CN117348340A - Negative photosensitive resin composition, cured film, method for producing same, EL element, and display device - Google Patents

Negative photosensitive resin composition, cured film, method for producing same, EL element, and display device Download PDF

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Publication number
CN117348340A
CN117348340A CN202210725485.5A CN202210725485A CN117348340A CN 117348340 A CN117348340 A CN 117348340A CN 202210725485 A CN202210725485 A CN 202210725485A CN 117348340 A CN117348340 A CN 117348340A
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Prior art keywords
negative photosensitive
photosensitive resin
resin composition
unsubstituted
substituted
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CN202210725485.5A
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钱彬
于培培
吴全领
张学龙
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Changzhou Lider Electronic New Material Co ltd
Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Changzhou Lider Electronic New Material Co ltd
Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Priority to CN202210725485.5A priority Critical patent/CN117348340A/en
Priority to PCT/CN2023/101514 priority patent/WO2023246811A1/en
Publication of CN117348340A publication Critical patent/CN117348340A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention provides a negative photosensitive resin composition, a cured film, a preparation method thereof, an EL element and a display device. The negative photosensitive resin composition comprises (A) an alkali-soluble resin containing a polyimide structure; (B) a radical polymerizable compound; (C) At least one photopolymerization initiator having a structure represented by the following formula (I); and optionally (D) a black dye and/or pigment; by applying the technical scheme of the invention, the negative photosensitive composition provided by the invention not only has excellent heat resistance and light-shading property, but also can not cause device pollution when no gas leakage is detected in a high-temperature environment after being applied to a light-emitting device, and has wide application prospect.

Description

Negative photosensitive resin composition, cured film, method for producing same, EL element, and display device
Technical Field
The invention relates to the technical field of photosensitive resin compositions, in particular to a negative photosensitive resin composition, a cured film, a preparation method of the cured film, an EL element and a display device.
Background
In recent years, in display with a thin display such as a smart phone, a tablet PC, and a television, a large number of products using an organic electroluminescence (hereinafter referred to as "EL") display have been developed.
The organic EL display has a self-light emitting element that emits light using energy generated by recombination of electrons injected from a cathode and holes injected from an anode, however, electron or hole movement tends to be hindered, and deterioration of light emitting efficiency of the self-light emitting element or loss of a light emitting material or deterioration of life of the self-light emitting element is liable to occur. Since the pixel dividing layer is formed at a position adjacent to the self-light emitting element, outgas from the pixel dividing layer and outflow of ion components may be a cause of a reduction in the lifetime of the organic EL display, and thus the pixel dividing layer is required to have high heat resistance. In the prior art, a supported photosensitive resin composition containing polyimide and oxime ester photopolymerization initiator with high heat resistance is generally used for solving the problem of high heat resistance, however, self-luminous devices prepared by using the composition often have the conditions of leakage of overflow gas and pollution to devices in a high-temperature environment.
In view of this, the present invention has been made.
Disclosure of Invention
The invention mainly aims to provide a negative photosensitive resin composition, a cured film, a preparation method thereof, an EL element and a display device, and aims to solve the problems that a self-luminous device prepared from the load photosensitive resin composition containing polyimide and oxime ester photopolymer initiator in the prior art has overflow gas leakage and pollutes the device in a high-temperature environment.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a negative photosensitive resin composition comprising: (a) an alkali-soluble resin containing a polyimide structure; (B) a radical polymerizable compound; (C) At least one photopolymerization initiator having a structure represented by the following formula (I); and optionally (D) a black dye and/or pigment;
wherein Ar is a substituted or unsubstituted C6-C30 aryl group; r is R 1 And R is 2 Each independently represents a substituted or unsubstituted C1-C15 straight chain alkyl group, a substituted or unsubstituted C3-C15 branched chain alkyl group, a substituted or unsubstituted C3-C15 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C4-C20 heteroaryl group; r is R 3 Is methyl.
Further, in the above formula (I), ar is selected from at least one of the following substituted or unsubstituted groups:
wherein R is 4 、R 5 、R 6 、R 7 And R is 8 Each independently represents hydrogen, a substituted or unsubstituted C1-C15 straight chain alkyl group, a substituted or unsubstituted C3-C15 branched alkyl group, or a substituted or unsubstituted C3-C15 cycloalkyl group.
