CN113773494B - Resin composition, resin film and display device - Google Patents

Resin composition, resin film and display device Download PDF

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CN113773494B
CN113773494B CN202111170261.4A CN202111170261A CN113773494B CN 113773494 B CN113773494 B CN 113773494B CN 202111170261 A CN202111170261 A CN 202111170261A CN 113773494 B CN113773494 B CN 113773494B
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resin composition
formula
resin
compound
film
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CN113773494A (en
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许翔
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/33—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being semiconductor devices, e.g. diodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Electroluminescent Light Sources (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The application provides a resin composition, a resin film and a display device, wherein at least one of the polymers of the resin composition contains two structures or one of the structures containing the following formulas:wherein R is 7 ‑R 9 Selected from C 1 ‑C 20 Alkyl, C of (2) 1 ‑C 20 Cycloalkyl, C 1 ‑C 20 Silane group, C of (C) 1 ‑C 20 Ester group, C 1 ‑C 20 Alkoxy, C 1 ‑C 24 Aromatic radicals, C 1 ‑C 24 One or more of heteroaryl, cyano, carboxyl, amino, alkylamino, nitro, amido and halogen, n is an integer of 0-2, m is an integer of 0-4, and o is an integer of 0-7. According to the technical scheme, the resin film with low transmittance can be obtained, and the display device with better visual effect can be obtained.

Description

Resin composition, resin film and display device
Technical Field
The present application relates to the field of display devices and display apparatuses, and more particularly, to a polymer material such as a resin composition and a resin film used in an organic electroluminescent display device.
Background
Organic electroluminescent (OLED) displays are considered to be the next generation of displays following Liquid Crystal Displays (LCDs). The light-weight and flexible foldable display has the characteristics of light weight, flexibility, folding property, wide viewing angle, low energy consumption and high contrast, and is widely applied to various fields such as mobile phones, televisions and the like.
For the organic electroluminescent display, it can be classified into bottom emission and top emission according to the manner of light emission, i.e., bottom emission is light coming out of the underside of the substrate, and top emission is light coming out of the opposite side of the substrate. For conventional organic electroluminescent devices, they form Thin Film Transistors (TFTs) and ITO electrodes of circuits, which have high reflectivity, seriously affecting the sensory visual effect. Many people have therefore begun to study methods for reducing their reflectivity; one of the most direct and effective methods from the viewpoint of the structure of an organic electroluminescent display is to reduce the reflectance of a flat film on a TFT substrate in the organic electroluminescent display.
For example, in KR20180021342, a black pigment is added to a substrate film so that the transmittance of the film is low in a wavelength range of 400nm or more, thereby obtaining a low-transmittance substrate film. In japanese patent laid-open No. 2008-122501, a method of adding a color-developing composition such as a leuco dye and a color-developing agent to a substrate film is proposed to reduce the transmittance of the cured substrate film.
In summary, the problem of improving the reflectivity of the organic electroluminescent display device is one of the important problems to be solved.
Disclosure of Invention
For the above prior art, for example, in KR20180021342 and patent publication 2008-122501, there are problems that only the transmittance in the visible light field with a specific wavelength is low, but the transmittance is not low enough in the visible light field range outside the specific range, and the light shielding performance is poor, so that the color chroma, saturation and the like of the display are low, i.e. the visibility is poor in the sense visual effect; meanwhile, the obtained substrate film has the problems of low service life, low yield and the like of the display device due to poor physical properties such as linear thermal expansion coefficient and the like of the cured substrate film.
The application aims to provide a resin composition and a resin film which have high light absorptivity and low transmissivity in the whole range of 400-700 nm, and can obtain excellent visual effect when being applied to an organic electroluminescent display device. Another object of the present application is to obtain a resin composition and a resin film excellent in characteristics such as linear thermal expansion coefficient and tensile modulus, and to be applied to an organic electroluminescent display device to solve the problems of low service life, low yield, and the like.
In one aspect of the present application, there is provided a resin composition comprising a polymer comprising a structure represented by formula 1 and/or formula 2:
wherein R is 1 、R 3 Each independently is a tetravalent organic residue;
wherein R is 2 、R 4 Each independently is a divalent organic residue or terminal residue, R 2 、R 4 Each independently selected from one or more of a divalent organic residue represented by formula 3 and/or a terminal residue represented by formula 4,
wherein R is 7 -R 9 Selected from C 1 -C 20 Alkyl, C of (2) 1 -C 20 Cycloalkyl, C 1 -C 20 Silane group, C of (C) 1 -C 20 Ester group, C 1 -C 20 Alkoxy, C 1 -C 24 Aromatic radicals, C 1 -C 24 One or more of heteroaryl, cyano, carboxyl, amino, alkylamino, nitro, amido and halogen, n is an integer of 0-2, m is an integer of 0-4, and o is an integer of 0-7;
wherein n R 7 M R 8 O R 9 The two may be the same or different. Each independent R 7 、R 8 、R 9 Independently selected from C 1 -C 20 Alkyl, C of (2) 1 -C 20 Cycloalkyl, C 1 -C 20 Silane group, C of (C) 1 -C 20 Ester group, C 1 -C 20 Alkoxy, C 1 -C 24 Aromatic radicals, C 1 -C 24 A heteroaryl group, a cyano group, a carboxyl group, an amino group, an alkylamino group, a nitro group, an amide group or a halogen.
