Porphyrin pigment derivative and preparation method thereof, low-temperature black photoresist and preparation method and application thereof

Abstract

The invention belongs to the technical field of photocuring, and particularly relates to a porphyrin pigment derivative and a preparation method thereof, a low-temperature black photoresist and a preparation method and application thereof. The porphyrin pigment derivative is obtained by adding an acrylic monomer into a porphyrin pigment to modify the porphyrin pigment, the black photoresist based on the porphyrin pigment derivative comprises the following components in parts by weight: 30-45 parts of black color paste, 1-5 parts of the porphyrin pigment derivative, 3-20 parts of alkali-soluble resin, 5-12 parts of a photosensitive monomer, 4-8 parts of a photoinitiator, 0.2-2 parts of a flatting agent, 0.5-3 parts of a silane coupling agent and 30-60 parts of an organic solvent. According to the black photoresist provided by the invention, the OD value can be effectively improved, and the dosage is small; the curing performance of the photoresist can be effectively improved, the falling problem is solved, and the photoresist can be well applied to OLED or Micro-LED.

Description

Technical Field

[0001] The invention belongs to the technical field of photocuring, and in particular relates to a porphyrin pigment derivative and a preparation method thereof, a low-temperature black photoresist and a preparation method and application thereof. Background Art

[0002] Photoresist, also known as photoresist, is a photosensitive resin composition composed of photosensitive resin, photoinitiator, diluent and solvent. It can transfer the required fine pattern from the mask to the substrate to be processed through photochemical reaction, exposure, development and other photolithography processes. Adding pigments (red, green and blue) to the photoresist makes a color photoresist (or color photosensitive / photosensitive resin composition). The color paste made of pigments is not only the main raw material of color photoresist, but also determines the quality of display.

[0003] The preparation of traditional photoresist color paste usually uses dyes and pigments to reduce light scattering and improve contrast, but dyes are not environmentally friendly; or by adding black chromium oxide, but the etching cost is high, the black matrix formed by chromium metal is low, the aspect ratio cannot meet higher process requirements, and the chromium reflectivity is high, which affects the display quality, and chromium wastewater is not environmentally friendly; furthermore, carbon black and carbon materials or color pigments are mixed. Carbon black and carbon materials have strong covering power and coloring power and have a high cost-effectiveness, but poor insulation performance, prone to electrostatic interference, and color pigments have poor light shielding properties. In addition, the existing organic pigments used in black photoresists, under the same dosage conditions, have disadvantages such as low OD value and high dosage compared with black inorganic pigments such as carbon black and oxide; secondly, as the black pigment increases and the film thickness increases, the curing performance of the black photoresist will gradually deteriorate, resulting in poor curing at the bottom of the film and problems such as falling off; in addition, most black photoresists have a high application temperature, basically greater than 200°C, and most of them are used in LEDs. There are relatively few black photoresists used in low temperature conditions, OLEDs and Micro-LEDs.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] The purpose of the present invention is to overcome the disadvantages of the above-mentioned prior art and provide a porphyrin pigment derivative and a preparation method thereof, a low-temperature black photoresist and a preparation method and application thereof.

[0006] The objective of the present invention is achieved through the following technical solutions:

[0007] In a first aspect, the present invention provides a porphyrin pigment derivative, wherein an acrylic acid monomer is added to the porphyrin pigment to modify the porphyrin pigment, thereby obtaining the porphyrin pigment derivative.

[0008] In a second aspect, the present invention provides a method for preparing a porphyrin pigment derivative for low-temperature black photoresist, which specifically comprises the following steps:

[0009] Step 1, dissolving an aldehyde-containing compound in a solvent and adding a five-membered heterocyclic compound to heat and react to obtain a porphyrin pigment;

[0010] Step 2: Add acrylic acid monomer to the porphyrin pigment and heat to react to obtain a porphyrin pigment derivative.

[0011] Specifically, the aldehyde-containing compound includes any one of benzaldehyde, 4-carboxybenzaldehyde, 4-hydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 2-hydroxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde and 4-ethoxybenzaldehyde.

[0012] Specifically, the solvent includes any one of pentane, formic acid, acetic acid, ethyl ether, acetone, propionic acid, anisole, 1-propanol, 2-propanol, methyl ethyl ketone, dimethyl sulfoxide, isopropylbenzene, ethyl acetate, ethyl formate, isobutyl acetate, methyl acetate, 3-methyl-1-butanol, methyl isobutyl ketone, 2-methyl-1-propanol, and propyl acetate.