Further, ar is selected from at least one of the following groups:
further, the photopolymerization initiator is selected from at least one of the following compounds:
further, the photopolymerization initiator is selected from at least one of the following compounds:
further, the alkali-soluble resin containing a polyimide structure is selected from at least one of polyimide, polyimide precursor, polybenzoxazole or polybenzoxazole precursor; and/or the radical polymerizable compound is an acrylic ester compound.
Further, the black dye is a dye specified by the dye index of solvent black 27 to 47; and/or the black pigment is selected from at least one of carbon black, carbon nanotubes, acetylene black, iron black, aniline black, titanium black, perylene pigments or lactam pigments.
Further, the negative photosensitive resin composition comprises (A) 30-80 parts by weight of an alkali-soluble resin containing a polyimide structure; (B) 10-50 parts of a radical polymerizable compound; (C) 2-8 parts of a photopolymerization initiator; and optionally (D) 2-8 parts of black dye and/or pigment.
Further, the negative photosensitive resin composition further comprises an auxiliary agent, wherein the auxiliary agent comprises at least one of a sensitizer, a photoinitiator, a leveling agent, a dispersing agent, a curing agent, a surfactant, a defoaming agent or a storage enhancer. In order to achieve the above object, according to a second aspect of the present invention, there is also provided a cured film, the raw material of which is any one of the negative photosensitive resin compositions provided in the first aspect.
According to a third aspect of the present invention, there is also provided a method for producing a cured film provided in the above second aspect, the method comprising: step S1, dissolving or dispersing a negative photosensitive resin composition in a solvent to obtain a negative photosensitive coating liquid; step S2, coating the negative photosensitive coating liquid on the surface of a substrate, removing the solvent to obtain a coating film to be cured, preferably removing the solvent by heating, wherein the heating temperature is preferably 70-130 ℃; step S3, initiating polymerization is carried out on the film to be cured, the film to be cured is cured to form a film, and the initiation polymerization is preferably carried out by an energy radiation mode; and S4, sequentially carrying out development treatment, washing and heating on the film to obtain a cured film, wherein the development treatment time is preferably 30-180S, the heating temperature is preferably 100-350 ℃, and the heating time is preferably 2-20 min.
According to a fourth aspect of the present invention, there is also provided an EL element comprising any one of the negative photosensitive resin compositions provided in the first aspect or the cured film provided in the second aspect.
According to a fifth aspect of the present invention, there is also provided a display device comprising any one of the negative photosensitive resin composition provided in the first aspect, the cured film provided in the second aspect, or the EL element provided in the fourth aspect.
By applying the technical scheme of the invention, the negative photosensitive composition provided by the invention not only has excellent heat resistance and light-shading property, but also can not cause device pollution when no gas leakage is detected in a high-temperature environment after being applied to a light-emitting device, and has wide application prospect.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed in the background of the present application, the self-luminescent devices prepared in the prior art using a supported photosensitive resin composition comprising a high-heat polyimide and an oxime ester-based photopolymerization initiator tend to suffer from leakage of out-gassing and contamination of the devices under high-temperature conditions. In order to solve this problem, the present application provides a negative photosensitive resin composition, a cured film, a method for producing the same, an EL element, and a display device.
In an exemplary embodiment of the present application, there is provided a negative photosensitive resin composition including the following components: (a) an alkali-soluble resin containing a polyimide structure; (B) a radical polymerizable compound; (C) At least one photopolymerization initiator having a structure represented by the following formula (I) and optionally (D) a black dye and/or fuel.
In the formula (I), ar is a substituted or unsubstituted C6-C30 aryl group; r is R 1 And R is 2 Each independently represents a substituted or unsubstituted C1-C15 straight chain alkyl group, a substituted or unsubstituted C3-C15 branched chain alkyl group, a substituted or unsubstituted C3-C15 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C4-C20 heteroaryl group; r is R 3 Is methyl.
By applying the technical scheme, the negative photosensitive composition provided by the invention not only has excellent heat resistance and light shading property, but also can not cause device pollution when no gas leakage is detected in a high-temperature environment after being applied to a light-emitting device, and has wide application prospect.
In order to further reduce the gas leakage property of the photovoltaic device produced from the negative photosensitive resin composition, it is preferable that Ar is at least one selected from the group consisting of:
wherein the R is 4 、R 5 、R 6 、R 7 And R is 8 Each independently represents hydrogen, a substituted or unsubstituted C1-C15 straight chain alkyl group, a substituted or unsubstituted C3-C15 branched alkyl group, or a substituted or unsubstituted C3-C15 cycloalkyl group.
