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

Abstract

The present application provides a negative photosensitive resin composition, a cured film and a method for producing the same, an EL element, and a display device. The negative photosensitive resin composition contains (A) an alkali-soluble resin containing a polyimide structure, (B) a radically polymerizable compound, (C) a photoinitiator having a structure represented by at least one of the following formula (I), and, if necessary, (D) a black dye and / or a pigment. By adopting the embodiments of the present application, the negative photosensitive composition provided by the present application not only has excellent heat resistance and light-shielding properties, but also no gas leakage is detected in a high-temperature environment after being applied to a light-emitting device, no contamination of the device is caused, and it is expected to be widely applied. JPEG2025520977000027.jpg66170

Description

Technical Field

[0001] [Cross - Reference to Related Applications] This application claims the priority of a Chinese patent application filed with the China National Intellectual Property Administration on June 24, 2022, with application number 202210725485.5 and titled "Negative Photosensitive Resin Composition, Cured Film and Method for Producing the Same, EL Element and Display Device", and all of its contents are incorporated herein by reference.

[0002] [Technical Field] This application relates to the technical field of photosensitive resin compositions, and specifically, to negative photosensitive resin compositions, cured films and methods for producing the same, EL elements and display devices.

Background Art

[0003] In recent years, in displays equipped with thin - film displays such as smartphones, tablet PCs, and televisions, many products having organic electroluminescence (hereinafter abbreviated as "EL") displays have been developed.

[0004] An organic EL display is a self - luminous element that emits light by the energy generated from the recombination of electrons injected from the cathode and holes injected from the anode. However, the movement of electrons or holes is often inhibited, which causes a decrease in the luminous efficiency of the self - luminous element or the deactivation of the light - emitting material, and easily reduces the lifespan of the self - luminous element. Since the pixel - dividing layer is formed at a position adjacent to the self - luminous element, outgassing from the pixel - dividing layer and the outflow of ionic components can be one of the causes of the reduction in the lifespan of the organic EL display. Therefore, high heat resistance is required for the pixel - dividing layer. In the prior art, usually, a negative photosensitive resin composition having a high - heat - resistant polyimide and an oxime ester - based photoinitiator is adopted to solve the problem of high heat resistance. However, self - luminous devices manufactured with such compositions often have outgas leakage and device contamination in a high - temperature environment.

[0005] In view of this, the present application is proposed.

Summary of the Invention

[0006] The main object of the present application is to solve the problems of outgas leakage and device contamination in a high-temperature environment of a self-luminous device manufactured with a negative photosensitive resin composition containing polyimide and an oxime ester-based photopolymerization initiator in the prior art, and to provide a negative photosensitive resin composition, a cured film, a method for producing the same, an EL element, and a display device. [Means for Solving the Problems]

[0007] In order to achieve the above object, according to a first aspect of the present application, a negative photosensitive resin composition containing the following components is provided. (A) An alkali-soluble resin containing a polyimide structure (B) A radically polymerizable compound (C) A photopolymerization initiator having a structure represented by at least one of the following formulas (I), and, if necessary, (D) a black dye and / or pigment: [Chemical formula] [In the formula, Ar is a substituted or unsubstituted C6-C30 aryl group. R1 and R2 are each independently a substituted or unsubstituted C1-C15 linear alkyl group, a substituted or unsubstituted C3-C15 branched 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. R3 is a methyl group.]

[0008] In the formula (I), Ar is at least one selected from the group consisting of the following substituted or unsubstituted groups: [Chemical formula] However, each of R4, R5, R6, R7, and R8 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, Furthermore, Ar is at least one selected from the group consisting of the following groups.

Chemical formula

[0009] Furthermore, the photopolymerization initiator is at least one selected from the group consisting of compounds having the following structures,

Chemical formula

[0010]

Chemical formula

[0011]

Chemical formula

[0012] Furthermore, the photopolymerization initiator is at least one selected from the group consisting of compounds having the following structures.

