Negative photosensitive resin composition, cured film and method for preparing the same, EL element, and display apparatus

Abstract

The present invention provides a negative-type photosensitive resin composition, a cured film, a method for manufacturing the same, an EL element, and a display device. The negative-type photosensitive resin composition comprises: (A) an alkali-soluble resin containing a polyimide structure; (B) a free radical polymerizable compound; (C) at least one photopolymerization initiator having a structure represented by the following formula (I); and a preferred (D) black dye and / or pigment. By applying the technical solution of the present invention, the negative-type photosensitive composition provided by the present invention not only possesses excellent heat resistance and light-blocking properties, but also, when applied to a light-emitting element, does not detect gas leakage even in high-temperature environments and does not cause device contamination, thus having a wide range of application prospects.

Description

Technology Field

[0001] The present invention claims priority to a Chinese patent application filed with the National Intellectual Property Administration of China on June 24, 2022, with application number 202210725485.5 and title of the invention "Negative type photosensitive resin composition, cured film and method for manufacturing the same, EL element and display device," the entire contents of which are incorporated by reference into the present invention.

[0002] The present invention relates to the field of photosensitive resin composition technology, specifically to a negative-type photosensitive resin composition, a cured film and a method for manufacturing the same, an EL element and a display device. Background Technology

[0003] In recent years, many products utilizing organic electroluminescent (hereinafter abbreviated as "EL") displays have been developed for display devices equipped with thin displays, such as smartphones, tablet PCs, and TVs.

[0004] Organic EL displays possess self-luminous elements that emit light using energy generated by the recombination of electrons injected from the cathode and holes injected from the anode; however, since the movement of electrons or holes is often obstructed, the luminous efficiency of the self-luminous elements decreases or the light-emitting material becomes deactivated, which tends to shorten the lifespan of the self-luminous elements. Since the pixel segmentation layer is formed in a location adjacent to the self-luminous elements, degassing and leakage of ionic components from the pixel segmentation layer can cause the lifespan of the organic EL display to be shortened, thus requiring high heat resistance of the pixel segmentation layer. In prior art, the problem of high heat resistance was generally solved by using a negative-type photosensitive resin composition containing high-heat-resistant polyimide-based and oxime ester-based photopolymerization initiators; however, self-luminous elements manufactured using such compositions often experience leakage of overflowed gas in high-temperature environments, contaminating the elements.

[0005] Considering this, the present invention is proposed. The problem to be solved

[0006] The main objective of the present invention is to provide a negative-type photosensitive resin composition, a cured film, a method for manufacturing the same, an EL device, and a display device to solve the problem of the prior art in which gas overflowing in a high-temperature environment leaks and contaminates a self-luminous device manufactured with a negative-type photosensitive resin composition comprising a polyimide-based and oxime ester-based photopolymerization initiator. means of solving the problem

[0007] To achieve the above objective, according to a first aspect of the present invention, a negative-type photosensitive resin composition is provided, said composition comprising: (A) an alkali-soluble resin having a polyimide structure; (B) a free radical polymerizable compound; (C) at least one photopolymerization initiator having a structure represented by the following formula (I); and a preferred (D) a black dye and / or pigment;

[0008] Equation (I)

[0009] Here, Ar is a substituted or unsubstituted C6-C30 aryl; R1 and R2 each independently represent a substituted or unsubstituted C1-C15 straight-chain alkyl, a substituted or unsubstituted C3-C15 branched-chain alkyl, a substituted or unsubstituted C3-C15 cycloalkyl, a substituted or unsubstituted C6-C20 aryl, or a substituted or unsubstituted C4-C20 heteroaryl; and R3 is methyl.

[0010] In addition, in the above formula (I), Ar is at least one selected from the following substituted or unsubstituted groups.

[0011]

[0012] .

[0013] Here, R4, R5, R6, R7 and R8 each independently represent hydrogen, a substituted or unsubstituted C1-C15 straight-chain alkyl, a substituted or unsubstituted C3-C15 branched-chain alkyl, or a substituted or unsubstituted C3-C15 cycloalkyl.

