Low-temperature curable photosensitive resin composition and display using same

Abstract

The invention relates to a low-temperature curing type photosensitive resin composition, which comprises the following components: (a) 30 to 80 weight percent of alkaline water soluble light-cured resin; (b) 10 to 60 wt% of a photopolymerizable monomer; (c) 0.1 to 10 wt% of a photoinitiator; (d) 0.1 to 6 wt% of a coupling agent; (e) other additives, wherein the content of each component is based on 100 wt% of the total solid content of the composition; wherein the alkaline water soluble photocurable resin is prepared by a substance comprising: (i) an at least partially terminated diisocyanate; (ii) an ethylenically unsaturated carboxylic acid; and (iii) an unsaturated epoxide, wherein the alkaline water soluble photocurable resin has a weight average molecular weight of 10,000 to 50,000 and an acid value of 80 to 200 mg KOH / g. The low-temperature curing type photosensitive resin composition can be rapidly cured at the temperature of 120 DEG C or below, meanwhile, fine patterns of photoresist are achieved, and a cured product has excellent chemical reagent resistance and heat resistance.

Description

Technical Field

[0001] This invention relates to the field of photosensitive materials technology, and more particularly to low-temperature curing photosensitive resin compositions and displays using the same. Background Technology

[0002] Traditional photoresists, especially negative photoresists, typically require curing at temperatures above 200°C to meet chemical and heat resistance requirements. However, high-temperature processing can easily lead to substrate deformation, warping, or performance degradation, and also suffers from drawbacks such as high energy consumption or narrow process windows. Traditional high-temperature photoresists have shown significant limitations for high-resolution, flexible, and large-size display technologies (such as OLED and Micro-LED panels). Low-temperature curing photoresists are more suitable for the product structure and performance requirements of new display devices.

[0003] However, conventional low-temperature curing systems often suffer from incomplete curing, poor film thickness uniformity, and / or insufficient bottom reaction due to insufficient crosslinking density, leading to development residue or peeling problems. Therefore, most currently used low-temperature curing photoresists require the addition of curing agents to the formulation to enable better crosslinking and curing at low temperatures (below 120°C) to meet the required performance. For this purpose, anhydride-based and amine-based curing agents are typically added to photoresist formulations. Anhydride-based curing agents have higher curing temperatures than amine-based curing agents, and their cured products have poor chemical resistance, which is detrimental to subsequent display panel manufacturing processes. While amine-based curing agents have low curing temperatures and good curing effects, their poor stability makes them unsuitable as mainstream curing agents for low-temperature curing photoresists. Furthermore, these curing agents have a significant impact on photoresist performance; in particular, the addition of curing agents to the formulation poses a significant risk to the transportation and storage of the photoresist. In recent years, some latent curing agents have also been used in low-temperature curing photoresists and have achieved good curing results. They are usually closed isocyanate-based curing agents, but their long-term storage stability is poor and the desealing rate of latent curing agents sometimes lags behind the curing crosslinking rate, which leads to incomplete curing and affects the performance of photoresists after curing. Therefore, their use in photoresists is also limited.

[0004] Patent application CN 120004805 A discloses a photocurable blocked isocyanate compound and a low-temperature curing photoresist. By introducing end-capped isocyanate groups, the curing temperature is lowered, allowing the photoresist structure to crosslink at low temperatures. This ensures good resolution while providing the cured photoresist product with good chemical resistance and thermal stability. However, the curing time of this photoresist is relatively long, reducing the production efficiency of panel production lines. Furthermore, the resin used alone has poor developability and must be used in combination with other acrylic resins, which increases the cost.

[0005] Therefore, there is a need for a low-temperature curing photosensitive resin composition that can achieve faster curing at temperatures below 120°C without the addition of a curing agent, while simultaneously achieving fine patterns in the photoresist and producing a cured product with excellent chemical resistance and heat resistance. Summary of the Invention

[0006] In view of this, on the one hand, the present invention provides a low-temperature curing photosensitive resin composition comprising the following components: (a) Alkali-soluble light-curing resin, 30 to 80% by weight. (b) Photopolymerizable monomers, 10 to 60% by weight; (c) Photoinitiator, 0.1 to 10% by weight; (d) Coupling agent, 0.1 to 6% by weight; (e) Other additives, The content of each component is based on the total solid content of the composition, 100% by weight. The alkaline water-soluble photocurable resin is prepared by comprising: (i) at least partially capped diisocyanate; (ii) olefinic unsaturated carboxylic acid; and (iii) unsaturated epoxide, wherein the alkaline water-soluble photocurable resin has a weight-average molecular weight of 10,000 to 50,000 and an acid value of 80 to 200 mg KOH / g.

