WO2023246811A1 - Negative photosensitive resin composition, cured film and preparation method therefor, el element, and display apparatus - Google Patents

Negative photosensitive resin composition, cured film and preparation method therefor, el element, and display apparatus Download PDF

Info

Publication number
WO2023246811A1
WO2023246811A1 PCT/CN2023/101514 CN2023101514W WO2023246811A1 WO 2023246811 A1 WO2023246811 A1 WO 2023246811A1 CN 2023101514 W CN2023101514 W CN 2023101514W WO 2023246811 A1 WO2023246811 A1 WO 2023246811A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative photosensitive
resin composition
photosensitive resin
unsubstituted
substituted
Prior art date
Application number
PCT/CN2023/101514
Other languages
French (fr)
Chinese (zh)
Inventor
钱彬
Original Assignee
常州强力先端电子材料有限公司
常州强力电子新材料股份有限公司
常州力得尔电子新材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 常州强力先端电子材料有限公司, 常州强力电子新材料股份有限公司, 常州力得尔电子新材料有限公司 filed Critical 常州强力先端电子材料有限公司
Publication of WO2023246811A1 publication Critical patent/WO2023246811A1/en

Links

Classifications

    • 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

Definitions

  • the present application relates to the technical field of photosensitive resin compositions. Specifically, it relates to a negative photosensitive resin composition, a cured film and a preparation method thereof, an EL element and a display device.
  • EL organic electroluminescence
  • Organic EL displays have self-luminous elements that emit light using the energy generated by the recombination of electrons injected from the cathode and holes injected from the anode.
  • the movement of electrons or holes is often hindered, which easily affects the luminous efficiency of the self-luminous element.
  • the reduction or loss of the luminescent material will reduce the life of the self-luminous element. Since the pixel dividing layer is formed adjacent to the self-luminous element, degassing and outflow of ion components from the pixel dividing layer may cause a reduction in the life of the organic EL display. Therefore, the pixel dividing layer is required to have high heat resistance. sex.
  • supported photosensitive resin compositions containing highly heat-resistant polyimides and oxime ester photopolymerization initiators are usually used to solve the problem of high heat resistance.
  • self-contained photosensitive resin compositions prepared using such compositions Light-emitting devices often leak gas and contaminate the devices in high-temperature environments.
  • the main purpose of this application is to provide a negative photosensitive resin composition, a cured film and a preparation method thereof, an EL element and a display device to solve the problem of polyimide and oxime ester photopolymer initiators in the prior art.
  • the self-luminous device prepared from the loaded photosensitive resin composition has the problem of leakage of overflow gas and contamination of the device in a high temperature environment.
  • a negative photosensitive resin composition which composition includes the following components: (A) an alkali-soluble resin containing a polyimide structure; (B) ) Radically polymerizable compound; (C) At least one photopolymerization initiator having a structure represented by the following formula (I); and optionally (D) black dye and/or pigment;
  • Ar is a substituted or unsubstituted C6-C30 aryl group
  • R 1 and R 2 each independently represent a substituted or unsubstituted C1-C15 linear alkyl group, a substituted or unsubstituted C3-C15 branched chain Alkyl group, substituted or unsubstituted C3-C15 cycloalkyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C4-C20 heteroaryl group;
  • R 3 is methyl.
  • Ar is selected from at least one of the following substituted or unsubstituted groups:
  • Ar is selected from at least one of the following groups:
  • photopolymerization initiator is selected from at least one compound with the following structure:
  • 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 carbon black, carbon nanotubes, acetylene black, iron black, aniline black, titanium black, titanium black, perylene at least one type of pigment or lactam pigment.
  • the above-mentioned negative photosensitive resin composition also includes auxiliaries, which include sensitizers, photoinitiators, leveling agents, dispersants, curing agents, surfactants, defoaming agents or storage enhancers. of at least one.
  • auxiliaries which include sensitizers, photoinitiators, leveling agents, dispersants, curing agents, surfactants, defoaming agents or storage enhancers. of at least one.
  • auxiliaries which include sensitizers, photoinitiators, leveling agents, dispersants, curing agents, surfactants, defoaming agents or storage enhancers. of at least one.
  • auxiliaries which include sensitizers, photoinitiators, leveling agents, dispersants, curing agents, surfactants, defoaming agents or storage enhancers. of at least one.
  • a cured film is also provided.
  • the raw material of the cured film is any negative photosensitive resin composition provided in the first aspect.
  • Step S3 initiate polymerization of the film to be cured, and solidify the film to be cured to form a film, preferably by initiating polymerization by energy radiation;
  • Step S4 sequentially develop, wash and heat the film to obtain a cured film, wherein, developing The treatment time is preferably 30 to 180 seconds, the heating temperature is preferably 100 to 350°C, and the heating time is preferably 2 to 20 minutes.
  • a display device which includes any negative photosensitive resin composition provided in the first aspect, the cured film provided in the second aspect, or the fourth aspect.
  • EL components provided by the company.
  • this application provides a negative photosensitive resin composition, a cured film and a preparation method thereof, an EL element, and a display device.
  • the negative photosensitive composition provided by this application not only has excellent heat resistance and light protection, but also has no gas leakage detected in a high temperature environment after being applied to a light-emitting device, and will not cause device pollution and has broad application prospects.
  • Ar is selected from at least one of the following groups:
  • R 4 , R 5 , R 6 , R 7 and R 8 each independently represent hydrogen, a substituted or unsubstituted C1-C15 linear alkyl group, a substituted or unsubstituted C3-C15 branched alkyl group. group, substituted or unsubstituted C3-C15 cycloalkyl group.
  • the above-mentioned photopolymerization initiator is selected from at least one of the following compounds, in order to further reduce the possibility of gas leakage when the above-mentioned negative photosensitive resin composition is applied to optoelectronic devices, and further Avoid device contamination.
  • the above-mentioned negative photosensitive resin composition further includes auxiliary agents, which include but are not limited to sensitizers, photoinitiators, leveling agents, dispersants, Mixing aids formed from any one or more of curing agents, surfactants, defoaming agents or storage enhancers.
  • auxiliary agents include but are not limited to sensitizers, photoinitiators, leveling agents, dispersants, Mixing aids formed from any one or more of curing agents, surfactants, defoaming agents or storage enhancers.
  • the mass parts of the alkali-soluble resin containing the polyimide structure are, for example, 30 parts, 35 parts, 40 parts, 50 parts, 55 parts, and 60 parts. , 65 parts, 70 parts, 80 parts or a range value consisting of any two values;
  • the mass parts of the free radical polymerizable compound are, for example, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts , 45 parts, 50 parts or a range of any two values;
  • the mass parts of the photopolymerization initiator are 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or any two parts A range of numerical 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 a range of any two parts.
  • a cured film is also provided, and the raw material of the cured film is any negative photosensitive resin composition provided in the above-mentioned first typical embodiment.
  • a method for preparing the above-mentioned cured film includes the following steps: Step S1, dissolving or dispersing the negative photosensitive resin composition in a solvent to obtain a negative photosensitive resin composition.
  • Type photosensitive coating liquid Step S2, apply the negative photosensitive coating liquid on the surface of the substrate, remove the solvent, and obtain a film to be cured;
  • Step S3 initiate polymerization of the film to be cured, and the film to be cured is solidified to form Film; step S4, the film is developed, washed and heated in sequence to obtain a cured film.
  • the preparation method of the cured film provided by this application is simple in process, easy to operate, suitable for large-scale production, and can effectively improve preparation efficiency and reduce production costs.
  • the above-mentioned negative photosensitive coating liquid be filtered before coating, such as using a filter with a pore size of 0.05-1.0 ⁇ m. Microporous filters, etc.
  • dispersion and mixing equipment such as ball mills, sand mills, bead mills, paint mixers, swing mills, etc. Kneaders, paddle mixers, planetary mixers, Henschel mixers and other scraper types, roller types such as 3-roller mixers, crushers, colloid mills, ultrasonics, homogenizers, rotation/revolution mixing Machine etc. From the viewpoint of dispersion efficiency and micro-dispersion, it is preferable to use a bead mill for dispersion and mixing.
  • step S3 there is no restriction on the form of the energy source for initiating polymerization.
  • Ultraviolet light, visible light, infrared ray, electron beam, and laser lamp energy can all be used to initiate polymerization of the negative photosensitive resin provided in the first typical embodiment of the present application. composition and achieves rapid curing.
  • the development process includes developing the film by contacting it with a developer, removing unnecessary portions, and forming a pattern on the film.
  • the developer in the above developer solution includes, but is not limited to, inorganic alkaline compounds, primary amine compounds, secondary amine compounds, tertiary amine compounds, alcohol amine compounds, quaternary ammonium salt compounds or cyclic amine alkali compounds. Any one or more formed mixed developers.
  • the above-mentioned developer is obtained by dissolving and/or dispersing the developer in a solvent.
  • the solvent of the developer includes an aqueous solution and an optional organic solvent.
  • the organic solvent includes but is not limited to aqueous organic solvents such as methanol and ethanol.
  • surfactants and other additives can also be added to the developer.
  • the EL element provided by this application uses a cured film formed of the above-mentioned negative photosensitive resin composition as a partition wall. No gas leakage is detected in a high-temperature environment, and it does not cause pollution to photoelectric devices. It has broad application prospects.
  • This Comparative Example 1 provides a cured film, which is different from Example 1 in that the negative photosensitive resin composition is composed of A1, B1, C7 and carbon black, and the mass ratio of the four is 65:25 ⁇ 5 ⁇ 5.
  • A1 Polyimide resin: brand GCPI-PAA
  • Carbon black Brand: KetjenblackEC600JD.