[0014] In addition, Ar is at least one selected from the following devices.

[0015]

[0016] .

[0017] In addition, the photopolymerization initiator is at least one selected from compounds having the following structure.

[0018]

[0019]

[0020]

[0021] .

[0022] In addition, the photopolymerization initiator is at least one selected from compounds having the following structure.

[0023] .

[0024] Additionally, the alkali-soluble resin containing a polyimide structure is at least one selected from polyimide, a polyimide precursor, polybenzoxazole, or a polybenzoxazole precursor; and / or, the free radical polymerizable compound is an acrylate-based compound.

[0025] Additionally, the black dye is a dye defined by the color index of solvent black 27 to 47; and / or, the black pigment is at least one selected from carbon black, carbon nanotubes, acetylene black, iron black, aniline black, titanium black, perylene-based pigments or lactam-based pigments.

[0026] In addition, based on parts by mass, the negative-type photosensitive resin composition comprises (A) 30 to 80 parts of an alkali-soluble resin containing a polyimide structure; (B) 10 to 50 parts of a free radical polymerizable compound; (C) 2 to 8 parts of a photopolymerization initiator; and preferably (D) 2 to 8 parts of a black dye and / or pigment.

[0027] Additionally, the negative-type photosensitive resin composition further comprises an auxiliary agent, said auxiliary agent comprises at least one of a sensitizer, a photoinitiator, a leveling agent, a dispersant, a curing agent, a surfactant, an antifoaming agent, or a storage enhancer. To achieve the above objective, according to a second aspect of the present invention, a cured film is further provided, said cured film being any negative-type photosensitive resin composition provided in the first aspect.

[0028] According to a third aspect of the present invention, a method for manufacturing a cured film provided in the second aspect is further provided, the method comprising: a step S1 of obtaining a negative-type photosensitive coating solution by dissolving or dispersing a negative-type photosensitive resin composition in a solvent; a step S2 of coating the negative-type photosensitive coating solution onto a substrate surface and removing the solvent to obtain a film to be cured, preferably by heating to remove the solvent, and the heating temperature preferably being 70 to 130°C; a step S3 of initiating polymerization of the film to be cured and curing the film to be cured to form a film, preferably by initiating polymerization through energy radiation; and a step S4 of obtaining a cured film by sequentially performing a developing treatment, washing, and heating on the film, wherein the developing treatment 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.

[0029] According to a fourth aspect of the present invention, an EL element is further provided, wherein the EL element comprises any negative-type photosensitive resin composition provided in the first aspect or a cured film provided in the second aspect.

[0030] According to a fifth aspect of the present invention, a display device is further provided, wherein the display device comprises any negative-type photosensitive resin composition provided in the first aspect, a cured film provided in the second aspect, or an EL element provided in the fourth aspect. Effects of the invention

[0031] By applying the technical solution of the present invention, the negative-type photosensitive composition provided by the present invention not only possesses excellent heat resistance and light-blocking properties, but also has a wide range of application prospects because, when applied to a light-emitting device, no gas leakage is detected even in high-temperature environments, thereby preventing device contamination. Specific details for implementing the invention

[0032] It should be noted that, unless contradictory, the embodiments and features of the embodiments of the present invention may be combined with one another. The present invention will be described in detail below with reference to embodiments.

[0033] As analyzed in the background art of the present invention, in the prior art, self-luminous devices manufactured using negative-type photosensitive resin compositions comprising high-heat-resistant polyimide-based and oxime ester-based photopolymerization initiators often experience leakage of overflowed gas in high-temperature environments, thereby contaminating the device. To solve this problem, the present invention provides a negative-type photosensitive resin composition, a cured film, a method for manufacturing the same, an EL device, and a display device.

[0034] In a typical embodiment of the present invention, a negative-type photosensitive resin composition is provided, said composition comprising: (A) an alkali-soluble resin containing a polyimide structure; (B) a free radical polymerizable compound; (C) at least one photopolymerization initiator having a structure represented by the following formula (I); and a preferred (D) black dye and / or pigment.