In some embodiments of the present application, when Ar is selected from at least one of the following groups, the gas leakage resistance of the photovoltaic device prepared from the negative photosensitive resin composition is more excellent.
In this application, "×" represents the attachment site of a chemical group.
In some preferred embodiments of the present application, it is preferable that the photopolymerization initiator is at least one selected from the following compounds, so as to further reduce the possibility of gas leakage of the negative photosensitive resin composition applied to the optoelectronic device and further avoid contamination of the device.
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In some embodiments of the present application, when the photopolymerization initiator is selected from at least one of the following compounds, the gas leakage resistance of the negative-type photosensitive resin composition including the same is more remarkable.
The above-mentioned alkali-soluble resin containing a polyimide structure is not limited, and any alkali-soluble resin containing a polyimide structure having excellent heat resistance may be used, and particularly when the above-mentioned alkali-soluble resin containing a polyimide structure is selected from any one or a mixture of a plurality of polyimides, polyimide precursors, polybenzoxazoles or polybenzoxazole precursors, the heat resistance of the photoelectric device produced therefrom is more excellent.
The type of the radical polymerizable compound is not limited, and any radical polymerizable compound that can be initiated using the photopolymerization initiator may be used, and from the viewpoint of improving the initiation efficiency, the radical polymerizable compound is preferably an acrylic compound, and includes, but is not limited to, a mixed resin formed of any one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, pentaerythritol tetraacrylate, and trimethylolpropane triacrylate.
The type of the black dye or black pigment is not limited, and any substance capable of providing black coloring ability may be used. In order to further improve the dispersibility and coloring performance of the black dye, it is preferable that the black dye is a dye defined by the dye index (c.i.) of solvent black 27 to 47. In order to further improve the dispersibility and colorability of the black pigment, it is preferable that the black pigment is a mixed pigment of any one or more of carbon black, carbon nanotubes, acetylene black, iron black, aniline black, titanium black, perylene pigments and lactam pigments.
In order to further improve the performance of the negative photosensitive resin composition, it is preferable that the negative photosensitive resin composition further includes an auxiliary agent including, but not limited to, a mixed auxiliary agent formed of any one or more of a sensitizer, a photoinitiator, a leveling agent, a dispersant, a curing agent, a surfactant, an antifoaming agent, and a storage enhancer.
In some embodiments of the present application, in order to further improve the heat resistance, light shielding property, and gas leakage prevention property of an optoelectronic device to which the negative photosensitive resin composition is applied, it is preferable that the negative photosensitive resin composition includes: 30-80 parts by mass of an alkali-soluble resin containing a polyimide structure, 10-50 parts by mass of a radical-polymerizable compound, 2-8 parts by mass of a photopolymerization initiator, and optionally 2-8 parts by mass of a black dye and/or pigment.
Typically, but not limited to, in the negative photosensitive resin composition, the mass fraction of the alkali-soluble resin containing a polyimide structure is, for example, 30 parts, 35 parts, 40 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 80 parts or any two values in the range; the mass fraction of the radical polymerizable compound is, for example, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts or a range value consisting of any two values; the mass fraction of the photopolymerization initiator is, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or a range value composed of any two values; the mass fraction of the black dye and/or pigment is, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or any two values.
In another exemplary embodiment of the present application, there is also provided a cured film, the raw material of which is any one of the negative photosensitive resin compositions provided in the first exemplary embodiment described above.
The cured film provided by the application is prepared from the negative photosensitive resin composition serving as a raw material, has excellent light resistance and photophobic performance, has no gas leakage in a high-temperature environment, cannot cause pollution of photoelectric devices, and has a wide application prospect.
In a third exemplary embodiment of the present application, there is also provided a method for preparing the above cured film, the method comprising the steps of: step S1, dissolving or dispersing a negative photosensitive resin composition in a solvent to obtain a negative photosensitive coating liquid; step S2, coating the negative photosensitive coating liquid on the surface of a substrate, and removing the solvent to obtain a film to be cured; step S3, initiating polymerization of the film to be cured, and curing the film to be cured to form a film; and step S4, sequentially performing development treatment, washing and heating on the film to obtain a cured film.