Landscapes

  • 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 present application provides a negative photosensitive resin composition, a cured film and a preparation method therefor, an EL element, and a display apparatus. 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 the structure as shown in the following formula (I); and optionally (D) a black dye and/or pigment. By applying the technical solution of the present application, a negative photosensitive composition provided by the present application has excellent heat resistance and light shielding performance; when the negative photosensitive composition is applied to a light-emitting device, no gas leakage can be detected in a high-temperature environment, no device pollution is caused, and the negative photosensitive composition has a wide application prospect.

Description

负型感光性树脂组合物、固化膜及其制备方法、EL元件和显示装置Negative photosensitive resin composition, cured film and preparation method thereof, EL element and display device
相关申请的交叉引用Cross-references to related applications
本申请要求在2022年06月24日提交中国专利局、申请号为202210725485.5、申请名称为“负型感光性树脂组合物、固化膜及其制备方法、EL元件和显示装置”的中国专利申请的优先权，全部内容通过引用结合在本申请中。This application is required to be submitted to the China Patent Office on June 24, 2022, with the application number 202210725485.5 and the application name "Negative photosensitive resin composition, cured film and preparation method thereof, EL element and display device". priority, the entire contents of which are incorporated herein by reference.
技术领域Technical field
本申请涉及感光性树脂组合物技术领域，具体而言，涉及一种负型感光性树脂组合物、固化膜及其制备方法、EL元件和显示装置。The present application relates to the technical field of photosensitive resin compositions. Specifically, it relates to a negative photosensitive resin composition, a cured film and a preparation method thereof, an EL element and a display device.
背景技术Background technique
近年来，在智能手机、平板PC和电视等具有薄型显示器的显示中，开发出了大量使用了有机电致发光(以下简称“EL”)显示器的制品。In recent years, a large number of products using organic electroluminescence (hereinafter referred to as "EL") displays have been developed for displays with thin displays such as smartphones, tablet PCs, and televisions.
有机EL显示器具有使用由从阴极注入的电子与从阳极注入的空穴的再结合产生的能量而发光的自发光元件，然而电子或空穴移动往往会受到阻碍，容易造成自发光元件的发光效率的降低或发光材料的失或，降低自发光元件的寿命。像素分割层由于在与自发光元件相邻的位置形成，因此从像素分割层的脱气、离子成分的流出可能成为有机EL显示器寿命降低的一个原因，因此要求像素分割层具有较高的耐热性。现有技术中通常使用包含高耐热性的聚酰亚胺和肟酯系光聚合引发剂的负载型感光性树脂组合物来解决高耐热性的问题，然而应用这类组合物制备的自发光器件在高温环境下往往存在外溢气体渗漏，污染器件的情况。Organic EL displays have self-luminous elements that emit light using the energy generated by the recombination of electrons injected from the cathode and holes injected from the anode. However, the movement of electrons or holes is often hindered, which easily affects the luminous efficiency of the self-luminous element. The reduction or loss of the luminescent material will reduce the life of the self-luminous element. Since the pixel dividing layer is formed adjacent to the self-luminous element, degassing and outflow of ion components from the pixel dividing layer may cause a reduction in the life of the organic EL display. Therefore, the pixel dividing layer is required to have high heat resistance. sex. In the prior art, supported photosensitive resin compositions containing highly heat-resistant polyimides and oxime ester photopolymerization initiators are usually used to solve the problem of high heat resistance. However, self-contained photosensitive resin compositions prepared using such compositions Light-emitting devices often leak gas and contaminate the devices in high-temperature environments.
有鉴于此，特提出本申请。In view of this, this application is filed.
发明内容Contents of the invention
本申请的主要目的在于提供一种负型感光性树脂组合物、固化膜及其制备方法、EL元件和显示装置，以解决现有技术中包含聚酰亚胺和肟酯系光聚合物引发剂的负载型感光性树脂组合物制备得到的自发光器件在高温环境下存在外溢气体渗漏，污染器件的问题。The main purpose of this application is to provide a negative photosensitive resin composition, a cured film and a preparation method thereof, an EL element and a display device to solve the problem of polyimide and oxime ester photopolymer initiators in the prior art. The self-luminous device prepared from the loaded photosensitive resin composition has the problem of leakage of overflow gas and contamination of the device in a high temperature environment.
为了实现上述目的，根据本申请的第一个方面，提供了一种负型感光性树脂组合物，该组合物包括以下组分：(A)含有聚酰亚胺结构的碱溶性树脂；(B)自由基聚合性化合物；(C) 至少一种具有如下式(I)所示结构的光聚合引发剂；以及可选的(D)黑色染料和/或颜料；
In order to achieve the above objects, according to the first aspect of the present application, a negative photosensitive resin composition is provided, which composition includes the following components: (A) an alkali-soluble resin containing a polyimide structure; (B) ) Radically polymerizable compound; (C) At least one photopolymerization initiator having a structure represented by the following formula (I); and optionally (D) black dye and/or pigment;
其中，Ar为取代或非取代的C6-C30的芳基；R1和R2各自独立地表示取代或非取代的C1-C15的直链烷基、取代或非取代的C3-C15的支链烷基、取代或非取代的C3-C15的环烷基、取代或非取代的C6-C20的芳基、取代或非取代的C4-C20的杂芳基；R3为甲基。Among them, Ar is a substituted or unsubstituted C6-C30 aryl group; R 1 and R 2 each independently represent a substituted or unsubstituted C1-C15 linear alkyl group, a substituted or unsubstituted C3-C15 branched chain Alkyl group, substituted or unsubstituted C3-C15 cycloalkyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C4-C20 heteroaryl group; R 3 is methyl.
进一步的，上述式(I)中，Ar选自取代或非取代的如下基团中的至少一种：
Further, in the above formula (I), Ar is selected from at least one of the following substituted or unsubstituted groups:
其中，R4、R5、R6、R7和R8各自独立地表示氢、取代或非取代的C1-C15的直链烷基，取代或非取代的C3-C15的支链烷基、取代或非取代的C3-C15的环烷基。Among them, R 4 , R 5 , R 6 , R 7 and R 8 each independently represent hydrogen, a substituted or unsubstituted C1-C15 linear alkyl group, a substituted or unsubstituted C3-C15 branched alkyl group, Substituted or unsubstituted C3-C15 cycloalkyl.
进一步地，Ar选自如下基团中的至少一种：
Further, Ar is selected from at least one of the following groups:
进一步地，上述光聚合引发剂选自具有如下结构化合物中的至少一种：


Further, the above-mentioned photopolymerization initiator is selected from at least one compound with the following structure:


进一步地，上述光聚合引发剂选自具有如下结构化合物中的至少一种：
Further, the above-mentioned photopolymerization initiator is selected from at least one compound with the following structure:
进一步地，含有聚酰亚胺结构的碱溶性树脂选自聚酰亚胺、聚酰亚胺前体、聚苯并噁唑或聚苯并噁唑前体中的至少一种；和/或，自由基聚合性化合物为丙烯酸酯类化合物。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 radically polymerizable compound is an acrylate compound.
进一步地，黑色染料为以溶剂黑27～47的染料索引规定的染料；和/或，黑色颜料选自炭黑、碳纳米管、乙炔黑、铁黑、苯胺黑、钛黑、钛黑、苝系颜料或内酰胺系颜料中的至少一种。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 carbon black, carbon nanotubes, acetylene black, iron black, aniline black, titanium black, titanium black, perylene at least one type of pigment or lactam pigment.
进一步地，按质量份数计，上述负型感光性树脂组合物包括(A)30-80份含有聚酰亚胺结构的碱溶性树脂；(B)10-50份自由基聚合性化合物；(C)2-8份光聚合引发剂；以及可选的(D)2-8份黑色染料和/或颜料。Further, in terms of parts by mass, the above-mentioned negative photosensitive resin composition includes (A) 30-80 parts of an alkali-soluble resin containing a polyimide structure; (B) 10-50 parts of a radically polymerizable compound; (B) C) 2-8 parts of photopolymerization initiator; and optionally (D) 2-8 parts of black dye and/or pigment.
进一步地，上述负型感光性树脂组合物还包括助剂，该助剂包括增感剂、光引发剂、流平剂、分散剂、固化剂、表面活性剂、消泡剂或储存增强剂中的至少一种。为了实现上述目的，根据本申请的第二个方面，还提供了一种固化膜，该固化膜的原料为上述第一个方面提供的任一种负型感光性树脂组合物。Further, the above-mentioned negative photosensitive resin composition also includes auxiliaries, which include sensitizers, photoinitiators, leveling agents, dispersants, curing agents, surfactants, defoaming agents or storage enhancers. of at least one. In order to achieve the above object, according to the second aspect of the present application, a cured film is also provided. The raw material of the cured film is any negative photosensitive resin composition provided in the first aspect.
根据本申请的第三个方面，还提供了上述第二个方面提供的固化膜的制备方法，该制备方法包括：步骤S1，将负型感光性树脂组合物溶解或分散于溶剂中，得到负型感光性涂布液；步骤S2，将负型感光性涂布液涂布在基板表面，去除溶剂，得到待固化被膜，优选通过加热的方式将溶剂去除，加热的温度优选为70～130℃；步骤S3，将待固化被膜进行引发聚合，待固化被膜固化形成被膜，优选通过能量辐射的方式进行引发聚合；步骤S4，将被膜依次进行显影处理、洗涤和加热，得到固化膜，其中，显影处理的时间优选为30～180s，加热的温度优选为100～350℃，加热的时间优选为2～20min。 According to the third aspect of the present application, a method for preparing the cured film provided in the second aspect is also provided. The preparation method includes: step S1, dissolving or dispersing the negative photosensitive resin composition in a solvent to obtain a negative photosensitive resin composition. Type photosensitive coating liquid; step S2, apply the negative photosensitive coating liquid on the surface of the substrate, remove the solvent, and obtain a film to be cured. The solvent is preferably removed by heating, and the heating temperature is preferably 70 to 130°C. ; Step S3, initiate polymerization of the film to be cured, and solidify the film to be cured to form a film, preferably by initiating polymerization by energy radiation; Step S4, sequentially develop, wash and heat the film to obtain a cured film, wherein, developing The treatment time is preferably 30 to 180 seconds, the heating temperature is preferably 100 to 350°C, and the heating time is preferably 2 to 20 minutes.
根据本申请的第四个方面，还提供了一种EL元件，该EL元件包括上述第一方面提供的任一种负型感光性树脂组合物或上述第二方面提供的固化膜。According to a fourth aspect of the present application, an EL element is also provided, which includes any negative photosensitive resin composition provided in the first aspect or the cured film provided in the second aspect.
根据本申请的第五个方面，还提供了一种显示装置，该显示装置包括上述第一方面提供的任一种负型感光性树脂组合物、上述第二方面提供的固化膜或上述第四方面提供的EL元件。According to the fifth aspect of the present application, there is also provided a display device, which includes any negative photosensitive resin composition provided in the first aspect, the cured film provided in the second aspect, or the fourth aspect. EL components provided by the company.
应用本申请的技术方案，本申请提供的负型感光性组合物不仅具备优异的耐热性和避光性，而且其应用于发光器件后在高温环境下未检测到气体渗漏，不会造成器件污染，具有广阔的应用前景。Applying the technical solution of this application, the negative photosensitive composition provided by this application not only has excellent heat resistance and light protection, but also has no gas leakage detected in a high temperature environment after being applied to a light-emitting device, and will not cause device pollution and has broad application prospects.
具体实施方式Detailed ways
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将并结合实施例来详细说明本申请。It should be noted that, as long as there is no conflict, the embodiments and features in the embodiments of this application can be combined with each other. The present application will be described in detail below in conjunction with examples.
如本申请背景技术所分析的，现有技术中采用包含高热性的聚酰亚胺和肟酯系光聚合引发剂的负载性感光性树脂组合物制备的自发光器件在高温环境下往往存在外溢气体渗漏，污染器件的情况。为了解决该问题，本申请提供了一种负型感光性树脂组合物、固化膜及其制备方法、EL元件和显示装置。As analyzed in the background of this application, self-luminous devices prepared in the prior art using a loaded photosensitive resin composition containing a highly thermal polyimide and an oxime ester photopolymerization initiator often have overflow in a high temperature environment. Gas leakage and contamination of devices. In order to solve this problem, this application provides a negative photosensitive resin composition, a cured film and a preparation method thereof, an EL element, and a display device.
在本申请的一种典型实施方式中，提供了一种负型感光性树脂组合物，该组合物包括以下组分：(A)含有聚酰亚胺结构的碱溶性树脂；(B)自由基聚合性化合物；(C)至少一种具有如下式(I)所示结构的光聚合引发剂以及可选的(D)黑色染料和/或燃料。
In a typical embodiment of the present application, a negative photosensitive resin composition is provided, which composition includes the following components: (A) an alkali-soluble resin containing a polyimide structure; (B) free radicals Polymerizable compound; (C) at least one photopolymerization initiator having a structure represented by the following formula (I) and optionally (D) black dye and/or fuel.
上述式(I)中，Ar为取代或未被取代的C6-C30的芳基；R1和R2各自独立地表示取代或未取代的C1-C15的直链烷基、取代或非取代的C3-C15的支链烷基、取代或非取代的C3-C15的环烷基、取代或非取代的C6-C20的芳基、取代或非取代的C4-C20的杂芳基；R3为甲基。In the above formula (I), Ar is a substituted or unsubstituted C6-C30 aryl group; R 1 and R 2 each independently represent a substituted or unsubstituted C1-C15 linear alkyl group, a substituted or unsubstituted C3-C15 branched alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl; R 3 is methyl.
应用本申请的技术方案，本申请提供的负型感光性组合物不仅具备优异的耐热性和避光性，而且其应用于发光器件后在高温环境下未检测到气体渗漏，不会造成器件污染，具有广阔的应用前景。 Applying the technical solution of this application, the negative photosensitive composition provided by this application not only has excellent heat resistance and light protection, but also has no gas leakage detected in a high temperature environment after being applied to a light-emitting device, and will not cause device pollution and has broad application prospects.
为了进一步降低上述负型感光性树脂组合物制备得到的光电器件的气体渗漏性，优选Ar选自如下基团中的至少一种：
In order to further reduce the gas leakage of the photoelectric device prepared from the above-mentioned negative photosensitive resin composition, it is preferred that Ar is selected from at least one of the following groups:
其中，所述R4、R5、R6、R7和R8各自独立地表示氢、取代或未取代的C1-C15的直链烷基、取代或非取代的C3-C15的支链烷基、取代或非取代的C3-C15的环烷基。Wherein, R 4 , R 5 , R 6 , R 7 and R 8 each independently represent hydrogen, a substituted or unsubstituted C1-C15 linear alkyl group, a substituted or unsubstituted C3-C15 branched alkyl group. group, substituted or unsubstituted C3-C15 cycloalkyl group.
在本申请的一些实施例中，当Ar选自如下基团中的至少一种时，上述负型感光性树脂组合物制备得到的光电器件的防气体渗漏性更为优异。

In some embodiments of the present application, when Ar is selected from at least one of the following groups, the gas leakage prevention property of the optoelectronic device prepared from the above negative photosensitive resin composition is more excellent.

在本申请中，“*”代表化学基团的连接位点。In this application, "*" represents the attachment site of a chemical group.
在本申请的一些优选实施例中，优选上述光聚合引发剂选自如下化合物中的至少一种，以利于进一步降低上述负型感光性树脂组合物应用于光电器件的气体渗漏可能性，进一步避免器件被污染。


In some preferred embodiments of the present application, it is preferred that the above-mentioned photopolymerization initiator is selected from at least one of the following compounds, in order to further reduce the possibility of gas leakage when the above-mentioned negative photosensitive resin composition is applied to optoelectronic devices, and further Avoid device contamination.