[0035] Equation (I)

[0036] In the above formula (I), Ar is a substituted or unsubstituted C6-C30 aryl; R1 and R2 each independently represent a substituted or unsubstituted C1-C15 straight-chain alkyl, a substituted or unsubstituted C3-C15 branched-chain alkyl, a substituted or unsubstituted C3-C15 cycloalkyl, a substituted or unsubstituted C6-C20 aryl, or a substituted or unsubstituted C4-C20 heteroaryl; and R3 is methyl.

[0037] By applying the technical solution of the present invention, the negative-type photosensitive composition provided by the present invention not only possesses excellent heat resistance and light-blocking properties, but also has a wide range of application prospects because, when applied to a light-emitting device, no gas leakage is detected even in high-temperature environments, thereby preventing device contamination.

[0038] To further reduce gas leakage of the photoelectric device manufactured with the above negative-type photosensitive resin composition, preferably, Ar is at least one selected from the following groups, and

[0039]

[0040] Here, R4, R5, R6, R7 and R8 each independently represent hydrogen, a substituted or unsubstituted C1-C15 straight-chain alkyl, a substituted or unsubstituted C3-C15 branched-chain alkyl, or a substituted or unsubstituted C3-C15 cycloalkyl.

[0041] In some embodiments of the present invention, when Ar is at least one selected from the following, the gas leakage prevention performance of the photoelectric device manufactured with the negative-type photosensitive resin composition is even better.

[0042]

[0043]

[0044] .

[0045] In the present invention, "*" indicates the connection part of the chemical group.

[0046] In some preferred embodiments of the present invention, the photopolymerization initiator is preferably at least one selected from the following compounds, which is advantageous for further reducing the possibility of gas leakage and further preventing device contamination when the negative-type photosensitive resin composition is applied to a photovoltaic device.

[0047]

[0048]

[0049]

[0050] .

[0051] In some embodiments of the present invention, when the photopolymerization initiator is at least one selected from the following compounds, the gas leakage prevention performance of the negative-type photosensitive resin composition containing it is more remarkable.

[0052] .

[0053] 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 selected from one or more mixtures of polyimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor, the heat resistance of the photovoltaic device manufactured therefrom is even better.

[0054] The types of the above free radical polymerizable compounds are not limited, and any free radical polymerizable compound that can be initiated using the above photopolymerization initiator may be used. In terms of improving initiation efficiency, the above free radical polymerizable compound is preferably an acrylate-based compound comprising, but not limited to, a mixed resin formed of one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, pentaerythritol tetraacrylate, or trimethylolpropane triacrylate.

[0055] The type of black dye or black pigment is not limited, and any material having the ability to color black can be used. To further improve the dispersion performance and coloring performance of the black dye, the black dye is preferably a dye defined by a color index (CI) of solvent black 27 to 47. To further improve the dispersion performance and coloring performance of the black pigment, the black pigment is preferably selected from a mixed pigment formed from one or more of carbon black, carbon nanotubes, acetylene black, iron black, aniline black, titanium black, perylene-based pigments, or lactam-based pigments.

[0056] To further improve the performance of the above negative-type photosensitive resin composition, preferably, the negative-type photosensitive resin composition further comprises an auxiliary agent, and said auxiliary agent comprises, but is not limited to, a mixed auxiliary agent formed of any one or more of a sensitizer, a photoinitiator, a leveling agent, a dispersant, a curing agent, a surfactant, an antifoaming agent, or a storage reinforcing agent.

[0057] In some embodiments of the present invention, to further improve the photothermal resistance, light-blocking performance, and gas leakage prevention performance of a photovoltaic device to which the negative-type photosensitive resin composition is applied, the negative-type photosensitive resin composition preferably comprises 30 to 80 parts by mass of an alkali-soluble resin containing a polyimide structure, 10 to 50 parts by mass of a free radical polymerizable compound, 2 to 8 parts by mass of a photopolymerization initiator, and 2 to 8 parts by mass of a preferred black dye and / or pigment.