[0007] In a preferred embodiment, when preparing the alkaline water-soluble photocurable resin, the molar ratio of the diisocyanate (calculated as uncapped diisocyanate) to the olefinic unsaturated carboxylic acid is 1:(1.3-5), preferably 1:(1.5-4), more preferably 1:(1.6-3), and even more preferably 1:(1.8-2.3).

[0008] In a preferred embodiment, when preparing the alkaline water-soluble photocurable resin, the molar ratio of the olefinic unsaturated carboxylic acid to the unsaturated epoxide used is 1:(0.5-1.2), preferably 1:(0.6-1.1), more preferably 1:(0.7-1.0), and even more preferably 1:(0.8-1.0).

[0009] In a preferred embodiment, when preparing the alkaline water-soluble photocurable resin, the molar amount of diisocyanate used is a moles, the amount of end-capping agent used is b moles, the amount of olefinic unsaturated carboxylic acid used is c moles, and the amount of unsaturated epoxide used is d moles, which satisfy the following relationship: 0.50≤c / (2a+db)≤1.40, preferably 0.55≤c / (2a+db)≤1.30, more preferably 0.60≤c / (2a+db)≤1.25, more preferably 0.65≤c / (2a+db)≤1.20, and even more preferably 0.66≤c / (2a+db)≤1.15.

[0010] In a preferred embodiment, the diisocyanate is selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hydrogenated phenylmethane diisocyanate, hexamethylene diisocyanate, and any combination thereof.

[0011] In a preferred embodiment, the end-capping agent used is selected from acetanilides, such as acetanilide or N-methylacetamide; caprolactams, such as caprolactam or N-acetylcaprolactam; pyridines, such as 2-hydroxypyridine, 3-hydroxyquinoline, piperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine or 4-(dimethylamino)-2,2,6,6-tetramethylpiperidine; oximes, such as butanone oxime, 3-hydroxy-3-methyl-2-butanone oxime, 4,4-dimethylcyclohexanone oxime, cyclohexanone oxime, acetone oxime or acetaldehyde oxime; phenols, such as 2-dimethylaminomethylphenol or 3-pentadecanylphenol; piperidinones, such as 2,2,6,6-tetramethyl-4-piperidinone; or any combination thereof.

[0012] In a preferred embodiment, the olefinic unsaturated carboxylic acid is a compound containing an unsaturated double bond and a carboxylic acid group. Preferably, it is selected from C2-C8 olefinic carboxylic acids, such as (meth)acrylic acid, 2-pentenoic acid, 3-hexenoic acid, butenoic acid, 2-ethylacrylic acid, cyclopentenic acid (such as 1-cyclopentenic acid), cyclohexenic acid (such as 3-cyclohexene-1-carboxylic acid), maleic acid, and any combination thereof.

[0013] In a preferred embodiment, the unsaturated epoxide is an epoxy compound containing unsaturated double bonds, preferably selected from glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and any combination thereof.

[0014] In a preferred embodiment, the amount of the alkaline water-soluble photocurable resin is 35 to 76% by weight, preferably 45 to 74% by weight, more preferably 50 to 72% by weight, and even more preferably 60 to 70% by weight or 62 to 68% by weight, based on the total solid content of the composition of 100% by weight.

[0015] On the other hand, the present invention also relates to displays prepared using the low-temperature curing photosensitive resin composition of the present invention.

[0016] Surprisingly, the low-temperature curing photosensitive resin composition of the present invention can be rapidly cured below 120°C, while achieving fine patterns in the photoresist and the cured product has excellent chemical resistance and heat resistance. Attached Figure Description

[0017] Figures 1-7 Microscopic magnified images of the cured films of the photosensitive resin compositions prepared according to Examples 1-6 and Comparative Example 1 are shown respectively. Detailed Implementation

[0018] It should be noted that, unless otherwise defined, the technical or scientific terms used in this application shall have the ordinary meaning as understood by one of ordinary skill in the art.

[0019] In this invention, acid value refers to the value obtained by acid-base titration using KOH standard solution according to GB / T2895-2008. Weight-average molecular weight was determined by gel permeation chromatography (GPC) according to GB / T 21863-2008 "Gel permeation chromatography (GPC) using tetrahydrofuran as eluent" (equivalent to German standard DIN 55672-1:2007 "Gel permeation chromatography (GPC) Part 1: Using tetrahydrofuran (THF) as eluent"). Solid content was determined according to GB / T 1725-2007.