[0013]

Chemical formula

[0014] Furthermore, the alkali-soluble resin containing the polyimide structure is at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor, and / or the radically polymerizable compound is an acrylate compound.

[0015] Furthermore, the black dye is a dye defined in the dye index of Solvent Black 27 to 47, and / or the black pigment is at least one selected from the group consisting of carbon black, carbon nanotubes, acetylene black, iron black, aniline black, titanium black, perylene-based pigments or lactam-based pigments.

[0016] Furthermore, in parts by mass, the negative photosensitive resin composition contains (A) 30 to 80 parts of an alkali-soluble resin containing a polyimide structure, (B) 10 to 50 parts of a radically polymerizable compound, (C) 2 to 8 parts of a photopolymerization initiator, and optionally (D) 2 to 8 parts of a black dye and / or pigment.

[0017] Furthermore, the negative photosensitive resin composition further contains an auxiliary agent, and the auxiliary agent is at least one of a sensitizer, a photoinitiator, a leveling agent, a dispersant, a curing agent, a surfactant, an antifoaming agent or a storage stabilizer.

[0018] In order to achieve the above object, according to the second aspect of the present application, there is further provided a cured film made from any of the negative photosensitive resin compositions provided by the first aspect as a raw material.

[0019] According to the third aspect of the present application, there is further provided a method for manufacturing the cured film provided by the second aspect. The manufacturing method includes a step S1 of dissolving or dispersing the negative photosensitive resin composition in a solvent to obtain a negative photosensitive coating solution; a step S2 of applying the negative photosensitive coating solution onto the surface of a substrate and removing the solvent to obtain a film to be cured, preferably removing the solvent by heating, and the heating temperature is preferably 70 to 130°C; a step S3 of initiating the polymerization of the film to be cured and curing the film to be cured to form a film, preferably initiating the polymerization by energy irradiation; and a step S4 of sequentially developing, washing and heating the film to obtain a cured film, the developing time is preferably 30 to 180 s, the heating temperature is preferably 100 to 350°C, and the heating time is preferably 2 to 20 min.

[0020] According to the fourth aspect of the present application, there is further provided an EL element including any negative photosensitive resin composition provided by the first aspect or a cured film provided by the second aspect.

[0021] According to the fifth aspect of the present application, there is further provided a display device including any negative photosensitive resin composition provided by the first aspect, a cured film provided by the second aspect, or an EL element provided by the fourth aspect.

[0022] By applying the embodiments of the present application, the negative photosensitive composition provided by the present application not only has excellent heat resistance and light-shielding properties, but also no gas leakage is detected in a high-temperature environment after being applied to a light-emitting device, no contamination of the device is caused, and there is a prospect of wide application.

Embodiments for Carrying Out the Invention

[0023] Unless there is a contradiction, the embodiments in the present application and the features in the embodiments may be combined with each other. Hereinafter, the present application will be described with reference to the embodiments.

[0024] As analyzed in the background art of the present application, in the prior art, a self-luminous device manufactured from a negative photosensitive resin composition containing a polyimide with high heat resistance and an oxime ester-based photoinitiator often has outgas leakage and contamination of the device in a high-temperature environment. To solve this problem, the present application provides a negative photosensitive resin composition, a cured film and a method for manufacturing the same, an EL element, and a display device.

[0025] In one representative embodiment of the present application, a negative photosensitive resin composition is provided, and the composition includes (A) an alkali-soluble resin containing a polyimide structure, (B) a radically polymerizable compound, (C) a photoinitiator having a structure represented by the following formula (I), and optionally (D) a black dye and / or a pigment.

[0026]

Chemical formula

[0027] In the above formula (I), Ar is a substituted or unsubstituted C6-C30 aryl group. R1 and R2 are each independently a substituted or unsubstituted C1-C15 linear alkyl group, a substituted or unsubstituted C3-C15 branched 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. R3 is a methyl group.