[0058] Typical but non-limiting, in the above negative-type photosensitive resin composition, the mass fraction of the alkali-soluble resin containing a polyimide structure is a range value consisting of, for example, 30 parts, 35 parts, 40 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 80 parts, or any two figures; the mass fraction of the free radical polymerizable compound is a range value consisting of, for example, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, or any two figures; and the mass fraction of the photopolymerization initiator is a range value consisting of, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, or any two figures; The mass fraction of the black dye and / or pigment is a range value consisting of, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, or any two numbers.

[0059] In another typical embodiment of the present invention, a cured film is further provided, said cured film is any negative-type photosensitive resin composition provided in the first typical embodiment.

[0060] Since the cured film provided by the present invention is manufactured using the negative-type photosensitive resin composition as a raw material, it not only possesses excellent light-thermal resistance and light-blocking performance but also has no gas leakage even in high-temperature environments, thus preventing contamination of photoelectric devices and having a wide range of application prospects.

[0061] In a third typical embodiment of the present invention, a method for manufacturing the cured film is further provided, wherein the manufacturing method comprises: a step S1 of obtaining a negative-type photosensitive coating solution by dissolving or dispersing a negative-type photosensitive resin composition in a solvent; a step S2 of obtaining a film to be cured by coating the negative-type photosensitive coating solution onto a substrate surface and removing the solvent; a step S3 of forming a film by initiating polymerization of the film to be cured and curing the film to be cured; and a step S4 of obtaining a cured film by sequentially performing a developing treatment, washing, and heating on the film.

[0062] The method for manufacturing a cured film provided by the present invention is simple in process, convenient to operate, and suitable for large-scale production, so it can effectively improve manufacturing efficiency and reduce production costs.

[0063] In step S1 above, the type of solvent is not limited, and it is preferable that the solvent be a low-boiling point solvent including, but not limited to, propylene glycol methyl ether acetate, for the sake of subsequent removal.

[0064] In order to prevent the composition from clumping or being unevenly dispersed in the coating solution and affecting the uniformity of the subsequent coating, it is preferable to filter the negative-type photosensitive coating solution before coating, for example, using a microporous filter with a pore size of 0.05 to 1.0 μm.

[0065] To prevent the above composition from being uniformly dispersed or dissolved in a solvent, it is preferable to disperse and mix using dispersion and mixing equipment known in the art, such as ball type (ball mill, sand mill, bead mill, paint mixer, swing mill, etc.), scraper type (kneader, paddle mixer, planetary mixer, Henschel mixer, etc.), roll type (roller type, 3-roller mixer, etc.), and crusher, colloid mill, ultrasonic, homogenizer, rotating / revolutionary mixer, etc. For dispersion efficiency and fine dispersion, it is preferable to use a bead mill for dispersion and mixing.

[0066] In step S2 above, the coating method is not limited and includes, but is not limited to, spray, roller coating, slit coating, or spin coating. The material of the substrate is not limited and is preferably a glass substrate.

[0067] In step S2 above, the method of solvent removal is not limited, and it is preferable to remove the solvent by heating. The heating conditions vary depending on the type of each component of the negative-type photosensitive resin composition, the mixing ratio, and the selection of the solvent. To further improve the solvent removal efficiency, the heating temperature is preferably 70 to 130°C, the heating time is 1 to 20 min when heating with a heating plate, and the initial heating time is 3 to 60 min when heating with an oven.

[0068] In step S3 above, the form of the energy source for initiating polymerization is not limited, and ultraviolet, visible light, infrared, electron beam, and laser light energy can all initiate the polymerization of the negative-type photosensitive resin composition provided in the first typical embodiment of the present invention through radiation and enable rapid curing. The energy source for initiating polymerization includes, but is not limited to, active light rays having a wavelength of 200 to 500 nm, such as 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 tripliwave lasers, He-Cd lasers, nitrogen lasers, Xe-Cl excimer lasers, Xe-F excimer lasers, semiconductor-excited solid-state lasers, i-rays, h-rays, g-rays, etc.; the energy source may include electron beams, α-rays, The radiation may be rays, gamma rays, X-rays, and neutron rays, etc., and preferably, the radiation is ultraviolet to visible light having a wavelength of 250 to 450 nm. The radiation intensity is 50 to 100 mJ / cm². 2 It is desirable.