[0013] Specifically, the five-membered heterocyclic compound includes any one of furan, thiophene, pyrrole, thiazole and imidazole.

[0014] Furthermore, the acrylic monomer includes any one of acrylic acid, methacrylic acid, 2-ethylacrylic acid, methacryloyloxyethyl succinic acid monoester, and methacryloyloxyethyl phthalic acid monoester.

[0015] The porphyrin pigment prepared by the present invention has the following advantages:

[0016] (I) Since acrylic monomers contain double bonds, they can copolymerize with active functional groups (such as amino groups, hydroxyl groups, etc.) on porphyrin pigment molecules through free radical polymerization to form chemical bonds. This chemical bonding can enhance the stability of the pigment in the polymer matrix. In addition, the introduction of acrylic monomers will increase the chain length and volume of the pigment surface, producing a steric hindrance effect, which helps to improve the dispersion of the pigment in the resin and reduce pigment aggregation, thereby improving the transparency and uniformity of the photoresist, and further affecting the optical and mechanical properties of the photoresist.

[0017] (ii) The introduction of acrylic monomers can enhance the absorption capacity of porphyrin pigments to light of a specific wavelength (such as ultraviolet light) by changing the molecular structure or electron distribution of the porphyrin pigments, thereby improving the photosensitivity of the photoresist.

[0018] (III) The introduction of acrylic monomers can improve the interfacial compatibility between porphyrin pigments and photoresist substrates, reduce interfacial defects, and thus improve the adhesion between photoresist and substrates. In addition, the polar groups of acrylic monomers may interact with the substrate surface through hydrogen bonds or chemical bonds, further enhancing adhesion.

[0019] Furthermore, the molar ratio of the aldehyde-containing compound to the five-membered heterocyclic compound is (0.5-1.5):1, and the mass ratio of the porphyrin pigment to the acrylic monomer is (4-8):1.

[0020] Furthermore, in step 1, the heating temperature is 100-150° C., and the reaction time is 6-10 h; in step 2, the heating temperature is 60-80° C., and the reaction time is 4-6 h.

[0021] Furthermore, the preparation method is specifically as follows:

[0022] Step 1, dissolving the aldehyde-containing compound in a solvent and adding a five-membered heterocyclic compound, and when the solution gradually turns black, reflux and keep warm for 6 to 10 hours. After the reaction is completed, cool to room temperature, refrigerate at a low temperature (about minus 10 degrees) for 4 to 6 hours, and then filter to obtain a solid; wash the solid with purified water, petroleum ether, and ethyl acetate in sequence, and vacuum dry and heat to obtain a porphyrin pigment;

[0023] Step 2: dissolving the porphyrin pigment in an ethanol solution and adding an acrylic acid monomer, heating to 60-80° C., and reacting for 4-6 hours under a N2 atmosphere. After the reaction is completed, cooling to room temperature to obtain a solid; washing the solid with deionized water and ethanol in turn, and vacuum drying the reaction to obtain a porphyrin pigment derivative.

[0024] In a third aspect, the present invention provides a low-temperature black photoresist, comprising, by weight: 30 to 45 parts of black color paste, 1 to 5 parts of porphyrin pigment derivatives, 3 to 20 parts of alkali-soluble resins, 5 to 12 parts of photosensitive monomers, 4 to 8 parts of photoinitiators, 0.2 to 2 parts of leveling agents, 0.5 to 3 parts of silane coupling agents and 30 to 60 parts of organic solvents; wherein the porphyrin pigment derivatives are prepared by the preparation method described in part or in whole as above.

[0025] Furthermore, the alkali-soluble resin includes any one of polyvinyl alcohol resin (acrylic resin SPC-W5001, Shanghai Showa Polymer), styrene-acrylic resin, epoxy-acrylic resin, polyurethane-acrylic resin, methacrylic acid-acrylate resin, acrylic acid-acrylate resin, styrene-maleate resin and rosin-modified maleate resin.

[0026] Preferably, the alkali-soluble resin is an acrylic resin having an acid value of 60 to 90 mgKOH / g, a molecular weight of 3000 to 5000, a PDI value (polymer dispersibility index) of ≤1.3, and containing a fluorene structure.