在本申请的一些实施例中，光聚合引发剂选自如下化合物中的至少一种时，包含其的负型感光性树脂组合物的防气体渗漏性更为显著。
In some embodiments of the present application, when the photopolymerization initiator is selected from at least one of the following compounds, the gas leakage prevention property of the negative photosensitive resin composition containing it is more significant.
上述含有聚酰亚胺结构的碱溶性树脂不作限制，任何具备优异耐热性的含有聚酰亚胺结构的碱溶性树脂均可，尤其是当上述含有聚酰亚胺结构的碱溶性树脂选自聚酰亚胺、聚酰亚胺前体、聚苯并噁唑或聚苯并噁唑前体中的任意一种或多种的混合物时，其制备得到的光电器件的耐热性能更为优异。The above-mentioned alkali-soluble resin containing a polyimide structure is not limited, and any alkali-soluble resin containing a polyimide structure with excellent heat resistance can be used, especially when the above-mentioned alkali-soluble resin containing a polyimide structure is selected from When any one or a mixture of polyimide, polyimide precursor, polybenzoxazole or polybenzoxazole precursor is used, the heat resistance of the optoelectronic device prepared is more excellent. .
上述自由基聚合性化合物的类型不作限制，任何能够采用上述光聚合引发剂进行引发的自由基聚合物性化合物均可，从提高引发效率的角度出发，优选上述自由基聚合性化合物为丙烯酸酯类化合物，包括但不限于甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、季戊四醇四丙烯酸酯或三羟甲基丙烷三丙烯酸酯中的任意一种或多种形成的混合树脂。The type of the above-mentioned radically polymerizable compound is not limited. Any radically polymerizable compound that can be initiated by the above-mentioned photopolymerization initiator can be used. From the perspective of improving the initiation efficiency, it is preferred that the above-mentioned radically polymerizable compound is an acrylate compound. , including but not limited to mixed resin formed from any one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, pentaerythritol tetraacrylate or trimethylolpropane triacrylate.
上述黑色染料或黑色颜料的类型不作限制，任何能够具备黑色着色能力的物质均可。为了进一步提高上述黑色染料的分散性能和着色性能，优选黑色染料为以溶剂黑27～47的染料索引(C.I.)规定的染料。为了进一步上述黑色颜料的分散性能和着色性能，优选黑色颜料选自炭黑、碳纳米管、乙炔黑、铁黑、苯胺黑、钛黑、苝系颜料或内酰胺系颜料中的任意一种或多种形成的混合颜料。The type of the above-mentioned black dye or black pigment is not limited, and any substance capable of black coloring can be used. In order to further improve the dispersion performance and coloring performance of the black dye, it is preferable that the black dye is a dye specified by the dye index (C.I.) of solvent black 27 to 47. In order to further improve the dispersion performance and coloring performance of the black pigment, it is preferable that the black pigment is selected from any one of carbon black, carbon nanotubes, acetylene black, iron black, aniline black, titanium black, perylene-based pigments or lactam-based pigments, or A variety of mixed pigments.
为了进一步提高上述负型感光性树脂组合物的性能，优选上述负型感光性树脂组合物还包括助剂，该助剂包括但不限于增感剂、光引发剂、流平剂、分散剂、固化剂、表面活性剂、消泡剂或储存增强剂中的任意一种或多种形成的混合助剂。In order to further improve the performance of the above-mentioned negative photosensitive resin composition, it is preferred that the above-mentioned negative photosensitive resin composition further includes auxiliary agents, which include but are not limited to sensitizers, photoinitiators, leveling agents, dispersants, Mixing aids formed from any one or more of curing agents, surfactants, defoaming agents or storage enhancers.
在本申请的一些实施例中，为了进一步提高应用上述负型感光性树脂组合物的光电器件的耐光热性能、避光性能以及防气体渗漏性能，优选上述负型感光性树脂组合物包括：30-80 质量份含有聚酰亚胺结构的碱溶性树脂，10-50质量份自由基聚合性化合物，2-8质量份光聚合引发剂以及可选的2-8份黑色染料和/或颜料。In some embodiments of the present application, in order to further improve the photothermal resistance, light-proofing performance and gas leakage prevention performance of the optoelectronic device using the above-mentioned negative photosensitive resin composition, it is preferred that the above-mentioned negative photosensitive resin composition includes: 30-80 The mass parts include an alkali-soluble resin containing a polyimide structure, 10-50 mass parts of a radically polymerizable compound, 2-8 mass parts of a photopolymerization initiator, and optionally 2-8 parts of a black dye and/or pigment.
典型但非限制性的，上述负型感光性树脂组合物中，含有聚酰亚胺结构的碱溶性树脂的质量份数如为30份、35份、40份、50份、55份、60份、65份、70份、80份或任意两个数值组成的范围值；自由基聚合性化合物的质量份数如为10份、15份、20份、25份、30份、35份、40份、45份、50份或任意两个数值组成的范围值；光聚合引发剂的质量份数如为2份、3份、4份、5份、6份、7份、8份或任意两个数值组成的范围值；黑色染料和/或颜料的质量分数如为2份、3份、4份、5份、6份、7份、8份或任意两个数值组成的范围值。Typical but not limiting, in the above-mentioned negative photosensitive resin composition, the mass parts of the alkali-soluble resin containing the polyimide structure are, for example, 30 parts, 35 parts, 40 parts, 50 parts, 55 parts, and 60 parts. , 65 parts, 70 parts, 80 parts or a range value consisting of any two values; the mass parts of the free radical polymerizable compound are, for example, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts , 45 parts, 50 parts or a range of any two values; the mass parts of the photopolymerization initiator are 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or any two parts A range of numerical 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 a range of any two parts.
在本申请的另一种典型实施方式中，还提供了一种固化膜，该固化膜的原料为上述第一种典型实施方式提供的任一种负型感光性树脂组合物。In another typical embodiment of the present application, a cured film is also provided, and the raw material of the cured film is any negative photosensitive resin composition provided in the above-mentioned first typical embodiment.
本申请提供的固化膜采用上述负型感光性树脂组合物为原料制备得到，不仅具备优异的耐光热性能和避光性能，而且在高温环境下也无气体渗漏性，不会造成光电器件的污染，具备广阔的应用前景。The cured film provided by this application is prepared using the above-mentioned negative photosensitive resin composition as raw material. It not only has excellent photothermal resistance and light-proofing properties, but also has no gas leakage in high-temperature environments and will not cause damage to the optoelectronic device. pollution and has broad application prospects.
在本申请的第三种典型实施方式中，还提供了上述固化膜的制备方法，该制备方法包括以下步骤：步骤S1，将负型感光性树脂组合物溶解于或分散于溶剂中，得到负型感光性涂布液；步骤S2，将该负型感光性涂布液涂布在基板表面，去除溶剂，得到待固化被膜；步骤S3，将该待固化被膜进行引发聚合，待固化被膜固化形成被膜；步骤S4，将被膜依次进行显影处理、洗涤和加热，得到固化膜。In a third typical embodiment of the present application, a method for preparing the above-mentioned cured film is also provided. The preparation method includes the following steps: Step S1, dissolving or dispersing the negative photosensitive resin composition in a solvent to obtain a negative photosensitive resin composition. Type photosensitive coating liquid; Step S2, apply the negative photosensitive coating liquid on the surface of the substrate, remove the solvent, and obtain a film to be cured; Step S3, initiate polymerization of the film to be cured, and the film to be cured is solidified to form Film; step S4, the film is developed, washed and heated in sequence to obtain a cured film.
本申请提供的固化膜的制备方法工艺简单，操作方便，适用于规模化生产，能够有效提高制备效率，降低生产成本。The preparation method of the cured film provided by this application is simple in process, easy to operate, suitable for large-scale production, and can effectively improve preparation efficiency and reduce production costs.
上述步骤S1中，溶剂的类型不作限制，从利于后续去除的角度出发，优选为低沸点溶剂，包括但不限于丙二醇甲醚醋酸酯。In the above step S1, the type of solvent is not limited. From the perspective of facilitating subsequent removal, it is preferably a low boiling point solvent, including but not limited to propylene glycol methyl ether acetate.
为了避免上述涂布液中存在组合物团聚或分散不均匀的情况影响后续涂布的均匀性，优选上述负型感光性涂布液在涂布前先进行过滤，如采用孔径0.05-1.0μm的微孔过滤器等。In order to avoid the agglomeration or uneven dispersion of the composition in the above-mentioned coating liquid, which affects the uniformity of subsequent coating, it is preferred that the above-mentioned negative photosensitive coating liquid be filtered before coating, such as using a filter with a pore size of 0.05-1.0 μm. Microporous filters, etc.