[0069] In step S4 above, the development process preferably includes a step of forming a pattern on the film by contacting the film with a developer solution to develop it and then removing unnecessary parts. The developer in the developer solution includes, but is not limited to, a mixed developer formed of one or more of inorganic basic compounds, primary amine compounds, secondary amine compounds, tertiary amine compounds, alcohol amine compounds, quaternary ammonium salt compounds, or cyclic amine basic compounds.

[0070] The above inorganic basic compounds are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, or water of ammonia; the above primary amine compounds are, for example, ethylamine, n-propylamine, etc.; the above secondary amine compounds are, for example, diethylamine, di-n-propylamine, etc.; the above tertiary amine compounds are, for example, triethylamine, methyldiethylamine, etc.; the above alcohol amine compounds are, for example, dimethylethanolamine, triethanolamine, etc.; the above quaternary ammonium salt compounds are, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc.; and the above cyclic amine basic compounds are, for example, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane, etc.

[0071] The above developer is obtained by dissolving and / or dispersing a developer in a solvent, and the solvent of the developer includes an aqueous solution and a preferred organic solvent, and the organic solvent includes, but is not limited to, aqueous organic solvents such as methanol and ethanol. To further improve the dispersion stability of the developer, an auxiliary agent such as a surfactant may be added to the developer.

[0072] The above development method is not limited and includes, but is not limited to, a combination of one or more development methods among the liquid filling method, the spray method, or the immersion method. To further improve the sufficiency of the development, the development time is preferably 30 to 180 seconds.

[0073] To prevent too much developer from adhering to the surface of the developed film and affecting performance, it is preferable to rinse the developed film with water, and the washing time is preferably 30 to 90 seconds. After removing unnecessary parts, the developed film is air-dried using compressed air or compressed nitrogen to form a pattern.

[0074] The above heating method is not limited, and to further improve heating efficiency, it is preferable to form a cured film by heating the patterned film at 100 to 350°C for 2 to 20 minutes.

[0075] In a fourth typical embodiment of the present invention, an EL element is further provided, wherein the EL element comprises a barrier, said barrier being any cured film provided in the third typical embodiment; or said barrier comprising any negative-type photosensitive resin composition provided in the first typical embodiment.

[0076] The EL element provided by the present invention uses a cured film formed from the negative-type photosensitive resin composition as a barrier, and since gas leakage is not detected even in high-temperature environments and does not cause contamination of the photoelectric element, it has a wide range of application prospects.

[0077] In a fifth typical embodiment of the present invention, a display device is further provided, said display device comprises any negative-type photosensitive resin composition provided in the first typical embodiment, any cured film provided in the second typical embodiment, or an EL element provided in the fourth typical embodiment.

[0078] The display device provided by the present invention uses the negative-type photosensitive resin composition provided in the first typical embodiment, so gas leakage is not detected even in high-temperature environments and does not cause contamination of the light-emitting element, thus having a wide range of application prospects.

[0079] The beneficial effects of the present invention will be explained in more detail below, together with examples and comparative examples.