[0027] Furthermore, the photosensitive monomer is at least one of a monofunctional photosensitive resin, a difunctional photosensitive resin or a multifunctional photosensitive resin, and contains monomers with multiple reactive functional groups such as unsaturated double bonds, hydroxyl groups, carboxyl groups, carbonyl groups, etc. By adding multifunctional monomers, it is possible to form a clear pixel pattern in the exposed part and prevent development and demolding.

[0028] Further, the photosensitive monomer can be selected from one or more of 1,6-hexanediol diacrylate (HDDA), dipropylene glycol diacrylate, tripropylene glycol diacrylate, 3-propoxylated glycerol triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 3-(trimethoxysilane)propyl acrylate, glycidyl methacrylate, benzyl methacrylate, and diphenylphosphoryl azide DPPA.

[0029] Preferably, the photosensitive monomer is a multifunctional photosensitive resin containing hydroxyl and carboxyl groups, and the photosensitive monomer is any one of 1,6-hexanediol diacrylate (HDDA), dipentaerythritol hexaacrylate (DPHA), trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PETTA), and diphenylphosphoryl azide (DPPA).

[0030] Further, the photoinitiator can be a free radical initiator, a cationic initiator, a macromolecular photoinitiator, etc.; preferably, the free radical initiator includes: 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, o-benzoyl-4'-(mercaptophenyl)benzoyl-hexyl-ketoxime, 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl]nonane-1,2-nonane-2-oxime-O-benzoate, 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl] Octanedione-1-one oxime-O-acetate, 1-[9-ethyl-6(2-methylbenzoyl)-9H-carboxylic acid-3-yl]-ethyl-1-tetrazol-O-benzoate, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), 1,2-butanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-[O-(4-methylbenzoyl oxime)], and the like, and mixtures thereof. Oxime ester compounds, such as OXE-1 and OXE-2, are preferred. Based on the absorbance of oxime ester photoinitiators in the exposure band and the absorbance in the total band, they can effectively reduce the line width growth produced during the subsequent preparation of photoresists. This is mainly due to the fact that they increase the curing rate of acrylic prepolymers and monomers in the photoresist composition during exposure.

[0031] Further, the silane coupling agent includes but is not limited to at least one of Sangjing Chemical (γ-methacryloxypropyltrimethoxysilane) A-174, Nanjing Xuanhao New Materials KH570, Nanjing Xuanhao New Materials KH-550, Shin-Etsu KBM-403, Shin-Etsu KBM-503, Shin-Etsu KBM-603, Shin-Etsu KBM-903, and Nengde New Materials A-171. Moreover, these silane coupling agents can be used alone or in combination.

[0032] Further, the leveling agent is to improve the leveling of the photoresist on the substrate, preferably a dimethylsiloxane leveling agent having a polyether structure or a polyester structure on the main chain. It can include Megaface F-470, F-471, F-475, F-482, F-489, F-554 and F-563 from Dainippon Ink & Chemicals Co., Ltd., DC3PA, DC7PA, SH11PA / SH21PA and SH8400 from Dow Corning Toray Silicones, TSF-4440 / TSF-4300 / TSF-4445 / TSF-4446 and TSF-4452 from GE Toshiba Silicones, BYK-333, BYK-310, BYK-307, BYK-354, BYK-399 and BYK-70 from BYK.

[0033] Furthermore, the organic solvent is used to dissolve organic components other than the pigment, improve the fluidity during grinding, and adjust the viscosity of the system. It can be selected from one or more of propylene glycol methyl ether, propylene glycol methyl ether acetate, cyclohexanone, acetone, 3-methoxybutyl acetate, ethylene glycol monoethyl ether, ethyl 2-hydroxypropionate, ethylene glycol methyl ether acetate, ethylene glycol dimethyl ether, r-butyrolactone, ethylene glycol diacetate, propylene glycol methyl ether acetate, and propylene glycol ethyl ether acetate.

[0034] Furthermore, the black color paste is a self-made grinding color paste with a solid content of 15-25wt%, which is obtained by mixing carbon black, dispersant, resin and solvent, and placing them on a coating rapid dispersing machine for 4-8h. The weight parts are as follows: 10-20 parts of carbon black, 2-5 parts of dispersant, 2-5 parts of resin, and 70-90 parts of solvent.