The preparation method of the cured film provided by the invention has the advantages of simple process and convenience in operation, is suitable for large-scale production, and can effectively improve the preparation efficiency and reduce the production cost.
In the above step S1, the type of the solvent is not limited, but a low boiling point solvent including but not limited to propylene glycol methyl ether acetate is preferable from the viewpoint of facilitating the subsequent removal.
In order to avoid the influence of agglomeration or uneven dispersion of the composition in the coating liquid on the uniformity of subsequent coating, it is preferable that the negative photosensitive coating liquid is filtered before coating, for example, a microporous filter having a pore diameter of 0.05 to 1.0 μm is used.
In order to avoid the above-mentioned composition not being uniformly dispersed or dissolved in the solvent, it is preferable to perform dispersion mixing by using a dispersion mixing apparatus such as a ball mill, a sand mill, a bead mill, a paint mixer, a swing mill, or the like, a blade type such as a kneader, a paddle type mixer, a planetary type mixer, a henschel mixer, or the like, a roll type such as a 3-roll type mixer, a kneader, a colloid mill, an ultrasonic wave, a homogenizer, a rotation/revolution mixer, or the like by a method known in the art. From the viewpoints of dispersion efficiency and microdispersion, it is preferable to use a bead mill for dispersion mixing.
In the above step S2, the coating method is not limited, and includes, but is not limited to, a spray method, a roll coating method, a slit method, or a spin coating method. The material of the substrate is not limited, and a glass substrate is preferable.
In the step S2, the solvent is removed by heating without limitation. The heating conditions vary depending on the kind and ratio of each component of the negative photosensitive resin composition and the choice of solvent. In order to further improve the solvent removal efficiency, the heating temperature is preferably 70-130 ℃, the heating time is 1-20min if heating by a heating plate is adopted, and the heating time is initially 3-60min if heating by an oven is adopted.
In the above step S3, the form of the energy source for initiating polymerization is not limited, and ultraviolet light, visible light, infrared light, electron beam, laser lamp energy can be used to initiate polymerization of the negative photosensitive resin composition provided in the first exemplary embodiment of the present application by irradiation and to achieve rapid curing. Such energy sources for initiating polymerization include, but are not limited to: active light rays such as ultra-high pressure mercury lamp, medium pressure mercury lamp, mercury xenon lamp, low pressure mercury lamp, metal halide lamp, xenon lamp, deuterium lamp, chemical lamp, LED lamp, fluorescent lamp, tungsten lamp, nd-YAG 3-fold wave laser, he-Cd laser, nitrogen laser, xe-Cl excimer laser, xe-F excimer laser, semiconductor excited solid laser, i-ray, h-ray, g-ray, etc. having a wavelength of 200 to 500 nm; the energy source may be electron beam, α ray, β ray, γ ray, X ray, neutron ray, etc., and radiation is preferably ultraviolet ray to visible ray having a wavelength of 250 to 450 nm. The intensity of the radiation is preferably 50-100mJ/cm 2 。
In the above step S4, the developing process preferably includes: the film is developed by contacting the film with a developer, and unnecessary portions are removed to form a pattern on the film. The developer in the developer includes, but is not limited to, a mixed developer formed by any one or more of inorganic alkali compounds, primary amine compounds, secondary amine compounds, tertiary amine compounds, alcohol amine compounds, quaternary ammonium salt compounds or cyclic amine alkali compounds.
The inorganic alkali compound is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate or ammonia water, etc.; such primary amine compounds as ethylamine, n-propylamine and the like; the secondary amine compounds include diethylamine and di-n-propylamine; the tertiary amine compounds are, for example, triethylamine, methyldiethylamine, etc.; the alcohol amine compound is dimethyl ethanolamine, triethanolamine, etc.; the quaternary ammonium salt compound is, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc.; the cyclic amine base compound is, for example, pyrrole, piperidine, 1, 8-diazabicyclo [5,4,0] -7-undecene, 1, 5-diazabicyclo [4,3,0] -5-nonane, etc.
The developer is obtained by dissolving and/or dispersing a developer in a solvent, wherein the solvent of the developer comprises an aqueous solution and an optional organic solvent, and the organic solvent comprises, but is not limited to, aqueous solution organic solvents such as methanol, ethanol and the like. In order to further improve the dispersion stability of the developer, an auxiliary agent such as a surfactant may be added to the developer.