[0080] Example 1

[0081] The present embodiment provides a cured film, and the cured film is,

[0082] Step (1) of obtaining a negative-type photosensitive resin composition by mixing an alkali-soluble resin A1 containing a polyimide structure, a free radical polymerizable compound B1, a photopolymerization initiator C1, and carbon black in a bead mill in a mass ratio of 80:10:5:5, and then dispersing and stirring for 3 hours;

[0083] Step (2) of obtaining a negative-type photosensitive coating solution by dispersing a negative-type photosensitive resin composition in 100 parts by mass of polypropylene glycol methyl ether acetate (PGMEA), which is a solvent;

[0084] Step (3): sequentially washing a glass substrate (size 100mm × 100mm × 1mm) with a neutral detergent (N-methylpyrrolidone, Aladin), water, and ethanol, then drying it; spin-coating the negative-type photosensitive coating solution onto the glass substrate; baking at 90°C for 125 seconds using a heating plate; removing the solvent; and cooling to room temperature to obtain a cured film attached to the substrate;

[0085] The above film was subjected to 100 mJ / cm² using a mercury lamp (RW-LED-YT200gl). 2 Step (4) of obtaining a cured film with a thickness of 1.5 μm by sufficiently exposing it to water; and

[0086] The above film is prepared according to step (5), which involves immersing the film in a 0.04% potassium hydroxide aqueous solution at 25°C for 60 seconds to develop it, then washing it with water and baking it at 235°C for 15 minutes to obtain a hardened film.

[0087] Example 2

[0088] The difference between this embodiment and Example 1 is that in step (1), A1 is replaced with an alkali-soluble resin A2 containing a polyimide structure, B1 is replaced with a free radical polymerizable compound B2, and C1 is replaced with a photoinitiator C2.

[0089] Example 3

[0090] The difference between this embodiment and Example 1 is that the negative type photosensitive resin composition is composed of A1, B1, C3 and carbon black, and the mass ratio of these four is 70:20:5:5.

[0091] Example 4

[0092] The difference between this embodiment and Example 1 is that the negative type photosensitive resin composition is composed of A1, B1, C1 and carbon black, and the mass ratio of these four is 60:30:5:5.

[0093] Example 5

[0094] The difference between this embodiment and Example 1 is that the negative type photosensitive resin composition is composed of A1, B1, C4 and carbon black, and the mass ratio of these four is 65:25:5:5.

[0095] Example 6

[0096] The difference between this embodiment and Example 1 is that the negative type photosensitive resin composition is composed of A2, B1, C5 and carbon black, and the mass ratio of these four is 60:30:5:5.

[0097] Example 7

[0098] The difference between this embodiment and Example 1 is that the negative type photosensitive resin composition is composed of A2, B2, C6 and carbon black, and the mass ratio of these four is 70:20:5:5.

[0099] Example 8

[0100] The difference between this embodiment and Example 1 is that the negative type photosensitive resin composition is composed of A2, B1, C5 and carbon black, and the mass ratio of these four is 60:30:5:5.

[0101] Example 9

[0102] The difference between this embodiment and Example 1 is that the negative type photosensitive resin composition is composed of A1, B2, C6 and carbon black, and the mass ratio of these four is 65:25:5:5.

[0103] Example 10

[0104] The difference between this embodiment and Example 1 is that the negative type photosensitive resin composition is composed of A1, B1, C4 and carbon black, and the mass ratio of these four is 50:40:5:5.

[0105] Example 11

[0106] The difference between this embodiment and Example 1 is that the negative type photosensitive resin composition is composed of A1, B2, C3 and carbon black, and the mass ratio of these four is 40:50:5:5.

[0107] Example 12

[0108] The difference between this embodiment and Example 1 is that the negative type photosensitive resin composition is composed of A1, B1, C2 and carbon black, and the mass ratio of these four is 40:50:5:5.

[0109] Example 13

[0110] The difference between this embodiment and Example 1 is that the negative type photosensitive resin composition is composed of A1, B1, C1 and carbon black, and the mass ratio of these four is 80:10:2:8.

[0111] Example 14

[0112] The difference between this embodiment and Example 1 is that the negative type photosensitive resin composition is composed of A1, B1, C4 and carbon black, and the mass ratio of these four is 50:40:8:2.

[0113] Comparative Example 1

[0114] Comparative Example 1 provides a cured film, and the difference from Example 1 is that the negative type photosensitive resin composition is composed of A1, B1, C7 and carbon black, and the mass ratio of these four is 65:25:5:5.