[0035] Preferably, carbon black is 13 parts, dispersant is 3.5 parts, resin is 3.5 parts, and solvent is 80 parts.

[0036] Furthermore, the carbon black is selected from common commercially available carbon black, such as pigment PUM6080, Shanghai Evonik Technology Carbon Black 4A, Mitsubishi Chemical MA-100, 2650; the dispersant is BYK-9770 from BYK.

[0037] Furthermore, the resin used to prepare the black color paste is the same as the above-mentioned alkali-soluble resin.

[0038] Furthermore, the solvent used to prepare the black color paste is the same as the above-mentioned organic solvent.

[0039] Preferably, the resin used to prepare the black color paste is an acrylic resin having an acid value of 60 to 90 mgKOH / g, a molecular weight of 3000 to 5000, a PDI value (polymer dispersibility index) of ≤1.3, and containing a fluorene structure.

[0040] In addition, the present invention also provides a method for preparing black photoresist, comprising adding raw materials in the following weight portions into a reaction container, mixing and stirring with an agitator to obtain black photoresist; in terms of weight portions, the raw materials include: 30 to 45 parts of black color paste, 1 to 5 parts of porphyrin pigment derivatives, 3 to 20 parts of alkali-soluble resins, 5 to 12 parts of photosensitive monomers, 3 to 8 parts of photoinitiators, 0.2 to 2 parts of leveling agents, 0.5 to 3 parts of silane coupling agents, and 30 to 60 parts of organic solvents.

[0041] Finally, the present invention also provides an application of a low-temperature black photoresist, which can be used in an environment below 200° C. and applied to OLED or Micro-LED devices.

[0042] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0043] 1) The porphyrin pigment derivative synthesized by the present invention can absorb more ultraviolet light or visible light, and can be added in a small amount to a black organic pigment system to effectively increase the OD value, and the dosage is less than that of the original black pigment, thus saving raw materials;

[0044] 2) The photoresist to which the synthetic porphyrin pigment derivative is added can effectively improve the curing performance of the photoresist and improve the peeling problem when the amount of black pigment used is increased or the film thickness is increased;

[0045] 3) The black photoresist of the present invention has a wide range of applications and adaptability. It can not only be used at temperatures below 200° C., but can also be well applied to OLED or Micro-LED to meet different production requirements and has high industrial value. DETAILED DESCRIPTION

[0046] Here, exemplary embodiments will be described in detail, and the embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Instead, they are only examples consistent with some aspects of the present invention described in detail in the appended claims.

[0047] The preparation method of the porphyrin pigment derivative disclosed in the present invention comprises:

[0048] Step 1, dissolving an aldehyde-containing compound in a solvent and adding a five-membered heterocyclic compound to heat and react to obtain a porphyrin pigment;

[0049] Step 2: Add acrylic acid monomer to the porphyrin pigment and heat to react to obtain a porphyrin pigment derivative.

[0050] The molar ratio of the aldehyde-containing compound to the five-membered heterocyclic compound is (0.5-1.5):1, and the mass ratio of the porphyrin pigment to the acrylic monomer is (4-8):1.

[0051] Furthermore, in step 1, the heating temperature is 100-150° C., and the reaction time is 6-10 h; in step 2, the heating temperature is 60-80° C., and the reaction time is 4-6 h.

[0052] In addition, based on the above-mentioned porphyrin pigment derivatives, the present invention also provides a method for preparing a black photoresist, comprising adding raw materials in the following parts by weight into a reaction container, mixing and stirring with an agitator to obtain a black photoresist; wherein each raw material, in parts by weight, specifically includes: 30 to 45 parts of black color paste, 1 to 5 parts of porphyrin pigment derivatives, 3 to 20 parts of alkali-soluble resin, 5 to 12 parts of photosensitive monomers, 4 to 8 parts of photoinitiators, 0.2 to 2 parts of leveling agents, 0.5 to 3 parts of silane coupling agents and 30 to 60 parts of organic solvents.

[0053] Specifically, the black color paste is a self-made grinding color paste with a solid content of 15-25wt%, which is obtained by mixing carbon black, dispersant, resin and solvent, and placing them on a coating rapid dispersing machine for 4-8 hours. Among them, the weight parts are as follows: 10-20 parts of carbon black, 2-5 parts of dispersant, 2-5 parts of resin, and 70-90 parts of solvent.

[0054] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described in detail below in conjunction with embodiments.