The method of the development treatment described above is not limited, and includes, but is not limited to, any one or a combination of a plurality of development methods of a liquid-filling method, a spray method, or a dipping method. In order to further improve the sufficiency of development, the development treatment time is preferably 30 to 180 seconds.
In order to avoid that excessive developing solution adheres to the surface of the developed film to affect the performance, the developed film is preferably rinsed with water for preferably 30 to 90 seconds, unnecessary portions are removed, and then air-dried with compressed air or compressed nitrogen, thereby patterning the developed film.
The heating method is not limited, and in order to further improve the heating efficiency, the patterned film is preferably heated at 100 to 350 ℃ for 2 to 20 minutes to form a cured film.
In a fourth exemplary embodiment of the present application, there is also provided an EL element including a partition wall which is any one of the cured films provided in the above third exemplary embodiment; alternatively, the partition wall may comprise any of the negative photosensitive resin compositions provided in the first exemplary embodiment.
The EL element provided by the application adopts the cured film formed by the negative photosensitive resin composition as the partition wall, gas leakage is not detected in a high-temperature environment, and the EL element can not cause pollution to photoelectric devices and has wide application prospect.
In a fifth exemplary embodiment of the present application, there is also provided a display device including any one of the negative photosensitive resin compositions provided in the first exemplary embodiment, any one of the cured films provided in the second exemplary embodiment, or the EL element provided in the fourth exemplary embodiment.
The display device provided by the application of the negative photosensitive resin composition provided by the first exemplary embodiment does not detect gas leakage in a high-temperature environment, cannot cause pollution of a light emitting device, and has a wide application prospect.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
The present example provides a cured film prepared according to the following steps:
(1) Respectively mixing alkali-soluble resin A1 containing a polyimide structure, free radical polymerizable compound B1, photopolymerization initiator C1 and carbon black in a mass part of 80:10:5:5, and dispersing and stirring in a bead mill for 3 hours to obtain a negative photosensitive resin composition;
(2) Dispersing the negative photosensitive resin composition in 100 parts by mass of solvent Polypropylene Glycol Methyl Ether Acetate (PGMEA) to obtain a negative photosensitive coating liquid;
(3) Sequentially cleaning a glass substrate (100 mm x 1mm in size) with neutral detergent (N-methylpyrrolidone, allatin), water and ethanol, drying, spin-coating the glass substrate with the negative photosensitive coating liquid, baking at 90deg.C for 125s by using a heating plate, removing the solvent, and cooling to room temperature to obtain a coating film to be solidified adhered to the substrate;
(4) The coating was formed using a mercury lamp (RW-LED-YT 200 gl) at 100mJ/cm 2 Performing sufficient exposure to obtain a cured film with a thickness of 1.5 μm;
(5) The film was immersed in a 0.04% potassium hydroxide aqueous solution at 25℃for 60 seconds to develop, then washed with water, and baked at 235℃for 15 minutes to obtain a cured film.
Example 2
This example is different from example 1 in that in step (1), an alkali-soluble resin A2 containing a polyimide structure is used instead of A1, a radical-polymerizable compound B2 is used instead of B1, and a photoinitiator C2 is used instead of C1.
Example 3
The present example is different from example 1 in that the negative photosensitive resin composition consists of A1, B1, C3 and carbon black, and the mass ratio of the four is 70:20:5:5.
Example 4
The present example is different from example 1 in that the negative photosensitive resin composition consists of A1, B1, C1 and carbon black, and the mass ratio of the four is 60:30:5:5.
Example 5
The present example is different from example 1 in that the negative photosensitive resin composition consists of A1, B1, C4 and carbon black, and the mass ratio of the four is 65:25:5:5.
Example 6
The present example is different from example 1 in that the negative photosensitive resin composition consists of A2, B1, C5 and carbon black, and the mass ratio of the four is 60:30:5:5.
Example 7
The present example is different from example 1 in that the negative photosensitive resin composition consists of A2, B2, C6 and carbon black, and the mass ratio of the four is 70:20:5:5.
Example 8
The present example is different from example 1 in that the negative photosensitive resin composition consists of A2, B1, C5 and carbon black, and the mass ratio of the four is 60:30:5:5.
Example 9
The present example is different from example 1 in that the negative photosensitive resin composition consists of A1, B2, C6 and carbon black, and the mass ratio of the four is 65:25:5:5.