Wherein the structure represented by formula 3 may be more specifically selected from the structures represented by formula 5, wherein R 10 -R 17 Each independently selected from H, C 1 -C 20 Alkyl, C of (2) 1 -C 20 Cycloalkyl of (c)、C 1 -C 20 Silane group, C of (C) 1 -C 20 Ester group, C 1 -C 20 Alkoxy, C 1 -C 24 Aromatic radicals, C 1 -C 24 Is selected from the group consisting of heteroaryl, cyano, carboxyl, amino, alkylamino, nitro, amido and halogen, and R 10 -R 12 Middle, R 13 -R 17 Each of which is a chemical bond; the structure represented by formula 4 may be more specifically selected from the structures represented by formula 6, wherein R 18 -R 25 Each independently selected from H, C 1 -C 20 Alkyl, C of (2) 1 -C 20 Cycloalkyl, C 1 -C 20 Silane group, C of (C) 1 -C 20 Ester group, C 1 -C 20 Alkoxy, C 1 -C 24 Aromatic radicals, C 1 -C 24 Is selected from the group consisting of heteroaryl, cyano, carboxyl, amino, alkylamino, nitro, amido and halogen, and R 18 -R 25 One of them is a chemical bond;
in formula 2, R 5 And R is 6 Each independently selected from H, C 1 -C 20 Alkyl, C of (2) 1 -C 20 A silane group, a metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion.
Preferably, said R 1 、R 3 Each independently selected from tetravalent C 6 -C 20 Aryl groups of (a).
Preferably, the number of carbon atoms in the structures of formula 3 and/or formula 4 is less than 40.
Preferably, the polymer comprises at least one rigid structural unit; the rigid structural units may be present in a copolymerized and/or blended form with the structures of formulae 1 and/or 2.
Preferably, the rigid structural unit is a mono-benzene, biphenyl or polycyclic aromatic hydrocarbon type structure.
Preferably, the molar content ratio of the structural units of formula 3 and/or formula 4 to all the structural units in the polymer is 0.1% or more molar and ratio to 10% or less molar ratio.
Preferably, one or more of pigment, dye, inorganic particles, photosensitizer and adhesive are also contained.
In another aspect of the present application, there is also provided a resin film prepared from the resin composition of the present application.
In another aspect, the present application also provides a display device, which includes a substrate, and the resin film provided by the present application is further disposed on the substrate.
According to the technical scheme provided by the application, the resin composition with excellent performance can be obtained, and the resin film prepared from the resin composition has excellent light absorptivity and lower transmittance in the wavelength range of 400-700 nm, namely, the Film Transistor (TFT) and the ITO electrode forming a circuit in the organic electroluminescent device can be effectively inhibited, the reflectivity of medium light is improved, and excellent sensory visual effects and the like are obtained. In addition, the resin film provided by the application has excellent physical properties, such as low linear thermal expansion coefficient, excellent mechanical properties and the like, so that the resin film can obtain the excellent characteristics of long service life and good yield when being applied to an organic electroluminescent display device.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the detailed description of non-limiting embodiments, made with reference to the following drawings.
Fig. 1 is a schematic cross-sectional structure of a TFT substrate formed with a planarizing film and an insulating layer according to an embodiment of the present application.
Detailed Description
In order that the objects and advantages of the application will become more apparent, a more complete description of the embodiments will now be described with reference to the embodiments, which will assist those skilled in the art in further understanding the application, however, the embodiments of the embodiments can be implemented in a variety of forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the example embodiments to those skilled in the art.
In one aspect of the present application, there are provided a resin composition, a resin film prepared therefrom, and a display device, wherein,
the resin composition comprises one or more polymers, wherein at least one polymer comprises a structure shown in a formula 1 and/or a formula 2:
wherein R is 1 、R 3 Each independently is a tetravalent organic residue;
wherein R is 2 、R 4 Each independently is a divalent organic residue or terminal residue, R 2 、R 4 One or more selected from the group consisting of divalent organic residues represented by formula 3 and/or terminal residues represented by formula 4. I.e., one or more of formula 3 may be included in the polymer, or one or more of formula 4 may be included alone or together.
Wherein R is 7 -R 9 Selected from C 1 -C 20 Alkyl, C of (2) 1 -C 20 Cycloalkyl, C 1 -C 20 Silane group, C of (C) 1 -C 20 Ester group, C 1 -C 20 Alkoxy, C 1 -C 24 Aromatic radicals, C 1 -C 24 One or more of heteroaryl, cyano, carboxyl, amino, alkylamino, nitro, amido and halogen, n is an integer of 0-2, m is an integer of 0-4, and o is an integer of 0-7;
wherein n R 7 M R 8 O R 9 The two may be the same or different. Each independent R 7 、R 8 、R 9 Independently selected from C 1 -C 20 Alkyl, C of (2) 1 -C 20 Cycloalkyl, C 1 -C 20 Silane group, C of (C) 1 -C 20 Ester group, C 1 -C 20 Alkoxy, C 1 -C 24 Aromatic radicals, C 1 -C 24 A heteroaryl group, a cyano group, a carboxyl group, an amino group, an alkylamino group, a nitro group, an amide group or a halogen.