[0055] Example 1

[0056] This embodiment provides a method for preparing a low-temperature black photoresist pigment derivative and a black photoresist, wherein the low-temperature black photoresist pigment derivative is a porphyrin pigment derivative, and the raw materials are as follows: the aldehyde-containing compound is 4-hydroxybenzaldehyde, the five-membered heterocyclic compound is pyrrole, the solvent is propionic acid, and the acrylic monomer is methacryloyloxyethyl phthalate.

[0057] Specifically, the preparation method of the porphyrin pigment derivative specifically includes:

[0058] Step 1, dissolving 0.1 mol of an aldehyde-containing compound in a solvent and adding 0.1 mol of a five-membered heterocyclic compound and heating to 100° C., when the solution gradually turns black, reflux and keep warm for 6 hours, after the reaction is completed, cool to room temperature, refrigerate for 4 hours, and then filter to obtain a solid, wash the solid with purified water, petroleum ether, and ethyl acetate in sequence, and vacuum dry and heat to obtain a 4-hydroxy-tetraphenylporphyrin pigment;

[0059] Step 2: Add 5 g of acrylic acid monomer to 10 g of 4-hydroxy-tetraphenylporphyrin pigment, heat to 60° C., and react for 4 hours under a N2 atmosphere. After the reaction is completed, cool to room temperature to obtain a solid; wash the solid with deionized water and ethanol in turn, and vacuum dry to obtain a porphyrin pigment derivative, named A-01.

[0060] Specifically, the raw materials of the black photoresist include: 38 parts of black color paste, 2 parts of porphyrin pigment derivatives, 5 parts of alkali-soluble resin, 10 parts of photosensitive monomers, 5 parts of photoinitiators, 1 part of leveling agents, 1 part of silane coupling agents and 38 parts of organic solvents.

[0061] Among them, the black color paste is the company's self-made color paste (solid content 20%, pigment is PUM6080, accounting for 13%, Mitsubishi Chemical), the resin used in the preparation of the color paste is the same as the alkali-soluble resin, which is acrylic resin SPC-W5001 (solid content 50%), the porphyrin pigment derivative is A-01, the photosensitive monomer is dipentaerythritol hexaacrylate, the photoinitiator is OXE-01, the silane coupling agent is A-174, the leveling agent is BYK-333, and the organic solvent is a mixture of propylene glycol methyl ether and propylene glycol methyl ether acetate, 12 parts of propylene glycol methyl ether and 26 parts of propylene glycol methyl ether acetate.

[0062] The preparation method of the above black photoresist is as follows: the above raw materials are added into a 100ml glass bottle according to weight, magnetically stirred for 2h, and mixed evenly to obtain a low-temperature black photoresist. The above black photoresist is subjected to 250rpm*60s spin coating, vacuum desolventizing for 2min, pre-baking at 110℃*90s, exposure energy of 200mj, 2.38% TMAH development for 60s, and post-baking curing at 150℃*30min to obtain a light-cured film (I).

[0063] Example 2

[0064] On the basis of Example 1, the difference from Example 1 is that the aldehyde-containing compound is 4-carboxybenzaldehyde, the five-membered heterocyclic compound is pyrrole, the solvent is acetone, and the acrylic acid monomer is acrylic acid.

[0065] The molar ratio of the aldehyde-containing compound to the five-membered heterocyclic compound is 0.5:1, and the mass ratio of the porphyrin pigment to the acrylic monomer is 4:1.

[0066] The heating temperature in step 1 is 120° C. and the reaction time is 8 hours; the heating temperature in step 2 is 60° C. and the reaction time is 4 hours. The obtained porphyrin pigment derivative is named A-02.

[0067] Specifically, the raw materials for preparing black photoresist include: 30 parts of black color paste, 2 parts of porphyrin pigment derivatives, 5 parts of alkali-soluble resin, 8 parts of photosensitive monomers, 3 parts of photoinitiators, 1 part of leveling agents, 1 part of silane coupling agents, and 50 parts of organic solvents.

[0068] Among them, the black color paste is a homemade color paste. The resin used in the preparation of the color paste is the same as the alkali-soluble resin, which is styrene-acrylic resin. The porphyrin pigment derivative is A-02, the photosensitive monomer is 1,6-hexanediol diacrylate, the initiator is OXE-02, the silane coupling agent is KBM-503, the leveling agent is BYK-310, and the organic solvent is ethylene glycol methyl ether acetate and ethylene glycol dimethyl ether mixed in a mass ratio of 1:1.