[0028] By applying the embodiments of the present application, the negative photosensitive composition provided by the present application not only has excellent heat resistance and light-shielding properties, but also no gas leakage is detected in a high-temperature environment after being applied to a light-emitting device, it does not cause contamination to the device, and has the prospect of being widely applied.

[0029] In order to further reduce the gas leakage of the optoelectronic device manufactured with the above negative photosensitive resin composition, preferably, Ar is at least one selected from the group consisting of the following groups.

[0030]

Chemical formula

[0031] Next, R4, R5, R6, R7 and R8 each independently represent 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.

[0032] In some embodiments of the present application, when Ar is at least one selected from the group consisting of the following groups, the gas leakage prevention property of the optoelectronic device manufactured with the above negative photosensitive resin composition is more excellent.

[0033]

Chemical formula

[0034] In the present application, "*" represents the bonding position of a chemical group.

[0035] In some preferred embodiments of the present application, when the negative photosensitive resin composition is applied to an optoelectronic device, in order to further reduce the possibility of gas leakage and further avoid contamination of the device, the photoinitiator is preferably at least one selected from the group consisting of the following compounds.

[0036] [Chemical formula]

[0037] [Chemical formula]

[0038] [Chemical formula]

[0039] In some embodiments of the present application, when the photoinitiator is at least one selected from the group consisting of the following compounds, the gas leakage prevention property of the negative photosensitive resin composition containing it becomes more remarkable.

[0040] [Chemical formula]

[0041] The alkali-soluble resin containing the above polyimide structure is not limited, and any alkali-soluble resin containing a polyimide structure having excellent heat resistance may be used. In particular, when the alkali-soluble resin containing the above polyimide structure is any one or a mixture of two or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole or polybenzoxazole precursor, the heat resistance performance of the manufactured optoelectronic device is more excellent.

[0042] There is no restriction on the type of the above radical polymerizable compound, and any radical polymerizable compound that can be initiated by the above photoinitiator may be used. From the viewpoint of improving the initiation efficiency, the radical polymerizable compound is preferably an acrylate compound, and examples thereof include a mixed resin formed of any one or two or more of methyl methacrylate, methyl methacrylate, butyl methacrylate, pentaerythritol tetraacrylate, or trimethylolpropane triacrylate, but are not limited thereto.

[0043] There is no restriction on the type of the above black dye or black pigment, and any substance having black coloring ability may be used. In order to further improve the dispersion performance and coloring performance of the above black dye, the black dye is preferably a dye defined 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 above black pigment, the black pigment is preferably a mixed pigment formed of any one or two or more selected from the group consisting of carbon black, carbon nanotube, acetylene black, iron black, aniline black, titanium black, perylene-based pigment, or lactam-based pigment.

[0044] In order to further improve the performance of the above negative photosensitive resin composition, the negative photosensitive resin composition preferably further contains an auxiliary agent, and examples of this auxiliary agent include a sensitizer, a photoinitiator, a leveling agent, a dispersant, a curing agent, a surfactant, an antifoaming agent, or a storage stabilizer, and include a mixed auxiliary agent formed of any one or two of them, but are not limited thereto.

[0045] In some embodiments of the present application, in order to further improve the light and heat resistance performance, light shielding performance, and gas leakage prevention performance of the optoelectronic device to which the above negative photosensitive resin composition is applied, the negative photosensitive resin composition preferably contains 30 to 80 parts by mass of an alkali-soluble resin containing a polyimide structure, 10 to 50 parts by mass of a radical polymerizable compound, 2 to 8 parts by mass of a photoinitiator, and 2 to 8 parts of a black dye and / or pigment as required.