Wherein the structure represented by formula 3 may be more specifically selected from the structures represented by formula 5, wherein R 10 -R 17 Each independently selected from H, C 1 -C 20 Alkyl, C of (2) 1 -C 20 Cycloalkyl, C 1 -C 20 Silane group, C of (C) 1 -C 20 Ester group, C 1 -C 20 Alkoxy, C 1 -C 24 Aromatic radicals, C 1 -C 24 Is selected from the group consisting of heteroaryl, cyano, carboxyl, amino, alkylamino, nitro, amido and halogen, and R 10 -R 12 Middle, R 13 -R 17 Each of which is a chemical bond; the structure represented by formula 4 may be more specifically selected from the structures represented by formula 6, wherein R 18 -R 25 Each independently selected from H, C 1 -C 20 Alkyl, C of (2) 1 -C 20 Cycloalkyl, C 1 -C 20 Silane group, C of (C) 1 -C 20 Ester group, C 1 -C 20 Alkoxy, C 1 -C 24 Aromatic radicals, C 1 -C 24 Is selected from the group consisting of heteroaryl, cyano, carboxyl, amino, alkylamino, nitro, amido and halogen, and R 18 -R 25 One of them is a chemical bond;
the structures represented by formulas 3 and 4 may be derived from azulene compounds.
In formula 2, R 5 And R is 6 Each independently selected from H, C 1 -C 20 Alkyl, C of (2) 1 -C 20 Silane, metal, ammonium, imidazolium orPyridinium ions.
The resin composition of the embodiment of the present application is suitable for preparing a substrate film for an organic electroluminescent display device, and therefore it is required to have a low thermal expansion coefficient. Meanwhile, when the resin film is used for the substrate of the organic electroluminescent device, the heat resistance of the resin film needs to be considered, and when the heat resistance is insufficient, the yield of the final organic electroluminescent device is reduced. Thus, the resin composition, R in the structure represented by formula 1 and/or formula 2 in the polymer 1 、R 3 Selected from tetravalent C 6 -C 20 And/or aryl residues of formula 3, wherein the number of carbon atoms in the structure of the polymer is less than 40.
More particularly preferably, said R 1 、R 3 Each independently selected from one of the following structures:
more specifically, the R 2 、R 4 May be independently selected from any one or more combinations of the structures shown in formula 3 and/or formula 4; more specifically, R 2 、R 4 Can be independently selected from any one or more combinations of structures shown in a formula 3, and R 2 、R 4 May be independently selected from any one or more combinations of the structures shown in formula 4.
In addition, the resin composition may contain, in addition to the structural units of formula 1 and/or formula 2, a structural unit a having the following rigidity:
wherein the rigid structural unit A may be copolymerized with structural units of formula 1 and/or formula 2 to form a polymer A, or may be present alone in a polymer B, wherein the rigid structural unit A may beTo be selected from one or more of the above structures. When polymer a and polymer B are present, they are present in the composition as a blend. The effect of the addition of the rigid structural unit A described above is that a resin composition having a lower coefficient of thermal expansion can be obtained.
Preferably, the polymer in the resin composition is one or more of polyimide and/or polyimide precursor. The polymer may include the structure represented by the formula 1, the structure represented by the formula 2, or both the structure represented by the formula 1 and the structure represented by the formula 2. In general, formula 1 may be obtained by a method of heating or chemically catalyzing the structure shown in formula 2.
The resin composition, wherein the polyimide and/or polyimide precursor has a main chain structure comprising at least one rigid structural unit; the rigid structural unit may preferably be one or more of a mono-benzene, biphenyl, and polycyclic aromatic hydrocarbon type structure. More particularly, it is preferred that one and/or more of the following structures:
in the present application, the polymer may include any one of formula 1 and/or formula 2, or may include a combination of a plurality of formulas 1 and/or 2; the resin composition provided by the application is also required to have good mechanical properties when applied to a flexible substrate film in an organic electroluminescent display device. The structures of formula 3 and/or formula 4 in the present application are more specifically preferred to be derived from azulene compounds, which are chemically bonded to the polymer backbone, so that stable chemical structures can be formed, while reducing the presence of foreign materials, better maintaining the original good mechanical properties of the polymer.
In the structure represented by the formula 3 and/or the formula 4, the form of the substituent is not limited, and the absorbance in different wavelength ranges can be finely adjusted according to the substituent, but the average absorbance value of the resin composition or the resin film formed therefrom in the entire wavelength range of 400nm to 800nm is not affected, and the average absorbance value is not less than 90%.
The main reason why the resin composition has excellent absorbance is that by introducing the structure shown in formula 3 and/or formula 4, the electron cloud of the structure interacts with the amide and imide structure, so that the resin composition can be prepared into a black resin film, and the light transmittance of the wavelength in the range of 400-800nm is effectively reduced. In addition, when some substituents are introduced in the structures shown in formula 3 and/or formula 4, absorbance in different wavelength ranges can be fine-tuned; for example, when R 7 -R 9 When the electron donating group is adopted, the electron cloud density on the azulene ring is increased, and the energy of electron transition is reduced, so that the absorption spectrum is subjected to red shift, and the maximum absorbance value is closer to the wavelength of 800 nm; and when R is 7 -R 9 When the fluorescent dye is an electron withdrawing group, the electron cloud density on an azulene ring can be reduced, and the energy of electron transition is improved, so that the absorption spectrum of the fluorescent dye is blue-shifted, and the maximum absorbance value of the fluorescent dye is closer to the position of 400 nm.
R as an electron withdrawing group 7 -R 9 May preferably be selected from one or more of nitro, halogen, cyano, amide, carboxyl, more preferably from cyano and amide; r as electron donating group 7 -R 9 Preferably selected from C 1 -C 20 Alkyl, C of (2) 1 -C 20 Ester group, C 1 -C 20 Alkoxy, C 1 -C 24 More preferably from methyl, methyl acetate, ethyl acetate.