为了避免上述组合物在溶剂中无法均匀分散或溶解，优选采用本领域公知方法进行分散混合设备进行分散混合，如球磨机、砂磨机、珠磨机、涂料混合器、摇摆磨机等球型，捏合机、桨式混合机、行星式混合机、亨舍尔混合机等刮刀型，3辊式混炼机等辊型，以及擂溃机、胶体磨、超声波、均化器、自转/公转混合机等。从分散效率和微分散化考虑，优选使用珠磨机进行分散混合。In order to avoid that the above composition cannot be uniformly dispersed or dissolved in the solvent, it is preferable to use well-known methods in the art for dispersion and mixing equipment, such as ball mills, sand mills, bead mills, paint mixers, swing mills, etc. Kneaders, paddle mixers, planetary mixers, Henschel mixers and other scraper types, roller types such as 3-roller mixers, crushers, colloid mills, ultrasonics, homogenizers, rotation/revolution mixing Machine etc. From the viewpoint of dispersion efficiency and micro-dispersion, it is preferable to use a bead mill for dispersion and mixing.
上述步骤S2中，涂布的方法不作限制，包括但不限于喷射法、辊涂法、狭缝法或旋转涂布法。基板的材质不作限制，优选为玻璃基板。In the above step S2, the coating method is not limited, including but not limited to spray method, roller coating method, slit method or spin coating method. The material of the substrate is not limited, but is preferably a glass substrate.
上述步骤S2中，去除溶剂的方式不作限制，优选采用加热的方式除去溶剂。加热条件根据负型感光性树脂组合物的各组分的种类、配比以及溶剂的选择而不同。为了进一步提高溶 剂的去除效率，优选加热温度为70-130℃，如采用加热板加热，则加热时间为1-20min，如采用烘箱加热，则加热初见为3-60min。In the above-mentioned step S2, the method of removing the solvent is not limited, and it is preferable to remove the solvent by heating. The heating conditions vary depending on the type and proportion of each component of the negative photosensitive resin composition and the selection of the solvent. In order to further improve the solubility For the removal efficiency of the agent, the preferred heating temperature is 70-130°C. If a heating plate is used for heating, the heating time is 1-20 minutes. If an oven is used for heating, the initial heating time is 3-60 minutes.
上述步骤S3中，对于进行引发聚合的能量源的形式不作限制，紫外线、可见光、红外线、电子束、激光灯能量均可通过辐射引发聚合本申请第一种典型实施方式提供的负型感光性树脂组合物，并实现快速固化。上述引发聚合的能量源包括但不限于：具有波长为200-500nm的超高压汞灯、高压汞灯、中压汞灯、汞氙灯、低压汞灯、金属卤化物灯、氙灯、氘灯、化学灯、LED灯、荧光灯、钨灯、Nd-YAG3倍波激光、He-Cd激光、氮激光、Xe-Cl准分子激光、Xe-F准分子激光、半导体激发固体激光、i射线、h射线、g射线等活性光线；上述能量源还可使为电子束、α射线、β射线、γ射线、X射线及中子射线等，优选放射线为具有250～450nm的波长的紫外线～可见光线。辐射的强度优选为50-100mJ/cm2。In the above step S3, there is no restriction on the form of the energy source for initiating polymerization. Ultraviolet light, visible light, infrared ray, electron beam, and laser lamp energy can all be used to initiate polymerization of the negative photosensitive resin provided in the first typical embodiment of the present application. composition and achieves rapid curing. The above-mentioned energy sources for initiating polymerization include, but are not limited to: ultra-high-pressure mercury lamps with wavelengths of 200-500 nm, high-pressure mercury lamps, medium-pressure mercury lamps, mercury-xenon lamps, low-pressure mercury lamps, metal halide lamps, xenon lamps, deuterium lamps, chemical Lamp, LED lamp, fluorescent lamp, tungsten lamp, Nd-YAG 3 times wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, semiconductor excited solid laser, i-ray, h-ray, Active rays such as g-rays; the energy source may also be electron beams, α-rays, β-rays, γ-rays, X-rays, neutron rays, etc. Preferably, the radiation is ultraviolet to visible rays with a wavelength of 250 to 450 nm. The intensity of radiation is preferably 50-100 mJ/cm 2 .
上述步骤S4中，优选所述显影处理包括：将被膜与显影液接触进行显影，将不要的部分除去而在被膜形成图案。上述显影液中的显影剂包括但不限于无机碱类化合物、伯胺类化合物、仲胺类化合物、叔胺类化合物、醇胺类化合物、季铵盐类化合物或环状胺类碱化合物中的任意一种或多种形成的混合显影剂。In step S4, it is preferable that the development process includes developing the film by contacting it with a developer, removing unnecessary portions, and forming a pattern on the film. The developer in the above developer solution includes, but is not limited to, inorganic alkaline compounds, primary amine compounds, secondary amine compounds, tertiary amine compounds, alcohol amine compounds, quaternary ammonium salt compounds or cyclic amine alkali compounds. Any one or more formed mixed developers.
上述无机碱类化合物如为氢氧化钠、氢氧化钾、碳酸钠、硅酸钠、偏硅酸钠或氨水等；上述伯胺类化合物如为乙基胺、正丙基胺等；上述仲胺类化合物如为二乙基胺、二-正丙基胺等；上述叔胺类化合物如为三乙胺、甲基二乙基胺等；上述醇胺类化合物如为二甲基乙醇胺、三乙醇胺等；上述季铵盐类化合物如为四甲基氢氧化铵、四乙基氢氧化铵、胆碱等；上述环状胺类碱化合物如为吡咯、哌啶、1，8-二氮杂二环[5，4，0]-7-十一碳烯、1，5-二氮杂二环[4，3，0]-5-壬烷等。The above-mentioned inorganic alkali compounds are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate or ammonia water, etc.; the above-mentioned primary amine compounds are, for example, ethylamine, n-propylamine, etc.; the above-mentioned secondary amines Examples of the above-mentioned tertiary amine compounds include diethylamine, di-n-propylamine, etc.; the above-mentioned tertiary amine compounds include triethylamine, methyldiethylamine, etc.; the above-mentioned alcoholamine compounds include dimethylethanolamine, triethanolamine, etc. etc.; the above-mentioned quaternary ammonium salt compounds are, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc.; the above-mentioned cyclic amine base compounds are, for example, pyrrole, piperidine, 1,8-diazabis Cycl[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane, etc.
上述显影液由显影剂溶解和/或分散在溶剂中得到，该显影液的溶剂包括水溶液以及可选的有机溶剂，该有机溶剂包括但不限于甲醇、乙醇等水溶液有机溶剂。为了进一步提高显影液的分散稳定性，还可以在显影剂中加入表面活性剂等助剂。The above-mentioned developer is obtained by dissolving and/or dispersing the developer in a solvent. The solvent of the developer includes an aqueous solution and an optional organic solvent. The organic solvent includes but is not limited to aqueous organic solvents such as methanol and ethanol. In order to further improve the dispersion stability of the developer, surfactants and other additives can also be added to the developer.
上述显影处理的方法不作限制，包括但不限于盛液法、喷淋法或浸渍法中的任意一种或多种显影方法的组合。为了进一步提高显影的充分性，优选显影处理的时间为30～180s。The above-mentioned development treatment method is not limited, and includes but is not limited to any one or a combination of multiple development methods including 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.
为了避免过多显影液附着于显影后的被膜表面，影响性能，优选采用水冲洗显影后的被膜，洗涤的时间优选为30～90s，将不要的部分除去，然后用压缩空气或压缩氮气使其风干，从而使得显影后的被膜形成图案。In order to prevent too much developer from adhering to the surface of the developed film and affecting its performance, it is best to rinse the developed film with water. The washing time is preferably 30 to 90 seconds. Remove the unnecessary parts, and then use compressed air or compressed nitrogen to rinse the film. Air-dry to form a pattern on the developed film.
上述加热的方式不作限制，为了进一步提高加热效率，优选将上述形成图案的被膜在100～350℃进行加热2～20min，从而形成固化膜。The heating method is not limited. In order to further improve the heating efficiency, it is preferable to heat the patterned film at 100 to 350° C. for 2 to 20 minutes to form a cured film.
在本申请的第四种典型实施方式中，还提供了一种EL元件，该EL元件包括间隔壁，该间隔壁为上述第三种典型实施方式提供的任一种固化膜；或，该间隔壁包含上述第一种典型实施方式提供的任一种负型感光性树脂组合物。 In the fourth exemplary embodiment of the present application, an EL element is also provided. The EL element includes a partition wall, and the partition wall is any cured film provided in the above-mentioned third exemplary embodiment; or, the partition wall The partition wall contains any one of the negative photosensitive resin compositions provided in the first exemplary embodiment.