[0046] Typically, in the above negative photosensitive resin composition, the parts by mass of the alkali-soluble resin containing a polyimide structure are, for example, 30 parts, 35 parts, 40 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 80 parts, or values within a range consisting of any two numerical values. The parts by mass of the radically polymerizable compound are, for example, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, or values within a range consisting of any two numerical values. The parts by mass of the photopolymerization initiator are, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, or values within a range consisting of any two numerical values. The parts by mass of the black dye and / or pigment are, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, or values within a range consisting of any two numerical values, but are not limited thereto.

[0047] In another representative embodiment of the present application, there is further provided a cured film made from any of the negative photosensitive resin compositions provided by the above first representative embodiment as a raw material.

[0048] The cured film provided by the present application is manufactured by adopting the above negative photosensitive resin composition as a raw material, and not only has excellent light and heat resistance performance and light shielding performance, but also has no gas leakage even in a high-temperature environment, does not cause contamination to optoelectronic devices, and has the potential for wide application.

[0049] In the third representative embodiment of the present application, there is further provided a method for manufacturing the above cured film. The manufacturing method includes a step S1 of dissolving or dispersing the negative photosensitive resin composition in a solvent to obtain a negative photosensitive coating solution; a step S2 of applying the negative photosensitive coating solution onto the surface of a substrate, removing the solvent, and obtaining a film to be cured; a step S3 of initiating polymerization of the film to be cured and curing the film to be cured to form a film; and a step S4 of sequentially subjecting the film to development treatment, washing, and heating to obtain a cured film.

[0050] The method for manufacturing the cured film provided by the present application has a simple process, convenient operation, is suitable for large-scale production, can effectively improve the manufacturing efficiency, and can reduce the production cost.

[0051] In the above step S1, there is no restriction on the type of solvent. From the perspective of subsequent removal, it is preferably a low-boiling solvent, such as, but not limited to, propylene glycol methyl ether acetate.

[0052] In order to avoid the subsequent coating uniformity being affected by the aggregation or non-uniform dispersion of the composition in the above coating solution, the above negative-type photosensitive coating solution is first filtered, for example, through a precision filtration filter with a pore size of 0.05 - 1.0 μm before coating.

[0053] In order to avoid the above composition being unable to be uniformly dispersed or dissolved in the solvent, it is preferable to perform dispersion mixing by using methods and dispersion mixing devices well-known in the art, such as ball mills, sand mills, bead mills, paint mixers, ball-type devices such as rocking mills, kneaders, paddle mixers, planetary mixers, blade-type devices such as Henschel mixers, roll-type devices such as three-roll kneaders, and crushing machines, colloid mills, ultrasonic waves, homogenizers, rotation-revolution mixers, etc. From the perspective of dispersion efficiency and fine dispersion, it is preferable to perform dispersion mixing with a bead mill.

[0054] In the above step S2, there is no restriction on the coating method, and examples include, but are not limited to, the spray method, roller coating method, slit method, or spinner method. There is no restriction on the material of the substrate, and it is preferably a glass substrate.

[0055] In the above step S2, there is no restriction on the method of removing the solvent, and it is preferable to remove the solvent by heating. The heating conditions vary depending on the types, mixing ratios of the components of the negative-type photosensitive resin composition, and the selection of the solvent. In order to further improve the removal efficiency of the solvent, preferably, the heating temperature is 70 - 130 °C. If heated with a heating plate, the heating time is 1 - 20 min, and if heated in an oven, the heating time is 3 - 60 min.

[0056] In the above step S3, there is no restriction on the form of the energy source for initiating polymerization. Any of ultraviolet rays, visible light, infrared rays, electron beams, and laser energy can be used to irradiate and initiate the polymerization of the negative photosensitive resin composition provided by the first representative embodiment of the present application, enabling rapid curing. Examples of the energy source for the above polymerization initiation include, but are not limited to, ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, mercury-xenon lamps, low pressure mercury lamps, metal halide lamps, xenon lamps, deuterium lamps, chemical lamps, LED lamps, fluorescent lamps, tungsten lamps, Nd-YAG triple wavelength lasers, He-Cd lasers, nitrogen lasers, Xe-Cl excimer lasers, Xe-F excimer lasers, semiconductor-excited solid state lasers, actinic rays such as i-line, h-line, and g-line. The above energy source may further be electron beams, α-rays, β-rays, γ-rays, X-rays, and neutron rays, etc. It is preferable that the radiation is ultraviolet to visible light with a wavelength of 250 to 450 nm. The irradiation intensity is preferably 50 to 100 mJ / cm 2 is preferable.