More specifically exemplified, the divalent residues of the structure shown in formula 3 may be derived from the following azulene compounds:
but are not limited to, one or more of these monomers.
More specifically exemplified, the monovalent residues of the structure shown in formula 4 may be derived from the following azulene compounds:
but are not limited to, one or more of these monomers.
The sum of the structural units represented by the formula 3 and/or the formula 4 is 0.1% by mole or more and 10% by mole or less of the total of the structural units in all the polymers of the resin composition; preferably 1% by mole or more and 9% by mole or less; more preferably 3% by mole or more and 8% by mole or less.
If the molar content of the structural unit containing the azulene is too small, the light absorption effect cannot meet the requirement; if the molar content of the structural unit containing azulene is too large, i.e., more than 10% by mole, the light absorption effect is very good, but the mechanical properties of the film may be lowered, failing to meet the use requirements of the organic electroluminescent display device substrate.
The resin composition of the application can also contain pigment and/or dye to obtain better and more uniform light absorption effect; from the viewpoint of heat resistance of the resin composition and the resin film obtained therefrom, it is preferable to include a pigment.
The pigment may also be an inorganic pigment and/or an organic pigment, wherein the organic pigment may be exemplified by azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, diazine, indanthrene, perylene, etc.; examples of the inorganic pigment include carbon black, acetylene black, lamp black, bone carbon, graphite, iron black, and titanium black, and among them, carbon black, perylene black, and aniline black are preferable. In addition, depending on the color type of the pigment, a black pigment, a blue pigment or a violet pigment may be preferable, and may be used alone or in combination of two or more. Among them, examples of the black pigment include organic black pigments such as aniline black, perylene black, and triamcinolone black; for other color pigments, specific classes may be represented according to pigment index numbers (c.i.), for example, as blue pigments, it may be cited as c.i. pigment blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79; among them, c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 may be more preferable; even more preferred is c.i. pigment blue 15:6.
For example, examples of violet pigments include c.i. pigment violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50; among them, c.i. pigment violet 19, 23 may be more preferable.
The resin composition of the application can further provide more other properties, and can also contain other additives such as a photosensitizer, a silane coupling agent, a crosslinking agent and the like; for example, when a sensitizer is added, photosensitivity can be imparted to the resin composition; the silane coupling agent is added, so that better adhesion performance can be given; the crosslinking agent is added, so that the mechanical properties of the material and the like can be better improved; the other additives are not limited to the kind according to the present application.
In another aspect of the present application, there is also provided a resin film prepared from the resin composition of the present application. The resin film prepared by the resin composition of the present application has very good absorbance, so that it can be understood that a black resin film. In particular, the black resin film contains a structural unit of azulene, and when the film thickness of the black resin film is about 10 μm, the absorbance of the black resin film between 400nm and 800nm is 90% or more, that is, the transmittance is 10% or less. When the black resin film is used in combination with a pigment and/or dye, the absorbance at a wavelength of 400nm to 800nm can be measured to be 95% or more, that is, the transmittance is 5% or less, when the thickness of the black resin film is about 10. Mu.m. In addition, the black resin film has a good effect of having a linear thermal expansion coefficient of less than 10 ppm/. Degree.C.in the range of 50-300 ℃; in addition, when the resin composition provided by the application is coated on a glass substrate, the residual stress value of the black resin film formed can reach less than 25MPa.
In another aspect, the present application also provides an organic electroluminescent display device, which includes a substrate, and the black resin film provided by the present application is further provided on the substrate. The black resin film can be suitably applied to an organic light emitting display device having a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode on a substrate.
The light emitting device shown with reference to fig. 1 is exemplified as an active matrix display device: comprising a substrate 1, a resin film 2 obtained from the resin composition of the present application, TFT3, a first insulating layer 4, an anode 5, a via 6, a second insulating layer 7, a recess 8, an organic light-emitting layer 9, and a cathode 10. A flexible organic electroluminescent device can be obtained if the substrate 1 is peeled off from the black resin film 2. When the black resin film is used, a display device having high contrast and small color difference shift can be obtained in the device to be manufactured.
In the embodiment of the present application, the preparation method of the resin composition, the resin film and/or the black resin film is as follows:
the preparation method of the resin composition comprises the following steps:
polymerization is carried out using a known method, for example, polymerization reaction using an acid anhydride and a diamine in a reaction solvent, and, at the same time as or after completion of the polymerization reaction, additives such as a capping agent, an esterifying agent, a salifying agent, etc. are added as needed; the reaction solvent may be used in the preparation process, and the solvent is an aprotic solvent, which is preferably selected from N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, rγ -butyrolactone, and the like. The resin composition can be finally obtained.
In addition, for the addition of pigments and/or dyes, known dispersion methods can be used to obtain; for example, a method of mixing with a dispersing machine such as a ball mill, a sand mill, a bead mill, a paint mixer, a roll mill such as a roll mill, a roll mixer such as a planetary mixer or a henschel mixer, a roll mill such as a 3-roll mixer, a kneader, a colloid mill, an ultrasonic wave, a homogenizer, a rotation/revolution mixer, or the like is used. The desired resin composition is finally obtained.