Example 10
The present example is different from example 1 in that the negative photosensitive resin composition consists of A1, B1, C4 and carbon black, and the mass ratio of the four is 50:40:5:5.
Example 11
The present example is different from example 1 in that the negative photosensitive resin composition consists of A1, B2, C3 and carbon black, and the mass ratio of the four is 40:50:5:5.
Example 12
The present example is different from example 1 in that the negative photosensitive resin composition consists of A1, B1, C2 and carbon black, and the mass ratio of the four is 40:50:5:5.
Example 13
The present example is different from example 1 in that the negative photosensitive resin composition consists of A1, B1, C1 and carbon black, and the mass ratio of the four is 80:10:2:8.
Example 14
The present example is different from example 1 in that the negative photosensitive resin composition consists of A1, B1, C4 and carbon black, and the mass ratio of the four is 50:40:8:2.
Comparative example 1
This comparative example 1 provides a cured film, which is different from example 1 in that the negative photosensitive resin composition consists of A1, B1, C7 and carbon black, and the mass ratio of the four is 65:25:5:5.
Comparative example 2
This comparative example 1 provides a cured film, which is different from example 1 in that the negative photosensitive resin composition consists of A2, B1, C8 and carbon black, and the mass ratio of the four is 60:30:5:5.
Specific information on the above A1, A2, B1, B2, C1-C8 and carbon black are as follows:
a1 polyimide resin with GCPI-PAA brand
A2 polyimide resin, brand JCL3030
B1, pentaerythritol tetraacrylate: brand number: A-TMMT
B2, trimethylolpropane triacrylate, brand: m309
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Carbon black: brand number: ketjenbackEC 600JD.
Test example 1
The cured films provided in the above examples and comparative examples were subjected to heat resistance evaluation and light shielding evaluation, respectively, and the results are shown in table 1 below.
The specific method for testing the heat resistance comprises the following steps: the cured films were baked in a convection oven at 230 ℃ for 30 minutes, and then the chromaticity of the colored pattern before and after heating was determined to be Δe×ab, and the case where Δe×ab was 3.0 or less was evaluated as excellent heat resistance.
The specific method for the light-shielding property test comprises the following steps: the cured film was irradiated at 180W for 60 hours at a temperature of 30 ℃, a humidity of 50%, and a black panel temperature of 63 ℃, and Δe×ab was determined from chromaticity of the colored pattern before and after irradiation, and was evaluated as excellent in heat resistance when Δe×ab was 3.0 or less.
TABLE 1
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Test example 2
The cured films provided in examples and comparative examples were subjected to gas leakage tests, and the results are shown in table 2 below.
The method for testing the gas leakage comprises the following steps:
and (3) respectively taking 5g of the cured films provided by the examples and the comparative examples by adopting a GC-MS test method, cutting, placing into a headspace bottle for standby, adopting headspace sample injection, and observing whether overflow gas is produced (except carbon dioxide and self-contained solvent peaks).
Instrument: agilent 7890B gas chromatograph;
chromatographic column: agilent HP-5ms column vaporization temperature: programming the temperature to 280 ℃): 60-3 min-20 ℃/min-280-10 min;
headspace conditions: heating box: quantitative loop at 110 ℃): 120 ℃ transmission line: equilibrium time at 140 ℃): 30min;
mass spectrometry conditions: ion source temperature: electron energy at 280 ℃): 70ev scan range (m/z): 30-400;
TABLE 2
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From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
the cured film prepared from the negative photosensitive composition provided by the application has the advantages that no gas leakage is detected in a high-temperature environment, the cured film can not cause device pollution after being applied to a light-emitting device, and the application prospect is wide.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A negative photosensitive resin composition, characterized in that the composition comprises the following components:
(A) An alkali-soluble resin containing a polyimide structure;
(B) A radical polymerizable compound;
(C) At least one photopolymerization initiator having a structure represented by the following formula (I);
optionally, a combination of a plurality of metal elements
(D) Black dyes and/or pigments;
wherein Ar is a substituted or unsubstituted C6-C30 aryl group; r is R 1 And R is 2 Each independently represents a substituted or unsubstituted C1-C15 straight chain alkyl group, a substituted or unsubstituted C3-C15 branched chain alkyl group, a substituted or unsubstituted C3-C15 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C4-C20 heteroaryl group; r is R 3 Is methyl.