[0057] In the above step S4, it is preferable that the above development process is carried out by bringing the film into contact with a developer to develop and remove unnecessary portions to form a pattern on the film. Examples of the developer in the above developer include, but are not limited to, mixed developers formed from any one or two 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.

[0058] The inorganic alkali compound is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, or an aqueous ammonium solution, etc. The primary amine compound is, for example, ethylamine, n-propylamine, etc. The secondary amine compound is, for example, diethylamine, di-n-propylamine, etc. The tertiary amine compound is, for example, triethylamine, methyldiethylamine, etc. The alcohol amine compound is, for example, dimethylethanolamine, triethanolamine, etc. The quaternary ammonium salt compound is, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc. The cyclic amine alkali compound is, for example, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane, etc.

[0059] The above developer is obtained by dissolving and / or dispersing a developer in a solvent. The solvent of the developer includes an aqueous solution and, if necessary, an organic solvent. Examples of the organic solvent include, but are not limited to, aqueous solutions of organic solvents such as methanol and ethanol. In order to further improve the dispersion stability of the developer, auxiliary agents such as surfactants may be further added to the developer.

[0060] The method of the above development process is not limited, and examples include any one or a combination of two or more development methods such as the puddle method, the shower method, or the dipping method, but are not limited thereto. In order to further improve the adequacy of development, the development time is preferably 30 to 180 s.

[0061] In order to avoid too much developer adhering to the surface of the film after development and affecting the performance, preferably, the film after development is washed with water. The washing time is preferably 30 to 90 s to remove unnecessary parts, and then air-dried with compressed air or compressed nitrogen gas to form a pattern on the film after development.

[0062] The above heating method is not limited. In order to further improve the heating efficiency, preferably, the film with the above pattern is heated at 100 to 350 °C for 2 to 20 minutes to form a cured film.

[0063] In the fourth representative embodiment of the present application, an EL element is further provided. The EL element has a partition wall, and the partition wall is any of the cured films provided by the above third representative embodiment, or the partition wall contains any of the negative photosensitive resin compositions provided by the above first representative embodiment.

[0064] The EL element provided by the present application employs a cured film formed of the above negative photosensitive resin composition as a partition wall, and no gas leakage is detected even in a high-temperature environment, no contamination to the optoelectronic device is caused, and it is expected to be widely applied.

[0065] In the fifth representative embodiment of the present application, a display device is further provided. The display device includes any of the negative photosensitive resin compositions provided by the above first representative embodiment, any of the cured films provided by the above second representative embodiment, or the EL element provided by the above fourth representative embodiment.

[0066] The display device provided by the present application employs the negative photosensitive resin composition provided by the first representative embodiment, and no gas leakage is detected even in a high-temperature environment, no contamination to the light-emitting device is caused, and it is expected to be widely applied.

Examples

[0067] Hereinafter, with reference to Examples and Comparative Examples, the beneficial effects of the present application will be further described.