The preparation method of the black resin film comprises the following steps:
the resin composition is applied onto a substrate by spin coating, slit printing, or the like. Examples of the substrate include a silicon wafer, a glass substrate, a metal substrate, and a ceramic substrate. After coating, pre-baking the resin composition and drying; wherein, the pre-drying method can use a heating drying and decompression drying mode; in the drying method, a temperature drying heat treatment is used at a drying temperature in the range of 200 ℃ to 500 ℃, and the black resin film is finally obtained. Among them, the resulting black resin film has excellent physical properties such as low thermal expansion coefficient, low residual stress, high tensile modulus strength, etc., while effectively reducing transmittance.
The preparation method of the organic electroluminescent display device comprises the following steps:
the application provides a resin composition, a resin film and a display device with the resin composition. The black resin film provided by the application can be applied to an organic light-emitting display device having a drive circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate.
The application is described below with reference to specific examples:
in the examples of the present application, the compounds used are as follows:
compound 1: pyromellitic dianhydride, CAS No:89-32-7
Compound 2:3,3', 4' -biphenyltetracarboxylic dianhydride, CAS No:2420-87-3
Compound 3:2,3,6, 7-naphthalene tetracarboxylic dianhydride, CAS No:3711-01-1
Compound 4:1,4,5, 8-naphthalene tetracarboxylic anhydride, CAS No:81-30-1
Compound 5: p-phenylenediamine, CAS No:106-50-3
Compound 6: (6-amino-2-naphthyl) amine, CAS No:2243-67-6
Compound 7:2, 6-diaminoanthracene, CAS No:46710-42-3
Compound 8:2, 6-diaminoazulene, CAS No:947157-92-8
Compound 9: 1-carboxamide, 3-aminoazulene, CAS No:730977-52-3
Compound 10:2, 5-diamino, 1, 3-diacetoxyethyl azulene, CAS No:13227-62-8
The preparation method of the pigment dispersion liquid comprises the following steps:
preparation of dispersion 1: c.i. pigment blue 15:6 (DIC Co., EP 193) 80g, BYK6919 (BYK Co.) 60g, alkali-soluble resin (Cyclomer P (ACA) Z250, daicel allnex co.Ltd.) 60g, and propylene glycol monomethyl ether acetate 600g were mixed to prepare a mixed solution, and then the mixed solution was dispersed using a ball mill using 0.5mm zirconia particles as a medium, to obtain a dispersion 1.
Preparation of dispersion 2: C.I. pigment violet 19 (TCI Co., product code: Q0057) 70g, BYK6919 (BYK Co.) 60g, alkali-soluble resin (Cyclomer P (ACA) Z250, daicel allnex co.Ltd.) 60g, and propylene glycol monomethyl ether acetate 650g were mixed to prepare a mixed solution, and then the mixed solution was dispersed using 0.5mm zirconia particles as a medium using a ball mill to obtain a dispersion 2.
Example 1
First, a resin polymer solution 1:
in a 2500ml four-necked flask equipped with a thermometer and a stirrer, dry nitrogen gas was introduced, and then compound 5 (0.92 mol,99.49 g), compound 8 (0.08 mol,12.66 g) and N-methylpyrrolidone (NMP, 1473 g) were added, the temperature was raised to 60℃and stirred until dissolved, then compound 1 (0.5 mol,109.06 g), compound 2 (0.5 mol,147.11 g) were added, and after reacting at 60℃for 6 hours, a polyimide precursor solution (resin polymer solution) was obtained, the solid content of the solution was 20%, and the polymer molecular weight was 80000.
Then, a resin composition solution 1 was prepared:
dispersion 1 (129 g,0.07 wt) was added to the resin polymer solution 1 under vigorous stirring, and stirred for 1 hour to obtain a resin composition solution 1.
Example 2
First, a resin polymer solution 2:
in a 2500ml four-necked flask equipped with a thermometer and a stirrer, dry nitrogen gas was introduced, then, compound 5 (0.96 mol,103.81 g), compound 10 (0.04 mol,12.09 g) and N-methylpyrrolidone (NMP, 1519 g) were added, the temperature was raised to 60℃and stirred until dissolved, then, compound 1 (0.4 mol,87.25 g) and compound 2 (0.6 mol,176.53 g) were added, and after reacting at 60℃for 6 hours, a polyimide precursor solution (resin polymer solution) was obtained, the solid content of the solution was 20%, and the molecular weight of the polymer was 85000.
Then, a resin composition solution 2 was prepared:
dispersion 2 (133 g,0.07 wt) was added to resin polymer solution 2 with vigorous stirring, and stirred for 1 hour to obtain resin composition solution 2.
Example 3
First, a resin polymer solution 3 is prepared:
in a 2500ml four-necked flask equipped with a thermometer and a stirrer, dry nitrogen gas was introduced, then compound 5 (0.96 mol,103.81 g), compound 9 (0.04 mol,6.33 g) and N-methylpyrrolidone (NMP, 1340 g) were added, the temperature was raised to 60℃and stirred until dissolved, then compound 1 (0.9 mol,196.31 g) and compound 3 (0.1 mol,26.82 g) were added, and after 6 hours of reaction at 60℃a polyimide precursor solution (resin polymer solution) was obtained, the solution solid content was 20%, and the polymer molecular weight was 70000.
Then, a resin composition solution 2 was prepared:
dispersion 1 (117 g,0.07 wt) was added to resin polymer solution 3 with vigorous stirring, and stirred for 1 hour to obtain resin composition solution 3.