[0069] The application process of the black photoresist is as follows: the black photoresist is spin-coated at 250 rpm for 60 seconds, vacuum desolventized for 2 minutes, pre-baked at 110°C for 90 seconds, exposed with 200 mj of energy, developed with 2.38% TMAH for 60 seconds, and post-baked for curing at 140°C for 30 minutes to obtain a photocured film (II).

[0070] Example 3

[0071] On the basis of Example 1, the difference from Example 1 is that benzaldehyde is selected as the aldehyde-containing compound, pyrrole is selected as the five-membered heterocyclic compound, anisole is selected as the solvent, and methacrylic acid is selected as the acrylic acid monomer.

[0072] The molar ratio of the aldehyde-containing compound to the five-membered heterocyclic compound is 1:1, and the mass ratio of the porphyrin pigment to the acrylic monomer is 6:1.

[0073] In step 1, the heating temperature is 125° C. and the reaction time is 8 hours; in step 2, the heating temperature is 70° C. and the reaction time is 5 hours. The obtained porphyrin pigment derivative is named A-03.

[0074] Specifically, the raw materials for preparing black photoresist include: 35 parts of black color paste, 3 parts of porphyrin pigment derivatives, 5 parts of alkali-soluble resin, 7 parts of photosensitive monomers, 3 parts of photoinitiators, 1 part of leveling agents, 1 part of silane coupling agents, and 45 parts of organic solvents.

[0075] Among them, the black color paste is a homemade color paste. The resin used in the preparation of the color paste is the same as the alkali-soluble resin, which is acrylic acid-acrylate resin. The porphyrin pigment derivative is A-03, the photosensitive monomer is trimethylolpropane triacrylate, the initiator is OXE-01, the silane coupling agent is KBM-403, the leveling agent is BYK-70, and the organic solvent is ethylene glycol diacetate and propylene glycol methyl ether acetate mixed in a mass ratio of 1:1.

[0076] The application process of the black photoresist is as follows: the black photoresist is spin-coated at 250 rpm for 60 seconds, vacuum desolventized for 2 minutes, pre-baked at 110°C for 90 seconds, exposed with 200 mj of energy, developed with 2.38% TMAH for 60 seconds, and post-baked for curing at 160°C for 30 minutes to obtain a photocured film (III).

[0077] Example 4

[0078] Based on Example 1, the difference from Example 1 is that the aldehyde-containing compound is 3,4-dihydroxybenzaldehyde, and the acrylic acid monomer is 2-ethylacrylic acid. The obtained porphyrin pigment derivative is named A-04.

[0079] The raw materials for preparing the black photoresist include: 40 parts of black color paste, 3 parts of porphyrin pigment derivatives, 7 parts of alkali-soluble resin, 8 parts of photosensitive monomers, 6 parts of photoinitiators, 0.5 parts of leveling agents, 0.5 parts of silane coupling agents, and 35 parts of organic solvents.

[0080] Among them, the black color paste is a homemade color paste. The resin used in the preparation of the color paste is the same as the alkali-soluble resin, which is epoxy-acrylic resin. The porphyrin pigment derivative is A-04, the photosensitive monomer is pentaerythritol triacrylate, the initiator is OXE-02, the silane coupling agent is A174, the leveling agent is BYK-307, and the organic solvent is ethylene glycol diacetate.

[0081] The application process of the black photoresist is as follows: the black photoresist is spin-coated at 250 rpm for 60 seconds, vacuum desolventized for 2 minutes, pre-baked at 110°C for 90 seconds, exposed at 200 mj of energy, developed at 2.38% TMAH for 60 seconds, and post-baked for curing at 170°C for 30 minutes to obtain a photocured film (IV).

[0082] Example 5

[0083] Based on Example 1, the difference from Example 1 is that the aldehyde-containing compound is 3,4-dihydroxybenzaldehyde, and the acrylic acid monomer is 2-ethylacrylic acid. The obtained porphyrin pigment derivative is named A-05.

[0084] The raw materials for preparing the black photoresist include: 35 parts of black color paste, 4 parts of porphyrin pigment derivatives, 10 parts of alkali-soluble resin, 6 parts of photosensitive monomers, 6 parts of photoinitiators, 1 part of leveling agents, 3 parts of silane coupling agents, and 35 parts of organic solvents.