[0068] <Example 1> This example provides a cured film manufactured according to the following steps. (1) An alkali-soluble resin A1 containing a polyimide structure, a radical polymerizable compound B1, a photoinitiator C1, and carbon black were each mixed with a bead mill at 80:10:5:5 (parts by mass), and dispersed and stirred for 3 hours to obtain a negative photosensitive resin composition. (2) The negative photosensitive resin composition was dispersed in 100 parts by mass of polypropylene glycol methyl ether acetate (PGMEA) as a solvent to obtain a negative photosensitive coating solution. (3) A glass substrate (size 100 mm × 100 mm × 1 mm) was sequentially washed with a neutral detergent (N-methylpyrrolidone, Aladdin), water, and ethanol and then dried. The negative photosensitive coating solution was spin-coated onto the glass substrate, baked at 90 °C for 125 seconds using a hot plate to remove the solvent, cooled to room temperature, and a film to be cured adhering to the substrate was obtained. (4) The above film was sufficiently exposed with a mercury lamp (RW-LED-YT200gl) at 100 mJ / cm 2 to obtain a cured film with a thickness of 1.5 μm. (5) The above film was immersed in a 0.04% aqueous potassium hydroxide 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.

[0069] <Example 2> This example is different from Example 1 in that, in step (1), an alkali-soluble resin A2 containing a polyimide structure is employed instead of A1, a radical polymerizable compound B2 is employed instead of B1, and a photoinitiator C2 is employed instead of C1.

[0070] <Example 3> This 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.

[0071] <Example 4> This 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.

[0072] <Example 5> This 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.

[0073] <Example 6> This 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.

[0074] <Example 7> This 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.

[0075] <Example 8> This 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.

[0076] <Example 9> This 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.

[0077] <Example 10> This 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.

[0078] <Example 11> This 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.

[0079] <Example 12> This 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.

[0080] <Example 13> This 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.

[0081] <Example 14> This 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.

[0082] <Comparative Example 1> This Comparative Example 1 provides a cured film and 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.

[0083] <Comparative Example 2> This Comparative Example 2 provides a cured film and 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.

[0084] The specific information of the above A1, A2, B1, B2, C1 - C8 and carbon black is as follows. A1: Polyimide resin: Model number GCPI - PAA A2: Polyimide resin: Model number JCL3030 B1: Pentaerythritol tetraacrylate: Model number: A - TMMT B2: Trimethylolpropane triacrylate: Model number: M309

[0085]

Chemical formula

[0086] [Chemical formula]

[0087] Carbon black: Model number: Ketjenblack EC600JD.

[0088] <Test Example 1> For each of the cured films provided by the above Examples and Comparative Examples, heat resistance evaluation and light shielding property evaluation were performed, and the results are shown in Table 1 below.

[0089] The specific method of the heat resistance test is as follows. Each of the above cured films was baked in a convection oven at 230 °C for 30 min, and then ΔE*ab was determined based on the chromaticity of the colored pattern before and after heating. When ΔE*ab is 3.0 or less, it is evaluated as having excellent heat resistance.

[0090] The specific method of the light shielding property test is as follows. Under the conditions of a temperature of 30 °C, a humidity of 50%, and a black panel temperature of 63 °C, the cured film was irradiated with 180 W for 60 h, and ΔE*ab was determined based on the chromaticity of the colored pattern before and after irradiation. When ΔE*ab is 3.0 or less, it is evaluated as having excellent heat resistance.

[0091]

Table 1

[0092] <Test Example 2> A gas leakage test was performed on the cured films provided by the Examples and Comparative Examples, and the results are shown in Table 2 below.

[0093] The method of the gas leakage test is as follows. The GC-MS test method was adopted. 5 g of each of the cured films provided by the above Examples and Comparative Examples was taken, cut, and then placed in a headspace vial for preparation. Headspace sampling was adopted to observe the generation of outgassing (the peak of the solvent contained in itself and excluding carbon dioxide). Machine: Agilent 7890B Gas Chromatography Column: Agilent HP-5ms Column, Vaporization Temperature: 280°C Programmed Temperature Rise: 60°C - 3 min - 20°C / min - 280°C - 10 min Headspace Conditions: Heating Oven: 110°C, Quantitative Ring: 120°C, Transfer Line: 140°C, Equilibration Time: 30 min Mass Spectrometry Conditions: Ion Source Temperature: 280°C, Electron Energy: 70 eV, Scanning Range (m / z): 30 - 400

[0094]

Table 2

[0095] As can be seen from the above description, the above embodiments of the present application have achieved the following technical effects.