Example 4
First, a resin polymer solution 4:
in a 2500ml four-necked flask equipped with a thermometer and a stirrer, dry nitrogen gas was introduced, then, compound 5 (0.8 mol,86.51 g), compound 6 (0.14 mol,22.15 g), compound 8 (0.04 mol,6.33 g) and N-methylpyrrolidone (NMP, 1606 g) were added, the temperature was raised to 60℃and stirred until dissolution, then, compound 2 (0.7 mol,205.95 g) and compound 3 (0.3 mol,80.45 g) were added, and after reacting at 60℃for 6 hours, a polyimide precursor solution (resin polymer solution) was obtained, the solid content of the solution was 20%, and the molecular weight of the polymer was 80000.
Then, a resin composition solution 2 was prepared:
dispersion 1 (140 g,0.07 wt) was added to resin polymer solution 4 with vigorous stirring, and stirred for 1 hour to obtain resin composition solution 4.
Example 5
First, a resin polymer solution 5 is prepared:
in a 2500ml four-necked flask equipped with a thermometer and a stirrer, dry nitrogen gas was introduced, then compound 5 (0.94 mol,101.65 g), compound 10 (0.01 mol,3.02 g) and N-methylpyrrolidone (NMP, 1585 g) were added, the temperature was raised to 60℃and stirred until dissolved, then compound 2 (0.9 mol,264.80 g) and compound 4 (0.1 mol,26.82 g) were added, and after reacting at 60℃for 6 hours, a polyimide precursor solution (resin polymer solution) was obtained, the solid content of the solution was 20%, and the polymer molecular weight was 65000.
Then, a resin composition solution 5 was prepared:
dispersion 2 (139 g,0.07 wt) was added to the resin polymer solution 5 under vigorous stirring, and stirred for 1 hour to obtain a resin composition solution 5.
Example 6
First, a resin polymer solution 6:
in a 2500ml four-necked flask equipped with a thermometer and a stirrer, dry nitrogen was introduced, and then, compound 5 (0.9 mol,97.33 g), compound 7 (0.05 mol,10.41 g), compound 8 (0.05 mol,7.91 g) and N-methylpyrrolidone (NMP, 1482 g) were added, the temperature was raised to 60℃and stirred until dissolved, then, compound 1 (0.5 mol,109.06 g), compound 2 (0.45 mol,132.40 g) and compound 4 (0.05 mol,13.41 g) were added, and after reacting at 60℃for 6 hours, a polyimide precursor solution (resin polymer solution) was obtained, the solid content of the solution was 20%, and the molecular weight of the polymer was 85000.
Then, a resin composition solution 6 was prepared:
dispersion 1 (130 g,0.07 wt) was added to the resin polymer solution 6 under vigorous stirring, and stirred for 1 hour to obtain a resin composition solution 6.
Example 7
First, a resin polymer solution 7 was prepared:
in a 2500ml four-necked flask equipped with a thermometer and a stirrer, dry nitrogen gas was introduced, then compound 5 (0.7 mol,75.70 g), compound 7 (0.29 mol,60.40 g) and N-methylpyrrolidone (NMP, 1706 g) were added, the temperature was raised to 60℃and stirred until dissolved, then compound 2 (0.8 mol,235.38 g), compound 3 (0.1 mol,26.82 g) and compound 4 (0.1 mol,26.82 g) were added, and after reacting at 60℃for 6 hours, a polyimide precursor solution (resin polymer solution) was obtained, the solid content of the solution was 20%, and the polymer molecular weight was 75000.
Then, a resin composition solution 7 was prepared:
dispersion 2 (149 g,0.07 wt) was added to the resin polymer solution 7 under vigorous stirring, and stirred for 1 hour to obtain a resin composition solution 7.
Example 8
First, a resin polymer solution 8 was prepared:
in a 2500ml four-necked flask equipped with a thermometer and a stirrer, dry nitrogen gas was introduced, then compound 5 (0.95 mol,102.73 g), compound 8 (0.03 mol,4.75 g) and N-methylpyrrolidone (NMP, 1607 g) were added, the temperature was raised to 60℃and stirred until dissolved, then compound 2 (1.00 mol,294.22 g) was added, and after reacting at 60℃for 6 hours, a polyimide precursor solution (resin polymer solution) was obtained, the solid content of the solution was 20%, and the molecular weight of the polymer was 65000.
Then, a resin composition solution 8 was prepared:
dispersion 1 (141 g,0.07 wt) was added to the resin polymer solution 8 under vigorous stirring, and stirred for 1 hour to obtain a resin composition solution 8.
Example 9
First, a resin polymer solution 9 was prepared:
in a 2500ml four-necked flask equipped with a thermometer and a stirrer, dry nitrogen gas was introduced, then compound 5 (0.85 mol,91.92 g), compound 8 (0.13 mol,20.57 g) and N-methylpyrrolidone (NMP, 1475 g) were added, the temperature was raised to 60℃and stirred until dissolved, then compound 1 (0.5 mol,109.06 g) and compound 2 (0.5 mol,147.11 g) were added, and after reacting at 60℃for 6 hours, a polyimide precursor solution (resin polymer solution) was obtained, the solid content of the solution was 20%, and the polymer molecular weight was 75000.
Then, a resin composition solution 9 was prepared:
dispersion 1 (129 g,0.07 wt) was added to the resin polymer solution 9 under vigorous stirring, and stirred for 1 hour to obtain a resin composition solution 9.
