregularities formed by the self-organization was formed. It is a must. Further, in Examples 1, 16, 14, and 17, it can be said that self-organization is produced after firing at 80 ° C for 5 minutes.

Examples 1 and 21 to 24, and Examples 14 and 25 to 28 are burned. An example of a temperature difference. It is known that the temperature at which the firing is performed after the spin coating is a structure having irregularities formed by self-organization even in any of 40 ° C to 120 ° C. Further, since the relative fluorescence intensity is stabilized when the firing temperature is 70 ° C or higher, it is preferable that the firing temperature is 70 ° C or higher.

Examples 1 and 18, and Examples 14, 19, and 20 are examples in which the solid content concentration of the composition for forming a structure, that is, the concentration of the polymer differs. It is known that the increase in film thickness due to an increase in the solid content concentration can be formed on a structure having irregularities formed by self-organization. Further, the relative fluorescence intensity was strong in Example 20 in which the solid content concentration was the highest and the average height of the convex portion was the highest, and it was found that the structure had a high solid concentration when it was placed at the forefront of the extracted light. It is advantageous to have a large film thickness.

Examples 1 and 29 to 32, and Examples 14 and 33 to 36 are examples in which the placement time after the completion of the spin coating is different. It was found that the standing time after the completion of the spin coating was a structure having irregularities formed by self-organization in any of 10 seconds to 72 hours. Since the placement time is directly linked to the tact time of the actual manufacturing process, and the shorter the placement time is, the shorter the manufacturing time is, so it is preferably 10 seconds to 10 minutes, preferably 10 seconds or more and 5 minutes.

Examples 1, 37 and 38, and Examples 14 and 39 to 46 are examples in which the mixing ratios of the polymers are different. From the viewpoint of an increase in relative fluorescence intensity, the mixing ratio of the first polymer to the second polymer of the dissimilar polymer is in the first polymer: the second polymer = 40: 60 (% by mass) to the first polymer. : It is preferable that the second polymer = 60:40 (% by mass) is contained, and it is found that the ratio of any of the polymers is 70% by mass or more.

Further, Example 4 and Comparative Example 12 are also examples in which the mixing ratio of the polymers is different. In the case of using a structure for forming a structure containing P8 containing polyamic acid and P7 containing polyimine, a structure having irregularities formed by self-organization is formed in Example 4, but polymerization is carried out. In Comparative Example 12 in which the ratio was set to polyimine: polyamine: 20:80 (% by mass), irregularities due to self-organization were not formed. This phenomenon is presumed to be due to the use of two different types of polyamidene in the case of the polyimine of P7 and the polyamine of P8, but the upper layer (polyimine) and the lower layer (polymerized) The proline acid was clearly separated, so that the surface of the film became the same as the single film of the upper layer of the polyimide, so that no self-organization occurred, and no fractal shape was observed.

In Comparative Examples 1 to 12, the relative fluorescence intensity was low and the light extraction efficiency was also inferior to the example having the structure in which the unevenness formed by self-organization was formed on the surface. Further, in Comparative Examples 1 to 12, although irregularities having a relatively high average height with respect to the convex portion were formed, as shown in FIG. 4, the unevenness formed in Comparative Example 2 or the like was not a bump formed by self-organization. . That is, no basic unit pattern was observed in the four directions of 50 μm, which was caused by the unevenness of the uniform film roughness in the plane of the film surface.

In Comparative Example 13, the relative fluorescence intensity when the light extraction film was not provided was the worst, and the light extraction efficiency was the worst. From this, it can be seen that when the polyimide and the polyimide precursor are used as the light extraction film, the light extraction efficiency can be improved, and the surface formed by the self-organization can be formed on the surface. When the object is created, the light extraction efficiency can be further improved.

Further, in the above-described Examples 1 to 46, even if the results were repeated 30 times, the same result (the unevenness due to self-organization and the average height of the convex portion) was obtained, and it was confirmed that the reproducibility was extremely excellent.

Claims (16)

A structure comprising a first polymer composed of polyamidene and a second polymer different from the first polymer, and having a first polymer and the first layer on a surface thereof 2 The irregularities formed by the self-organization of the polymer. The structure of claim 1, wherein the convex portion formed on the surface has an average height of 0.5 nm to 500 nm. The structure of claim 1, wherein the second polymer is composed of a polyimine different from the first polymer. The structure of claim 2, wherein the second polymer is composed of a polyimine different from the first polymer. The structure of claim 1, wherein at least one of the first polymer and the second polymer has a bond selected from a group capable of forming a hydrogen bond in or between molecules, and can be intramolecular or intermolecular At least one of the substituents forming a hydrogen bond. The structure of claim 2, wherein at least one of the first polymer and the second polymer has a bond selected from a group capable of forming a hydrogen bond in or between molecules, and can be intramolecular or intermolecular At least one of the substituents forming a hydrogen bond. The structure of claim 3, wherein at least one of the first polymer and the second polymer has a bond selected from a group capable of forming a hydrogen bond in or between molecules, and can be intramolecular or intermolecular At least one of the substituents forming a hydrogen bond. The structure of claim 4, wherein the first polymer and the aforementioned At least one of the second polymers is at least one selected from the group consisting of a bond selected to form a hydrogen bond in or between molecules, and a substituent capable of forming a hydrogen bond in or between molecules. The structure of claim 5, wherein the bond capable of forming a hydrogen bond in or between molecules is represented by the following formula (1), and the substituent capable of forming a hydrogen bond in or between molecules is a group selected from the group consisting of a hydroxyl group, a thiol group, an amine group, and a carboxyl group; The structure of claim 6, wherein the bond capable of forming a hydrogen bond in or between molecules is represented by the following formula (1), and the substituent capable of forming a hydrogen bond in or between molecules is a group selected from the group consisting of a hydroxyl group, a thiol group, an amine group, and a carboxyl group; The structure of claim 7, wherein the bond capable of forming a hydrogen bond in or between molecules is represented by the following formula (1), and the substituent capable of forming a hydrogen bond in or between molecules is a group selected from the group consisting of a hydroxyl group, a thiol group, an amine group, and a carboxyl group; The structure of claim 8, wherein the bond capable of forming a hydrogen bond in or between molecules is represented by the following formula (1), and the substituent capable of forming a hydrogen bond in or between molecules is a group selected from the group consisting of a hydroxyl group, a thiol group, an amine group, and a carboxyl group; A light extraction film comprising the structure of any one of claims 1 to 12. An electronic device characterized by having a light extraction film as claimed in claim 13. The electronic device of claim 14, which is a light emitting diode. A method for forming a structure, which is characterized in that the structure has a structure having irregularities on its surface, and is characterized in that it has the following steps: a composition for forming a structure containing the component (A) and the component (B) described below a coating step on the substrate, a standby placing step of standing after the coating step, and a firing step of baking after the standby standing step; (A) component: a first polymer composed of polyimine or a first polymer precursor composed of a polyimine precursor, and a component (B): a second polymer or a second polymerization different from the component (A) Precursor, and at least one of propylene glycol monomethyl ether.