[0085] Among them, the black color paste is a homemade color paste. The resin used in the preparation of the color paste is the same as the alkali-soluble resin, which is a polyurethane-acrylic resin. The porphyrin pigment derivative is A-05, the photosensitive monomer is pentaerythritol tetraacrylate, the initiator is OXE-02, the silane coupling agent is A174, the leveling agent is BYK-399, and the organic solvent is propylene glycol ethyl ether acetate.

[0086] The application process of the black photoresist is as follows: the black photoresist is subjected to spin coating at 250 rpm for 60 seconds, vacuum desolventizing for 2 minutes, pre-baking at 110°C for 90 seconds, exposure energy of 200 mj, 2.38% TMAH development for 60 seconds, and post-baking curing at 180°C for 30 minutes to obtain a photocured film (V).

[0087] Example 6

[0088] Based on Example 1, the difference from Example 1 is that the aldehyde-containing compound is 3,4-dihydroxybenzaldehyde, and the acrylic acid monomer is 2-ethylacrylic acid. The obtained porphyrin pigment derivative is named A-06.

[0089] The raw materials for preparing black photoresist include: 45 parts of black color paste, 4 parts of porphyrin pigment derivatives, 6 parts of alkali-soluble resin, 6 parts of photosensitive monomers, 5 parts of photoinitiators, 1 part of leveling agents, 3 parts of silane coupling agents, and 30 parts of organic solvents.

[0090] Among them, the black color paste is a homemade color paste. The resin used in the preparation of the color paste is the same as the alkali-soluble resin, which is methacrylic acid-acrylate resin. The porphyrin pigment derivative is A-06, the photosensitive monomer is diphenyl phosphoazide, the initiator is OXE-02, the silane coupling agent is KBM-603, the leveling agent is BYK-354, and the organic solvent is ethylene glycol dimethyl ether.

[0091] The application process of the black photoresist is as follows: the black photoresist is spin-coated at 250 rpm for 60 seconds, vacuum desolventized for 2 minutes, pre-baked at 110°C for 90 seconds, exposed with 200 mj of energy, developed with 2.38% TMAH for 60 seconds, and post-baked for curing at 180°C for 30 minutes to obtain a photocured film (VI).

[0092] Comparative Example 1

[0093] Compared with Example 1, Comparative Example 1 is different only in that no porphyrin pigment derivative is added to the black photoresist in Comparative Example 1, and the remaining components and addition amounts are the same as those in Example 1.

[0094] Comparative Example 2

[0095] Compared with Example 1, the only difference between Comparative Example 2 is that the amount of porphyrin pigment derivative added to the black photoresist in Comparative Example 1 is too much, and the other components and addition amounts are exactly the same as those in Example 1.

[0096] Comparative Example 3

[0097] The specific implementation of Comparative Example 3 is different from that of Example 1 only in that the raw materials for preparing the black photoresist in Comparative Example 3 include: 60 parts of black color paste, which is added in excessive amount.

[0098] Comparative Example 4

[0099] The specific implementation of Comparative Example 4 is different from that of Example 1 only in that the black photoresist in Comparative Example 4 is post-cured at 250° C. for 30 min, that is, the curing temperature is too high.

[0100] In order to further verify the effectiveness and feasibility of the technical solution provided by the present invention, the inventors conducted performance tests on the black photoresists of the above-mentioned embodiments 1 to 6 and comparative examples 1 to 4, as follows:

[0101] (1) Film thickness: Use a film thickness meter to measure the thickness of the film after light curing.

[0102] (2) OD value: The spectral measurement uses a blank quartz plate as the background, with a spectral range of 200nm-500nm and an interval of 1nm. The ultraviolet absorbance of the photoresist is measured, and the absorbance A at each wavelength is recorded. The absorbance at each wavelength is divided by the film thickness to obtain the absorbance of the photoresist per micrometer film thickness at each wavelength, that is, the OD value of the photoresist at each wavelength.

[0103] (3) Curing rate: The curing rate of the black photoresist was measured by Fourier transform infrared (FT-IR) real-time spectroscopy.