Comparative example 1
First, a resin polymer solution 10 is prepared:
in a 2500ml four-necked flask equipped with a thermometer and a stirrer, dry nitrogen gas was introduced, then compound 5 (1.00 mol,108.14 g) and N-methylpyrrolidone (NMP, 1457 g) were added, the temperature was raised to 60℃and stirred until dissolved, then compound 1 (0.5 mol,109.06 g), compound 2 (0.5 mol,147.11 g) were added, and after reacting at 60℃for 6 hours, a polyimide precursor solution (resin polymer solution) was obtained, the solid content of the solution was 20%, and the polymer molecular weight was 85000.
Then, a resin composition solution 10 was prepared:
dispersion 1 (128 g,0.07 wt) was added to the resin polymer solution 10 with vigorous stirring, and after stirring for 1 hour, a resin composition solution 10, comparative example 1, was obtained.
Comparative example 2
First, a resin polymer solution 11 is prepared:
in a 2500ml four-necked flask equipped with a thermometer and a stirrer, dry nitrogen gas was introduced, then compound 5 (1.00 mol,108.14 g) and N-methylpyrrolidone (NMP, 1457 g) were added, the temperature was raised to 60℃and stirred until dissolved, then compound 1 (0.5 mol,109.06 g), compound 2 (0.5 mol,147.11 g) were added, and after reacting at 60℃for 6 hours, a polyimide precursor solution (resin polymer solution) was obtained, the solid content of the solution was 20%, and the polymer molecular weight was 85000.
Then, a resin composition solution 11 was prepared:
dispersion 1 (128 g,0.07 wt) was added to resin polymer solution 11 with vigorous stirring, and after stirring for 1 hour, resin composition solution 11, comparative example 2, was obtained.
The method for measuring the relevant parameters of the resin films obtained in examples 1 to 9 and comparative examples 1 to 2 according to the present application is as follows:
(1) Method for measuring molecular weight
The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were measured using HLC-8020 manufactured by Tosoh, tosoh.
(2) Film thickness measuring method
The test was performed using a VM-1020 apparatus manufactured by Dainippon Scrren Mfg co., ltd.
(3) Method for measuring linear thermal expansion coefficient and absorbance
Sample preparation: the solution of the resin composition was spin-coated onto an 8-inch silicon wafer. Next, the film was pre-baked with a heating plate (using a coating and developing apparatus Act-8 made of Dong-electric) at 120℃for 3 minutes to prepare a pre-baked film. Baking with inert gas oven (Koyo Thermo Systems Co., ltd., apparatus CLH-21CD (V) -CCC) at a temperature of not more than 20ppm, heating to 400deg.C at a rate of 5deg.C/min, heating at 400deg.C for 1 hr, and cooling to 50deg.C at a rate of 5deg.C/min to obtain baked film. Then, the baked film was immersed in a hydrofluoric acid solution for 1 to 4 minutes, and then peeled off from the substrate, and air-dried to obtain a heat-treated film. In spin coating, the rotation speed was adjusted so that the film thickness after the heat treatment was controlled to about 10. Mu.m.
Testing the coefficient of linear thermal expansion: the obtained heat-treated film was prepared into a sample of a desired size for testing, and the sample was measured under a nitrogen flow using a mechanical analyzer (TMA 4000 manufactured by Perkin Elmer). The temperature raising method in the test was performed under the following conditions: step 1, heating to 300 ℃ at room temperature at a heating rate of 5 ℃/min, and removing water adsorbed by a sample; step 2, cooling from 300 ℃ to room temperature in an air atmosphere at a cooling rate of 5 ℃/min; step 3, the measurement is performed at a temperature rising rate of 5 ℃ per minute from room temperature, and then an average value of linear thermal expansion coefficients of 50 to 300 ℃ is obtained.
Testing absorbance: the resulting heat-treated film was measured by an ultraviolet-visible spectrophotometer (SHIMADZU UV-2600 i), and the average absorbance was measured at a wavelength ranging from 400nm to 800 nm.
(4) Determination of film residual stress
Sample preparation: a solution of the resin composition was spin-coated on a glass substrate (EAGLE, corning) 50mm by 0.7mm thick using a spin coater MS-B150, manufactured by MIKASA CO., LTDSlide); next, the resin film was obtained by baking with a heating plate (heating plate NEO HOTPLATE HI-1000 manufactured by Suwang ASONE) at 120℃for 3 minutes. The resin film was baked using an inert gas oven (Koyo Thermo Systems Co., ltd., apparatus CLH-21CD (V) -CCC) and the oxygen concentration was set to 20ppm or less, and the temperature was raised to 400℃at a rate of 5℃per minute, and the resin film was subjected to heat treatment at 400℃for 1 hour, and then cooled to 50℃at a rate of 5℃per minute, to prepare a baked resin film. The residual stress of the films was then tested using a film stress meter (Toho Technology, model FLX-2320). The residual stress is less than 20MPa and is good, the residual stress is less than 25MPa and is O, the residual stress is less than 40MPa and is delta, and the residual stress is greater than 40MPa and is gamma.
The required raw materials and test results for examples 1-9 and comparative examples 1,2 are shown in Table 1 below:
table 1: recipe and test results table
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Wherein the units of the values of the compounds 1 to 10 are mol, the units of the values of the dispersion are wt%, and the units of the values of the film thickness are μm; the unit of the thermal expansion coefficient value is ppm/DEG C; the tensile strength value is expressed in MPa; the residual stress is less than 20 and is zero, the residual stress is less than 25 and is O, the residual stress is less than 40 and is delta, and the residual stress is more than 40 and is gamma.