[0115] Comparative Example 2

[0116] Comparative Example 1 provides a cured film, and the difference from Example 1 is that the negative type photosensitive resin composition is composed of A2, B1, C8 and carbon black, and the mass ratio of these four is 60:30:5:5.

[0117] The specific information regarding the above A1, A2, B1, B2, C1-C8 and carbon black is as follows.

[0118] A1: Polyimide Resin: Product Name: GCPI-PAA

[0119] A2: Polyimide Resin: Product Name: JCL3030

[0120] B1: Pentaerythritol Tetraacrylate: Trade Name: A-TMMT

[0121] B2: Trimethylolpropane triacrylate: Product name: M309

[0122]

[0123]

[0124] Carbon Black: Product Name: KetjenblackEC600JD.

[0125] Test Example 1

[0126] Heat resistance and light-blocking properties were evaluated for the cured films provided in the above examples and comparative examples, respectively, and the results are shown in Table 1.

[0127] Specific method for heat resistance test: After baking each of the above-mentioned cured films in a convection oven at 230°C for 30 minutes, ΔE*ab was calculated from the color intensity of the coloring pattern before and after heating, and if ΔE*ab was 3.0 or less, it was evaluated as having excellent heat resistance.

[0128] Specific method for the light-blocking test: After irradiating the cured film with 180W for 60 hours under conditions of a temperature of 30℃, humidity of 50%, and a black panel temperature of 63℃, ΔE*ab was calculated from the color intensity of the coloring pattern before and after irradiation, and if ΔE*ab was 3.0 or less, it was evaluated as having excellent heat resistance.

[0129] heat resistance Light-blocking Example 1 0.42 0.43 Example 2 0.33 0.38 Example 3 0.40 0.42 Example 4 0.42 0.44 Example 5 0.38 0.42 Example 6 0.45 0.46 Example 7 0.43 0.44 Example 8 0.37 0.40 Example 9 0.40 0.42 Example 10 0.41 0.42 Example 11 0.35 0.40 Example 12 0.40 0.42 Example 13 0.38 0.41 Example 14 0.39 0.42 Comparative Example 1 0.42 0.44 Comparative Example 2 0.40 0.42

[0130] Test Example 2

[0131] Gas leakage tests were performed on the cured films provided in the examples and comparative examples, and the results are shown in Table 2.

[0132] The method for the gas leak test is as follows.

[0133] Using the GC-MS test method, 5g of the cured film provided in the above examples and comparative examples is taken, cut, and placed in a headspace bottle for later use, and whether overflow gas is generated is observed through headspace sampling (excluding carbon dioxide and self-containing solvent peaks).

[0134] Instrument: Agilent 7890B gas chromatograph;

[0135] Chromatography Column: Agilent HP-5ms Chromatography Column Vaporization Temperature: 280℃ Temperature Programming: 60℃-3min-20℃ / min-280℃-10min;

[0136] Headspace conditions: Heating box: 110℃ Quantitative loop: 120℃ Transfer line: 140℃ Equilibration time: 30 min;

[0137] Mass Spectrometry Conditions: Ion Source Temperature: 280℃ Electron Energy: 70 eV Scan Range (m / z): 30-400;

[0138] Gas leak situation Example 1 Not detected Example 2 Not detected Example 3 Not detected Example 4 Not detected Example 5 Not detected Example 6 Not detected Example 7 Not detected Example 8 Not detected Example 9 Not detected Example 10 Not detected Example 11 Not detected Example 12 Not detected Example 13 Not detected Example 14 Not detected Comparative Example 1 1.65 Comparative Example 2 1.98

[0139] From the above description, it can be seen that the above embodiment of the present invention achieves the following technical effects.

[0140] The cured film prepared from the negative-type photosensitive composition provided by the present invention does not detect gas leakage even in high-temperature environments and does not cause device contamination when applied to light-emitting devices, thus having a wide range of application prospects.