[0104] (4) Adhesion: Use a knife to cut 100 grids on one side of the photosensitive glass coated with the photoresist composition, attach 3M tape to the center of the grid, and quickly and continuously pull it off. The adhesion is evaluated based on the degree of coating shedding: no shedding is 5B, shedding degree less than 5% is 4B, shedding degree 5-15% is 3B, shedding degree 15-35% is 2B, shedding degree 35-65% is 1B, and shedding degree greater than 65% is 0B.

[0105] After testing, the performance results of the compositions in the embodiments and comparative examples are shown in Table 1 below:

[0106] Table 1

[0107]

[0108]

[0109] In summary, from the data in Table 1 and the above test, it can be seen that when a small amount (1 to 5 parts) of the porphyrin pigment derivative prepared by the present invention is added to the black photoresist, the OD value can be effectively improved, and the amount used is less than the original black pigment, saving raw materials; at the same time, when it is matched with black color paste, alkali-soluble resin, photosensitive monomer, photoinitiator and auxiliary agent, the prepared photoresist can effectively improve the curing performance of the photoresist and improve the shedding problem when the film thickness increases. However, the OD value in the comparative example is low, the adhesion is poor, and the scope of application is small.

[0110] The above description is only a specific embodiment of the present invention, so that those skilled in the art can understand or implement the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention.

[0111] It should be understood that the present invention is not limited to what has been described above and that various modifications and changes may be made without departing from its scope. The scope of the present invention is limited only by the appended claims.

Claims

1. A porphyrin pigment derivative, characterized in that: The porphyrin pigment is modified by adding acrylic monomer into the porphyrin pigment, thereby obtaining a porphyrin pigment derivative.

2. A method for preparing a porphyrin pigment derivative as claimed in claim 1, characterized in that: The specific steps include: Step 1, dissolving an aldehyde-containing compound in a solvent and adding a five-membered heterocyclic compound to heat and react to obtain a porphyrin pigment; Step 2: Add acrylic acid monomer to the porphyrin pigment and heat to react to obtain a porphyrin pigment derivative.

3. The method for preparing the porphyrin pigment derivative according to claim 2, characterized in that: The aldehyde-containing compound includes any one of benzaldehyde, 4-carboxybenzaldehyde, 4-hydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 2-hydroxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde and 4-ethoxybenzaldehyde.

4. The method for preparing the porphyrin pigment derivative according to claim 2, characterized in that: The solvent includes any one of pentane, formic acid, acetic acid, ethyl ether, acetone, propionic acid, anisole, 1-propanol, 2-propanol, methyl ethyl ketone, dimethyl sulfoxide, isopropylbenzene, ethyl acetate, ethyl formate, isobutyl acetate, methyl acetate, 3-methyl-1-butanol, methyl isobutyl ketone, 2-methyl-1-propanol, and propyl acetate.

5. The method for preparing the porphyrin pigment derivative according to claim 2, characterized in that: The five-membered heterocyclic compound includes any one of furan, thiophene, pyrrole, thiazole and imidazole.

6. The method for preparing the porphyrin pigment derivative according to claim 2, characterized in that: In step 1, the heating temperature is 100-150° C., and the reaction time is 6-10 hours; in step 2, the heating temperature is 60-80° C., and the reaction time is 4-6 hours.

7. A low-temperature black photoresist, characterized in that: The invention comprises, by weight: 30 to 45 parts of black color paste, 1 to 5 parts of porphyrin pigment derivative, 3 to 20 parts of alkali-soluble resin, 5 to 12 parts of photosensitive monomer, 4 to 8 parts of photoinitiator, 0.2 to 2 parts of leveling agent, 0.5 to 3 parts of silane coupling agent and 30 to 60 parts of organic solvent; the porphyrin pigment derivative is prepared by the preparation method as described in any one of claims 2 to 6.

8. The low temperature black photoresist according to claim 7, characterized in that: The alkali-soluble resin is selected from an acrylic resin having an acid value of 60 to 90 mgKOH / g, a molecular weight of 3000 to 5000, a PDI value of ≤1.3, and containing a fluorene structure.

9. A method for preparing a low-temperature black photoresist as claimed in claim 7 or 8, characterized in that: The raw materials are added into a reaction container according to corresponding weight parts, and mixed and stirred to obtain the product.

10. An application of the low-temperature black photoresist as claimed in claim 7 or 8, characterized in that: The low-temperature black photoresist can be used in an environment below 200° C. and applied to OLED or Micro-LED devices.

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