As shown in table 1, the resin composition of comparative example 1 did not contain the azulene structure of formula 3 or formula 4, and the technical effects of the absorbance and residual stress finally obtained were significantly inferior to those of examples 1 to 9. The resin composition of comparative example 2 used a larger amount of pigment dispersion than the structure of azulene in formula 3 or formula 4, and the mechanical properties of the resulting films were significantly inferior to those of examples 1-9.
In addition, the formulation monomer of example 9, which contains the formula 1 of formula 3 and the formula 2 in an amount exceeding 10% by mole, has relatively inferior technical effects compared to the preferred examples 1 to 8, but has a significant improvement effect compared to the technical effects of comparative example 1.
In summary, according to the resin polymer and the organic electroluminescent device having the same, the azulene compound structure is used, unlike other ways of preparing black polyimide films, namely, a way of doping black organic or inorganic dye into the polymer slurry, the azulene compound having a light absorption function of more than 400nm is directly added into the chain structure of the polymer, so that the polymer with uniformly distributed groups for reducing the transmissivity can be simply obtained, and in the subsequent film forming process, the added azulene compound is directly present in the chain structure, so that the variety and quantity of doped inorganic particles or organic dye are reduced, the influence on the overall performance of the film is small, and the film with excellent mechanical properties such as tensile strength, tensile modulus, breaking elongation and the like can be obtained.
Meanwhile, due to the planar structure of azulene molecules, the thermal expansion coefficient and the warping stress of the final film can be reduced to a certain extent, so that the film can be combined with a substrate (silicon wafer, glass plate) and the like more effectively, and the device performance and the yield are improved.
The black resin film with low light transmittance and excellent film performance can be obtained by using the resin composition provided by the application. Because of the excellent performance, the resin film can be used for an organic electroluminescent device substrate, and can also be used for the fields of liquid crystal display substrates, semiconductor light-emitting diode display substrates, flexible color filter substrates, flexible ink display screen substrates and the like.
And after the black substrate film obtained by using the resin composition provided by the application is used, the display device with high contrast, improved luminous efficiency and smaller chromatic aberration offset value can be obtained.
The foregoing is a further detailed description of the application in connection with the preferred embodiments, and it is not intended that the application be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the application, and these should be considered to be within the scope of the application.

Claims (9)

1. A resin composition comprising a polymer comprising a structure represented by formula 1 and/or formula 2:
wherein R is 1 、R 3 Each independently is a tetravalent organic residue;
wherein R is 2 、R 4 Each independently is a divalent organic residue or terminal residue, R 2 、R 4 Each independently selected from a divalent organic residue represented by formula 3 or a terminal residue represented by formula 4,
wherein R is 7 -R 9 Selected from C 1 -C 20 Alkyl, C of (2) 1 -C 20 Cycloalkyl, C 1 -C 20 Silane group, C of (C) 1 -C 20 Ester group, C 1 -C 20 Alkoxy, C 1 -C 24 Aromatic radicals, C 1 -C 24 One or more of heteroaryl, cyano, carboxyl, amino, alkylamino, nitro, amido and halogen, n is an integer of 0-2, m is an integer of 0-4, and o is an integer of 0-7;
R 5 and R is 6 Each independently selected from H, C 1 -C 20 Alkyl, C of (2) 1 -C 20 A silane group, a metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion.
2. The resin composition according to claim 1, wherein R is 1 、R 3 Each independently selected from tetravalent C 6 -C 20 Aryl groups of (a).
3. The resin composition of claim 1, wherein the number of carbon atoms in the structure of formula 3 is less than 40.
4. The resin composition of claim 1, wherein the polymer comprises at least one rigid structural unit.
5. The resin composition of claim 4, wherein the rigid structural unit is a mono-benzene, biphenyl or polycyclic aromatic hydrocarbon type structure.
6. The resin composition according to any one of claims 1 to 5, wherein the structural units of formula 3 and/or formula 4 are contained in an amount of 0.1 to 10% by mole based on the total structural units in the polymer.
7. The resin composition according to claim 1, further comprising one or more of a pigment, a dye, an inorganic particle, a sensitizer, and an adhesive.
8. A resin film prepared from the resin composition according to any one of claims 1 to 5 and 7.
9. A display device comprising a substrate on which the resin film according to claim 8 is provided.
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CN111601840A (en) * 2018-01-18 2020-08-28 东丽株式会社 Resin composition for display substrate, resin film for display substrate, laminate comprising same, image display device, organic EL display, and methods for producing same
WO2020175150A1 (en) * 2019-02-28 2020-09-03 東レ株式会社 Resin composition, black resin film, layered body and display device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004217602A (en) * 2003-01-17 2004-08-05 Kotobuki Seiyaku Kk Azulene derivative having anti-helicobacter pylori activity, method for producing the same and medicine containing the same
JP2008122501A (en) * 2006-11-09 2008-05-29 Sumitomo Chemical Co Ltd Positive type radiation-sensitive resin composition
WO2013133168A1 (en) * 2012-03-05 2013-09-12 日産化学工業株式会社 Polyamic acid and polyimide
CN104114606A (en) * 2012-03-05 2014-10-22 日产化学工业株式会社 Polyamic acid and polyimide
CN111601840A (en) * 2018-01-18 2020-08-28 东丽株式会社 Resin composition for display substrate, resin film for display substrate, laminate comprising same, image display device, organic EL display, and methods for producing same
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