[0096] The cured film produced by the negative photosensitive composition provided by the present application has no gas leakage detected in a high-temperature environment, does not cause contamination to the device after being applied to the light-emitting device, and has the potential for wide application.

[0097] The above are only preferred embodiments of the present application and are not intended to limit the present application. Those skilled in the art can make various changes and modifications to the present application. Any modifications, equivalent replacements, improvements, etc., made without departing from the spirit and principles of the present application should be included within the protection scope of the present application.

Claims

Claim 1 A negative photosensitive resin composition comprising the following components: (A) An alkali-soluble resin containing a polyimide structure (B) A radically polymerizable compound (C) A photoinitiator having a structure represented by at least one of the following formulas (I) 【Chemical 1】 [In the formula, Ar is a substituted or unsubstituted C6-C30 aryl group. R １ and R ２ each independently represents a substituted or unsubstituted C1-C15 linear alkyl group, a substituted or unsubstituted C3-C15 branched 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 ３ is a methyl group.] and, optionally, (D) a black dye and / or pigment. Claim 2 In the formula (I), Ar is at least one selected from the group consisting of substituted or unsubstituted following groups, 【Chemical Formula 2】 However, the R ４ , R ５ , R ６ , R ７ , and R 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, the negative photosensitive resin composition according to claim 1, wherein the Ar is at least one selected from the group consisting of the following groups. [Chemical Formula 3] Claim 3 The photoinitiator is at least one selected from the group consisting of compounds having the following structure, 【Chemical Formula 4】 [Chemical Formula 5] 【Chemical Formula 6】 Preferably, the negative photosensitive resin composition according to claim 1, wherein the photoinitiator is at least one selected from the group consisting of compounds having the following structure. 【Chemical Formula 7】 Claim 4 The alkali-soluble resin containing a polyimide structure is at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole or polybenzoxazole precursor, and / or the radically polymerizable compound is an acrylate compound. The negative photosensitive resin composition according to claim 1. Claim 5 The black dye is a dye defined in the dye index of Solvent Black 27-47, and / or the black pigment is at least one selected from the group consisting of carbon black, carbon nanotube, acetylene black, iron black, aniline black, titanium black, perylene-based pigment or lactam-based pigment. The negative photosensitive resin composition according to claim 1. Claim 6 By mass, the composition comprises 30-80 parts of (A) the alkali-soluble resin containing a polyimide structure, 10-50 parts of (B) the radically polymerizable compound, 2-8 parts of (C) the photoinitiator, and optionally 2-8 parts of (D) a black dye and / or pigment, Preferably, the composition further comprises an auxiliary agent, and the auxiliary agent is at least one of a sensitizer, a photoinitiator, a leveling agent, a dispersant, a curing agent, a surfactant, an antifoaming agent or a storage stabilizer. The negative photosensitive resin composition according to any one of claims 1-5. Claim 7 A cured film characterized by using the negative photosensitive resin composition according to any one of claims 1-6 as a raw material. Claim 8 The method for producing a cured film according to claim 7, wherein: a step S1 of dissolving or dispersing the negative photosensitive resin composition in a solvent to obtain a negative photosensitive coating solution; a step S2 of applying the negative photosensitive coating solution onto the surface of a substrate, removing the solvent to obtain a film to be cured, preferably removing the solvent by heating, and the temperature of the heating is preferably 70 to 130°C; a step S3 of initiating polymerization of the film to be cured, curing the film to be cured to form a film, preferably initiating polymerization by energy irradiation; a step S4 of subjecting the film to development treatment, washing, and heating in sequence to obtain the cured film, the time of the development treatment is preferably 30 to 180 s, the temperature of the heating is preferably 100 to 350°C, and the time of the heating is preferably 2 to 20 min; The production method is characterized by including the above steps.

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.

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