本申请提供的EL元件采用上述负型感光性树脂组合物形成的固化膜作为间隔壁，其在高温环境下仍然未检测到气体渗漏，不会造成光电器件污染，具有广阔的应用前景。The EL element provided by this application uses a cured film formed of the above-mentioned negative photosensitive resin composition as a partition wall. No gas leakage is detected in a high-temperature environment, and it does not cause pollution to photoelectric devices. It has broad application prospects.
在本申请的第五种典型实施方式中，还提供了一种显示装置，该显示装置包括上述第一种典型实施方式提供的任一种负型感光性树脂组合物、上述第二种典型实施方式提供的任一种固化膜或上述第四种典型实施方式提供的EL元件。In the fifth exemplary embodiment of the present application, a display device is also provided. The display device includes any negative photosensitive resin composition provided in the above-mentioned first exemplary embodiment, the above-mentioned second exemplary embodiment Any cured film provided by the method or the EL element provided by the above-mentioned fourth exemplary embodiment.
本申请提供的显示装置应用第一种典型实施方式提供的负型感光性树脂组合物，在高温环境下未检测到气体渗漏，不会造成发光器件污染，具有广阔的应用前景。The display device provided in this application uses the negative photosensitive resin composition provided in the first typical embodiment, has no gas leakage detected in a high temperature environment, does not cause pollution to the light-emitting device, and has broad application prospects.
下面将结合实施例和对比例，进一步说明本申请的有益效果。The beneficial effects of the present application will be further described below in conjunction with examples and comparative examples.
实施例1Example 1
本实施例提供了一种固化膜，其按照以下步骤制备得到：This embodiment provides a cured film, which is prepared according to the following steps:
(1)按照质量份数80∶10∶5∶5分别将含有聚酰亚胺结构的碱溶性树脂A1、自由基聚合性化合物B1、光聚合引发剂C1和炭黑混合在珠磨机中分散搅拌3h，得到负型感光性树脂组合物；(1) Mix the alkali-soluble resin A1 containing a polyimide structure, the radically polymerizable compound B1, the photopolymerization initiator C1 and the carbon black in a bead mill in proportions of 80:10:5:5 respectively and disperse them in a bead mill. Stir for 3 hours to obtain a negative photosensitive resin composition;
(2)将负型感光性树脂组合物分散在100质量份的溶剂聚丙二醇甲醚醋酸酯(PGMEA)中，得到负型感光性涂布液；(2) Disperse the negative photosensitive resin composition in 100 parts by mass of the solvent polypropylene glycol methyl ether acetate (PGMEA) to obtain a negative photosensitive coating liquid;
(3)将玻璃基板(大小100mm×100mm×1mm)用中性洗涤剂(N-甲基吡咯烷酮，阿拉丁)、水和乙醇依次清洗后干燥，在该玻璃基板上旋涂上述负型感光性涂布液，利用加热板在90℃烘烤125s，去除溶剂，冷却至常温后，得到附着于基板上的待固化被膜；(3) Wash the glass substrate (size 100 mm × 100 mm × 1 mm) with neutral detergent (N-methylpyrrolidone, Aladdin), water and ethanol in sequence, then dry it, and spin-coat the above-mentioned negative photosensitivity on the glass substrate The coating liquid is baked at 90°C for 125 seconds using a heating plate to remove the solvent. After cooling to normal temperature, a film to be cured attached to the substrate is obtained;
(4)将上述被膜使用汞灯(RW-LED-YT200gl)，以100mJ/cm2进行了充分曝光，得到厚度为1.5μm的固化的被膜；(4) The above film was fully exposed using a mercury lamp (RW-LED-YT200gl) at 100 mJ/cm 2 to obtain a cured film with a thickness of 1.5 μm;
(5)将上述被膜用0.04％氢氧化钾水溶液在25℃浸渍60s显影，然后采用水洗涤后在235℃实施15min进行烘烤，得到固化膜。(5) The above-mentioned film is immersed in 0.04% potassium hydroxide aqueous solution at 25°C for 60 seconds for development, then washed with water and baked at 235°C for 15 minutes to obtain a cured film.
实施例2Example 2
本实施例与实施例1的不同之处在于，步骤(1)中，采用含有聚酰亚胺结构的碱溶性树脂A2替换A1，采用自由基聚合性化合物B2替换B1，采用光引发剂C2替换C1。The difference between this example and Example 1 is that in step (1), the alkali-soluble resin A2 containing a polyimide structure is used to replace A1, the free radical polymerizable compound B2 is used to replace B1, and the photoinitiator C2 is used to replace A1. C1.
实施例3Example 3
本实施例与实施例1的不同之处在于，负型感光性树脂组合物由A1、B1、C3和炭黑组成，且四者的质量比为70∶20∶5∶5。The difference between this embodiment and Example 1 is that the negative photosensitive resin composition is composed of A1, B1, C3 and carbon black, and the mass ratio of the four is 70:20:5:5.
实施例4 Example 4
本实施例与实施例1的不同之处在于，负型感光性树脂组合物由A1、B1、C1和炭黑组成，且四者的质量比为60∶30∶5∶5。The difference between this embodiment and Example 1 is that the negative photosensitive resin composition is composed of A1, B1, C1 and carbon black, and the mass ratio of the four is 60:30:5:5.
实施例5Example 5
本实施例与实施例1的不同之处在于，负型感光性树脂组合物由A1、B1、C4和炭黑组成，且四者的质量比为65∶25∶5∶5。The difference between this embodiment and Example 1 is 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.
实施例6Example 6
本实施例与实施例1的不同之处在于，负型感光性树脂组合物由A2、B1、C5和炭黑组成，且四者的质量比为60∶30∶5∶5。The difference between this embodiment and Example 1 is that the negative photosensitive resin composition is composed of A2, B1, C5 and carbon black, and the mass ratio of the four is 60:30:5:5.
实施例7Example 7
本实施例与实施例1的不同之处在于，负型感光性树脂组合物由A2、B2、C6和炭黑组成，且四者的质量比为70∶20∶5∶5。The difference between this embodiment and Example 1 is 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.
实施例8Example 8
本实施例与实施例1的不同之处在于，负型感光性树脂组合物由A2、B1、C5和炭黑组成，且四者的质量比为60∶30∶5∶5。The difference between this embodiment and Example 1 is that the negative photosensitive resin composition is composed of A2, B1, C5 and carbon black, and the mass ratio of the four is 60:30:5:5.
实施例9Example 9
本实施例与实施例1的不同之处在于，负型感光性树脂组合物由A1、B2、C6和炭黑组成，且四者的质量比为65∶25∶5∶5。The difference between this embodiment and Example 1 is that the negative photosensitive resin composition is composed of A1, B2, C6 and carbon black, and the mass ratio of the four is 65:25:5:5.
实施例10Example 10
本实施例与实施例1的不同之处在于，负型感光性树脂组合物由A1、B1、C4和炭黑组成，且四者的质量比为50∶40∶5∶5。The difference between this embodiment and Example 1 is 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.
实施例11Example 11
本实施例与实施例1的不同之处在于，负型感光性树脂组合物由A1、B2、C3和炭黑组成，且四者的质量比为40∶50∶5∶5。The difference between this embodiment and Example 1 is 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.
实施例12Example 12
本实施例与实施例1的不同之处在于，负型感光性树脂组合物由A1、B1、C2和炭黑组成，且四者的质量比为40∶50∶5∶5。The difference between this embodiment and Example 1 is 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.
实施例13Example 13
本实施例与实施例1的不同之处在于，负型感光性树脂组合物由A1、B1、C1和炭黑组成，且四者的质量比为80∶10∶2∶8。 The difference between this embodiment and Example 1 is that the negative photosensitive resin composition is composed of A1, B1, C1 and carbon black, and the mass ratio of the four is 80:10:2:8.
实施例14Example 14
本实施例与实施例1的不同之处在于，负型感光性树脂组合物由A1、B1、C4和炭黑组成，且四者的质量比为50∶40∶8∶2。The difference between this embodiment and Example 1 is that the negative photosensitive resin composition is composed of A1, B1, C4 and carbon black, and the mass ratio of the four is 50:40:8:2.
对比例1Comparative example 1
本对比例1提供了一种固化膜，其与实施例1的不同之处在于，负型感光性树脂组合物由A1、B1、C7和炭黑组成，且四者的质量比为65∶25∶5∶5。This Comparative Example 1 provides a cured film, which is different from Example 1 in that the negative photosensitive resin composition is composed of A1, B1, C7 and carbon black, and the mass ratio of the four is 65:25 ∶5∶5.
对比例2Comparative example 2
本对比例1提供了一种固化膜，其与实施例1的不同之处在于，负型感光性树脂组合物由A2、B1、C8和炭黑组成，且四者的质量比为60∶30∶5∶5。This Comparative Example 1 provides a cured film, which is different from Example 1 in that the negative photosensitive resin composition is composed of A2, B1, C8 and carbon black, and the mass ratio of the four is 60:30 ∶5∶5.
上述A1、A2、B1、B2、C1-C8以及炭黑的具体信息如下：The specific information of the above-mentioned A1, A2, B1, B2, C1-C8 and carbon black is as follows:
A1：聚酰亚胺树脂：牌号GCPI-PAAA1: Polyimide resin: brand GCPI-PAA
A2：聚酰亚胺树脂：牌号JCL3030A2: Polyimide resin: brand JCL3030
B1：季戊四醇四丙烯酸酯：牌号：A-TMMTB1: Pentaerythritol tetraacrylate: Brand: A-TMMT
B2：三羟甲基丙烷三丙烯酸酯：牌号：M309