[0141] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the invention; those skilled in the art may make various modifications and variations to the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the scope of the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

Claim 1 A negative-type photosensitive resin composition, wherein the composition comprises: (A) an alkali-soluble resin having a polyimide structure; (B) a free radical polymerizable compound; and (C) at least one photopolymerization initiator having a structure represented by the following formula (I): Formula (I); and (D) comprising a black dye and / or black pigment; wherein R1 and R2 each independently represent a substituted or unsubstituted C1-C15 straight-chain alkyl, a substituted or unsubstituted C3-C15 branched-chain alkyl, a substituted or unsubstituted C3-C15 cycloalkyl, a substituted or unsubstituted C6-C20 aryl, or a substituted or unsubstituted C4-C20 heteroaryl; R3 is methyl; and Ar is at least one selected from the following substituted or unsubstituted groups, and A negative-type photosensitive resin composition characterized in that, wherein R4, R5, R6, R7, and R8 each independently represent hydrogen, a substituted or unsubstituted C1-C15 straight-chain alkyl, a substituted or unsubstituted C3-C15 branched-chain alkyl, or a substituted or unsubstituted C3-C15 cycloalkyl. Claim 2 A negative-type photosensitive resin composition according to claim 1, wherein in the above formula (I), Ar is at least one selected from the following substituted or unsubstituted groups: Claim 3 In claim 1, the photopolymerization initiator is, A negative-type photosensitive resin composition characterized by being at least one selected from compounds having a structure. Claim 4 In paragraph 3, the photopolymerization initiator is, A negative-type photosensitive resin composition characterized by being at least one selected from compounds having a structure. Claim 5 A negative-type photosensitive resin composition according to claim 1, wherein the alkali-soluble resin containing the polyimide structure is at least one selected from polyimide, polyimide precursor, polybenzoxazole, or polybenzoxazole precursor; and / or, the free radical polymerizable compound is an acrylate-based compound. Claim 6 A negative-type photosensitive resin composition according to claim 1, wherein the black dye is a dye defined by a color index of solvent black 27 to 47; and / or, the black pigment is at least one selected from carbon black, carbon nanotube, acetylene black, iron black, aniline black, titanium black, perylene-based pigment, or lactam-based pigment. Claim 7 A negative-type photosensitive resin composition according to claim 1, characterized in that, based on parts by mass, the composition comprises (A) 30 to 80 parts of an alkali-soluble resin containing the polyimide structure, (B) 10 to 50 parts of the free radical polymerizable compound, (C) 2 to 8 parts of the photopolymerization initiator, and (D) 2 to 8 parts of a black dye and / or pigment. Claim 8 A negative-type photosensitive resin composition according to claim 7, wherein the composition further comprises an auxiliary agent, and the auxiliary agent comprises at least one of a sensitizer, a photoinitiator, a leveling agent, a dispersant, a curing agent, a surfactant, an antifoaming agent, or a storage reinforcing agent. Claim 9 A cured film characterized in that, as a cured film, the raw material of the cured film is a negative-type photosensitive resin composition according to any one of claims 1 to 8. Claim 10 A method for manufacturing a cured film according to claim 9, wherein the manufacturing method comprises: a step S1 of obtaining a negative-type photosensitive coating solution by dissolving or dispersing the negative-type photosensitive resin composition in a solvent; a step S2 of obtaining a film to be cured by coating the negative-type photosensitive coating solution onto a substrate surface and removing the solvent; a step S3 of forming a film by initiating polymerization of the film to be cured and curing the film to be cured; and a step S4 of obtaining the cured film by sequentially performing development treatment, washing, and heating on the film. Claim 11 A method for manufacturing a cured film according to claim 10, wherein in step S2, the solvent is removed by heating, and the heating temperature is 70 to 130°C; and / or in step S3, the polymerization is initiated through energy radiation; and / or in step S4, the development treatment time is 30 to 180 s, the heating temperature is 100 to 350°C, and the heating time is 2 to 20 min. Claim 12 An EL element, wherein the EL element comprises a cured film according to claim 9. Claim 13 A display device, wherein the display device comprises an EL element according to claim 12.

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