2. The negative photosensitive resin composition according to claim 1, wherein in the formula (I), ar is selected from at least one of substituted or unsubstituted following groups:
wherein the R is 4 、R 5 、R 6 、R 7 And R is 8 Each independently represents hydrogen, a substituted or unsubstituted C1-C15 linear alkyl group, a substituted or unsubstituted C3-C15 branched alkyl group, or a substituted or unsubstituted C3-C15 cycloalkyl group;
preferably, ar is selected from at least one of the following groups:
3. the negative photosensitive resin composition according to claim 1, wherein the photopolymerization initiator is selected from at least one of the following structural compounds:
preferably, the photopolymerization initiator is selected from at least one of the following structural compounds:
4. the negative photosensitive resin composition according to claim 1, wherein the alkali-soluble resin containing a polyimide structure is selected from at least one of polyimide, a polyimide precursor, polybenzoxazole or a polybenzoxazole precursor;
and/or the free radical polymerizable compound is an acrylic ester compound.
5. The negative photosensitive resin composition according to claim 1, wherein the black dye is a dye specified by a dye index of solvent black 27 to 47; and/or the black pigment is at least one selected from carbon black, carbon nanotubes, acetylene black, iron black, aniline black, titanium black, perylene pigments or lactam pigments.
6. The negative-type photosensitive resin composition according to any one of claims 1 to 5, wherein the composition comprises, in parts by mass, (a) 30 to 80 parts of the alkali-soluble resin containing a polyimide structure, (B) 10 to 50 parts of the radical-polymerizable compound, (C) 2 to 8 parts of the photopolymerization initiator, and optionally (D) 2 to 8 parts of a black dye and/or pigment;
preferably, the composition further comprises an auxiliary agent comprising at least one of a sensitizer, a photoinitiator, a leveling agent, a dispersant, a curing agent, a surfactant, an antifoaming agent, or a storage enhancer.
7. A cured film, wherein the raw material of the cured film is the negative photosensitive resin composition according to any one of claims 1 to 6.
8. The method for producing a cured film according to claim 7, comprising:
step S1, dissolving or dispersing the negative photosensitive resin composition in a solvent to obtain a negative photosensitive coating liquid;
step S2, coating the negative photosensitive coating liquid on the surface of a substrate, removing the solvent to obtain a coating film to be solidified, and preferably removing the solvent by heating, wherein the heating temperature is preferably 70-130 ℃;
step S3, initiating polymerization is carried out on the film to be cured, the film to be cured is cured to form a film, and the initiation polymerization is preferably carried out by means of energy radiation;
and S4, sequentially carrying out development treatment, washing and heating on the coating to obtain the cured film, wherein the development treatment time is preferably 30-180S, the heating temperature is preferably 100-350 ℃, and the heating time is preferably 2-20 min.
9. An EL element comprising the negative photosensitive resin composition according to any one of claims 1 to 6 or the cured film according to claim 7.
10. A display device comprising the negative photosensitive resin composition according to any one of claims 1 to 6, the cured film according to claim 7, or the EL element according to claim 8.
CN202210725485.5A 2022-06-24 2022-06-24 Negative photosensitive resin composition, cured film, method for producing same, EL element, and display device Pending CN117348340A (en)

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JP4315429B2 (en) * 2003-09-26 2009-08-19 日本化薬株式会社 Negative coloring photosensitive composition
CN102459171B (en) * 2009-06-17 2014-07-09 东洋油墨Sc控股株式会社 Oxime ester compound, radical polymerization initiator, polymerizable composition, negative resist and image pattern
CN103819583B (en) * 2014-03-18 2016-05-18 常州强力电子新材料股份有限公司 A kind of containing two oxime ester lightlike initiating agents of nitro and its preparation method and application
CN104076606B (en) * 2014-07-15 2019-12-03 常州强力电子新材料股份有限公司 A kind of photosensitive composite and its application containing oxime ester lightlike initiating agent
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CN109666088A (en) * 2017-10-16 2019-04-23 北京英力科技发展有限公司 A kind of diketone oxime ester compound and its manufacturing method and application
KR102228630B1 (en) * 2018-12-28 2021-03-16 주식회사 삼양사 Carbazole multi β-oxime ester derivative compounds and, photopolymerization initiator and photoresist composition containing the same
JP7371554B2 (en) * 2020-03-30 2023-10-31 日油株式会社 Bisoxime ester photopolymerization initiator, polymerizable composition, cured product and method for producing the same

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