B2: Trimethylolpropane triacrylate: Brand: M309

炭黑：牌号：KetjenblackEC600JD。Carbon black: Brand: KetjenblackEC600JD.
试验例1Test example 1
将上述实施例和对比例提供的固化膜分别进行耐热性能评价和避光性评价，结果如下表1所示。The cured films provided in the above examples and comparative examples were respectively subjected to heat resistance performance evaluation and light shielding evaluation, and the results are shown in Table 1 below.
耐热性测试的具体方法为：分别将上述固化膜在对流式烘箱中在230℃下进行30min烘烤，然后对加热前后的着色图案的色度求出ΔE*ab，ΔE*ab为3.0以下的情况评价为耐热性优良。The specific method for the heat resistance test is: bake the above-mentioned cured films in a convection oven at 230°C for 30 minutes, and then calculate ΔE*ab from the chromaticity of the coloring pattern before and after heating, and ΔE*ab is less than 3.0 The case was evaluated as having excellent heat resistance.
避光性测试的具体方法为：在温度30℃、湿度50％、黑板(black panel)温度63℃的条件下以180W照射固化膜60h，由照射前后的着色图案的色度求出ΔE*ab，ΔE*ab为3.0以下的情况评价为耐热性优良。The specific method of light protection test is: irradiate the cured film at 180W for 60 hours under the conditions of temperature 30°C, humidity 50%, black panel temperature 63°C, and calculate ΔE*ab from the chromaticity of the coloring pattern before and after irradiation. , when ΔE*ab is 3.0 or less, it is evaluated that the heat resistance is excellent.
表1

Table 1

试验例2Test example 2
将实施例和对比例提供的固化膜进行气体渗漏测试，结果如下表2所示。The cured films provided in the examples and comparative examples were subjected to a gas leakage test, and the results are shown in Table 2 below.
气体渗漏测试的方法为：The method of gas leakage testing is:
采用GC-MS测试方法，分别取上述实施例和对比例提供的固化膜5g，裁剪后，放入顶空瓶中待用，采用顶空进样，观察是否有外溢气体产出(二氧化碳及自带溶剂峰除外)。Using the GC-MS test method, take 5g of the cured films provided in the above examples and comparative examples respectively. After cutting, put them into headspace bottles for later use. Use headspace sampling to observe whether there is any overflow gas production (carbon dioxide and natural gas). Except for solvent peaks).
仪器：安捷伦7890B气相色谱仪；Instrument: Agilent 7890B gas chromatograph;
色谱柱：安捷伦HP-5ms色谱柱汽化温度：280℃程序升温：60℃-3min-20℃/min-280℃-10min；Chromatographic column: Agilent HP-5ms chromatographic column vaporization temperature: 280℃ Programmed temperature rise: 60℃-3min-20℃/min-280℃-10min;
顶空条件：加热箱：110℃定量环：120℃传输线：140℃平衡时间：30min；Headspace conditions: Heating box: 110℃ Quantitative loop: 120℃ Transmission line: 140℃ Equilibration time: 30min;
质谱条件：离子源温度：280℃电子能量：70ev扫描范围(m/z)：30-400；Mass spectrometry conditions: Ion source temperature: 280°C Electron energy: 70ev Scanning range (m/z): 30-400;
表2

Table 2

从以上的描述中，可以看出，本申请上述的实施例实现了如下技术效果：From the above description, it can be seen that the above-mentioned embodiments of the present application achieve the following technical effects:
本申请提供的负型感光性组合物制备得到的固化膜在高温环境下未检测到气体渗漏，其应用于发光器件后也不会造成器件污染，具有广阔的应用前景。The cured film prepared from the negative photosensitive composition provided by this application has no gas leakage detected in a high-temperature environment, and will not cause device pollution after being applied to a light-emitting device, and has broad application prospects.
以上所述仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。 The above descriptions are only preferred embodiments of the present application and are not intended to limit the present application. For those skilled in the art, the present application may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of this application shall be included in the protection scope of this application.

Claims (10)

  1. 一种负型感光性树脂组合物，其特征在于，所述组合物包括以下组分：A negative photosensitive resin composition, characterized in that the composition includes the following components:
    (A)含有聚酰亚胺结构的碱溶性树脂；(A) Alkali-soluble resin containing polyimide structure;
    (B)自由基聚合性化合物；(B) Free radical polymerizable compound;
    (C)至少一种具有如下式(I)所示结构的光聚合引发剂；(C) At least one photopolymerization initiator having a structure represented by the following formula (I);
    以及可选的 and optional
    (D)黑色染料和/或颜料；(D) Black dyes and/or pigments;
    其中，Ar为取代或非取代的C6-C30的芳基；R1和R2各自独立地表示取代或非取代的C1-C15的直链烷基、取代或非取代的C3-C15的支链烷基、取代或非取代的C3-C15的环烷基、取代或非取代的C6-C20的芳基、取代或非取代的C4-C20的杂芳基；R3为甲基。Among them, Ar is a substituted or unsubstituted C6-C30 aryl group; R 1 and R 2 each independently represent a substituted or unsubstituted C1-C15 linear alkyl group, a substituted or unsubstituted C3-C15 branched chain Alkyl group, substituted or unsubstituted C3-C15 cycloalkyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C4-C20 heteroaryl group; R 3 is methyl.
  2. 根据权利要求1所述的负型感光性树脂组合物，其特征在于，所述式(I)中，Ar选自取代或非取代的如下基团中的至少一种：
    The negative photosensitive resin composition according to claim 1, wherein in the formula (I), Ar is selected from at least one of the following substituted or unsubstituted groups:
    其中，所述R4、R5、R6、R7和R8各自独立地表示氢、取代或非取代的C1-C15的直链烷基、取代或非取代的C3-C15的支链烷基、取代或非取代的C3-C15的环烷基；Wherein, R 4 , R 5 , R 6 , R 7 and R 8 each independently represent hydrogen, a substituted or unsubstituted C1-C15 linear alkyl group, a substituted or unsubstituted C3-C15 branched alkyl group. base, substituted or unsubstituted C3-C15 cycloalkyl;
    优选地，所述Ar选自如下基团中的至少一种：
    Preferably, the Ar is selected from at least one of the following groups:
  3. 根据权利要求1所述的负型感光性树脂组合物，其特征在于，所述光聚合引发剂选自具有如下结构化合物中的至少一种：


    The negative photosensitive resin composition according to claim 1, wherein the photopolymerization initiator is selected from at least one compound with the following structure:


    优选地，所述光聚合引发剂选自具有如下结构化合物中的至少一种：
    Preferably, the photopolymerization initiator is selected from at least one compound having the following structure:
  4. 根据权利要求1所述的负型感光性树脂组合物，其特征在于，所述含有聚酰亚胺结构的碱溶性树脂选自聚酰亚胺、聚酰亚胺前体、聚苯并噁唑或聚苯并噁唑前体中的至少一种；The negative photosensitive resin composition according to claim 1, wherein the alkali-soluble resin containing a polyimide structure is selected from the group consisting of polyimide, polyimide precursor, and polybenzoxazole. or at least one of polybenzoxazole precursors;
    和/或，所述自由基聚合性化合物为丙烯酸酯类化合物。And/or, the radically polymerizable compound is an acrylate compound.
  5. 根据权利要求1所述的负型感光性树脂组合物，其特征在于，所述黑色染料为以溶剂黑27～47的染料索引规定的染料；和/或，所述黑色颜料选自炭黑、碳纳米管、乙炔黑、铁黑、苯胺黑、钛黑、苝系颜料或内酰胺系颜料中的至少一种。The negative photosensitive resin composition according to claim 1, wherein 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 the group consisting of carbon black, At least one of carbon nanotubes, acetylene black, iron black, aniline black, titanium black, perylene-based pigments or lactam-based pigments.
  6. 根据权利要求1至5中任一项所述的负型感光性树脂组合物，其特征在于，按质量份数计，所述组合物包括(A)30-80份所述含有聚酰亚胺结构的碱溶性树脂、(B)10-50份所述自由基聚合性化合物、(C)2-8份所述光聚合引发剂、以及可选的(D)2-8份黑色染料和/或颜料；The negative photosensitive resin composition according to any one of claims 1 to 5, characterized in that, in parts by mass, the composition includes (A) 30-80 parts of the polyimide-containing The alkali-soluble resin of the structure, (B) 10-50 parts of the radically polymerizable compound, (C) 2-8 parts of the photopolymerization initiator, and optionally (D) 2-8 parts of black dye and/or or pigment;
    优选地，所述组合物还包括助剂，所述助剂包括增感剂、光引发剂、流平剂、分散剂、固化剂、表面活性剂、消泡剂或储存增强剂中的至少一种。Preferably, the composition further includes auxiliaries, which include at least one of a sensitizer, a photoinitiator, a leveling agent, a dispersant, a curing agent, a surfactant, a defoaming agent or a storage enhancer. kind.
  7. 一种固化膜，其特征在于，所述固化膜的原料为权利要求1至6中任一项所述的负型感光性树脂组合物。A cured film, characterized in that the raw material of the cured film is the negative photosensitive resin composition according to any one of claims 1 to 6.
  8. 根据权利要求7所述的固化膜的制备方法，其特征在于，所述制备方法包括：The preparation method of the cured film according to claim 7, characterized in that the preparation method includes:
    步骤S1，将所述负型感光性树脂组合物溶解或分散于溶剂中，得到负型感光性涂布液；Step S1, dissolve or disperse the negative photosensitive resin composition in a solvent to obtain a negative photosensitive coating liquid;
    步骤S2，将所述负型感光性涂布液涂布在基板表面，去除溶剂，得到待固化被膜，优选通过加热的方式将所述溶剂去除，所述加热的温度优选为70～130℃；Step S2, apply the negative photosensitive coating liquid on the surface of the substrate, remove the solvent, and obtain a film to be cured. The solvent is preferably removed by heating, and the heating temperature is preferably 70 to 130°C;
    步骤S3，将所述待固化被膜进行引发聚合，所述待固化被膜固化形成被膜，优选通过能量辐射的方式进行引发聚合；Step S3, initiating polymerization of the film to be cured, and curing the film to be cured to form a film, preferably by initiating polymerization by energy radiation;
    步骤S4，将所述被膜依次进行显影处理、洗涤和加热，得到所述固化膜，所述显影处理的时间优选为30～180s，所述加热的温度优选为100～350℃，所述加热的时间优选为2～20min。Step S4, the film is developed, washed and heated in sequence to obtain the cured film. The development time is preferably 30 to 180 s, and the heating temperature is preferably 100 to 350°C. The time is preferably 2 to 20 minutes.
  9. 一种EL元件，其特征在于，所述EL元件包括权利要求1至6中任一项所述的负型感光性树脂组合物或权利要求7所述的固化膜。An EL element, characterized in that the EL element includes the negative photosensitive resin composition according to any one of claims 1 to 6 or the cured film according to claim 7.
  10. 一种显示装置，其特征在于，所述显示装置包括权利要求1至6中任一项所述的负型感光性树脂组合物、权利要求7所述的固化膜或权利要求8所述的EL元件。 A display device, characterized in that the display device includes the negative photosensitive resin composition according to any one of claims 1 to 6, the cured film according to claim 7, or the EL according to claim 8. element.
PCT/CN2023/101514 2022-06-24 2023-06-20 Negative photosensitive resin composition, cured film and preparation method therefor, el element, and display apparatus WO2023246811A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210725485.5A CN117348340A (en) 2022-06-24 2022-06-24 Negative photosensitive resin composition, cured film, method for producing same, EL element, and display device
CN202210725485.5 2022-06-24

Publications (1)

Publication Number Publication Date
WO2023246811A1 true WO2023246811A1 (en) 2023-12-28

Family

ID=89361803

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/101514 WO2023246811A1 (en) 2022-06-24 2023-06-20 Negative photosensitive resin composition, cured film and preparation method therefor, el element, and display apparatus

Country Status (2)

Country Link
CN (1) CN117348340A (en)
WO (1) WO2023246811A1 (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005099584A (en) * 2003-09-26 2005-04-14 Nippon Kayaku Co Ltd Negative colored photosensitive composition
CN102459171A (en) * 2009-06-17 2012-05-16 东洋油墨Sc控股株式会社 Oxime ester compound, radical polymerization initiator, polymerizable composition, negative resist and image pattern
CN103819583A (en) * 2014-03-18 2014-05-28 常州强力电子新材料股份有限公司 Photoinitiator containing nitro dioxime ester and preparation method and application thereof
CN104076606A (en) * 2014-07-15 2014-10-01 常州强力电子新材料股份有限公司 Photoelectric sensitive composition containing oxime ester type photoinitiator and application thereof
US20180356729A1 (en) * 2016-03-30 2018-12-13 Toray Industries, Inc. Negative-type photosensitive resin composition, cured film, display device that includes the cured film, and production method therefor
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
KR20200081810A (en) * 2018-12-28 2020-07-08 주식회사 삼양사 Carbazole multi β-oxime ester derivative compounds and, photopolymerization initiator and photoresist composition containing the same
JP2021155642A (en) * 2020-03-30 2021-10-07 日油株式会社 Bis-oxime ester based photoinitiator, polymerizable composition, and cured product and production method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005099584A (en) * 2003-09-26 2005-04-14 Nippon Kayaku Co Ltd Negative colored photosensitive composition
CN102459171A (en) * 2009-06-17 2012-05-16 东洋油墨Sc控股株式会社 Oxime ester compound, radical polymerization initiator, polymerizable composition, negative resist and image pattern
CN103819583A (en) * 2014-03-18 2014-05-28 常州强力电子新材料股份有限公司 Photoinitiator containing nitro dioxime ester and preparation method and application thereof
CN104076606A (en) * 2014-07-15 2014-10-01 常州强力电子新材料股份有限公司 Photoelectric sensitive composition containing oxime ester type photoinitiator and application thereof
US20180356729A1 (en) * 2016-03-30 2018-12-13 Toray Industries, Inc. Negative-type photosensitive resin composition, cured film, display device that includes the cured film, and production method therefor
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
KR20200081810A (en) * 2018-12-28 2020-07-08 주식회사 삼양사 Carbazole multi β-oxime ester derivative compounds and, photopolymerization initiator and photoresist composition containing the same
JP2021155642A (en) * 2020-03-30 2021-10-07 日油株式会社 Bis-oxime ester based photoinitiator, polymerizable composition, and cured product and production method thereof

Also Published As

Publication number Publication date
CN117348340A (en) 2024-01-05

Similar Documents

Publication Publication Date Title
US9383480B2 (en) Photocurable acrylate composition
TWI431036B (en) Photosensitive resin composition and light blocking layer using the same
KR101981579B1 (en) Photosensitive Composition for Display Device, Black Matrix Having the Composition, and Process for forming Patterns of Black Matrix Using the Composition
TWI534538B (en) Negative photosensitive resin composition
JP7283300B2 (en) Photosensitive coloring composition, color filter and display element
KR101583538B1 (en) Multifunctional thiol compound-containing photosensitive resin composition for black resist black matrix for color filter using the same and color filter
JP2008122750A (en) Photosensitive resist composition for color filter, and the color filter
TW201015220A (en) Colored radiation sensitive composition, color filter and color liquid crystal display element
JP5191567B2 (en) Positive photosensitive resin composition, method for forming cured film, cured film, organic EL display device, and liquid crystal display device
WO2015080217A1 (en) Coloring resin composition, color filter, liquid crystal display device and organic el display device
WO2019024547A1 (en) Positive photoresist composition, via hole formation method, display substrate, and display device
JP2008249987A (en) Photosensitive resist composition and color filter
TWI414539B (en) Photosensitive resin composition and light blocking layer using the same
WO2023246811A1 (en) Negative photosensitive resin composition, cured film and preparation method therefor, el element, and display apparatus
JP7318533B2 (en) Photosensitive resin composition for color filter, color filter, image display device, and method for producing color filter
JP6977679B2 (en) Colored resin composition, color filter and image display device
JP2009169049A (en) Photosensitive resist composition for color filter and color filter
TW201706712A (en) Compositions and methods for forming a pixel-defining layer
TWI825269B (en) Yellow colored hardening composition
CN1205454A (en) Photosensitive resin compsns. and display components using same
JP2023168206A (en) Photosensitive composition, colored cured object and manufacturing method therefor, and display device
KR102383693B1 (en) Colored photosensitive composition, color filter and image display device
JP2016186572A (en) Photosensitive resin composition
TW201704868A (en) Photosensitive resin composition for dry etching, and method for producing resist pattern for dry etching
TW202116827A (en) Colored resin composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23826458

Country of ref document: EP

Kind code of ref document: A1