[0020] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0021] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0022] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0023] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0024] The terms “above” and “below” used in this application include the number itself. For example, “above one” means one or more, and “above one of A and B” means “A”, “B” or “A and B”.

[0025] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0026] Unless otherwise specified, in this application, the term "arbitrary combination" refers to any combination of any two, (if any) three, four, five, or even all of the alternative examples preceding this statement.

[0027] Unless otherwise stated, all contents and percentages in the context of this application are based on weight.

[0028] In this invention, unless otherwise stated, all operations are performed at room temperature (25°C) and atmospheric pressure (101 kPa).

[0029] This invention provides a low-temperature curing photosensitive resin composition comprising the following components: (a) Alkali-soluble light-curing resin, 30 to 80% by weight. (b) Photopolymerizable monomers, 10 to 60% by weight; (c) Photoinitiator, 0.1 to 10% by weight; (d) Coupling agent, 0.1 to 6% by weight; (e) Other additives, The content of each component is based on the total solid content of the composition, 100% by weight. The alkaline water-soluble photocurable resin is prepared by comprising: (i) at least partially capped diisocyanate; (ii) olefinic unsaturated carboxylic acid; and (iii) unsaturated epoxide, wherein the alkaline water-soluble photocurable resin has a weight-average molecular weight of 10,000 to 50,000 and an acid value of 80 to 200 mg KOH / g.

[0030] In this invention, the term diisocyanate refers to a compound containing two isocyanate groups (-NCO).

[0031] In a preferred embodiment, the relative molecular weight of the diisocyanate may be 90-500, preferably 100-400, more preferably 120-300, and even more preferably 130-200.

[0032] In a preferred embodiment, the diisocyanate is selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hydrogenated phenylmethane diisocyanate, hexamethylene diisocyanate, and any combination thereof. Preferably, the toluene diisocyanate includes toluene-2,3-diisocyanate, toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene-2,6-diisocyanate, toluene-3,4-diisocyanate, toluene-3,5-diisocyanate, or any combination thereof, with toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, or any combination thereof being more preferred.

[0033] In a preferred embodiment, the diisocyanate is selected from toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and any combination thereof.

[0034] In this invention, the expression "at least partially capped" means that at least 10 mol%, preferably at least 30 mol%, more preferably at least 45 mol%, even more preferably at least 60 mol%, further preferably at least 80 mol%, and even more preferably 99 mol% of the isocyanate groups in the diisocyanate are capped by a capping agent. The capping agent can be decapped in a temperature range greater than 80°C to 120°C. Preferably, in this invention, at least partially capped diisocyanates do not include 100% isocyanate groups being capped.

[0035] In a preferred embodiment, the capping agent may be selected from acetanilides, such as acetanilide or N-methylacetamide; caprolactams, such as caprolactam or N-acetylcaprolactam; pyridines, such as 2-hydroxypyridine, 3-hydroxyquinoline, piperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine or 4-(dimethylamino)-2,2,6,6-tetramethylpiperidine; oximes, such as butanone oxime, 3-hydroxy-3-methyl-2-butanone oxime, 4,4-dimethylcyclohexanone oxime, cyclohexanone oxime, acetone oxime or acetaldehyde oxime; phenols, such as 2-dimethylaminomethylphenol or 3-pentadecanylphenol; piperidinones, such as 2,2,6,6-tetramethyl-4-piperidinone; or any combination thereof.

[0036] Preferably, the capping agent is selected from phenolic capping agents, such as 2-dimethylaminomethylphenol or 3-pentadecanylphenol; piperidinone capping agents, such as 2,2,6,6-tetramethyl-4-piperidinone; ketoxime capping agents, such as butanone oxime, 3-hydroxy-3-methyl-2-butanone oxime or 4,4-dimethylcyclohexanone oxime; and any combination thereof.

[0037] In this invention, the reaction between the capping agent and the isocyanate group is well known to those skilled in the art; that is, the active hydrogen of the capping agent reacts with the isocyanate group to generate a carbamoyl group. Furthermore, in this invention, unless otherwise stated, "capping" refers to capping the isocyanate group using a capping agent.

[0038] In a preferred embodiment, the olefinic unsaturated carboxylic acid is a compound containing an unsaturated double bond and a carboxylic acid group, selected from C2-C8 alkenyl carboxylic acids, such as (meth)acrylic acid, 2-pentenoic acid, 3-hexenoic acid, butenoic acid, 2-ethylacrylic acid, cyclopentenic acid (such as 1-cyclopentenic acid), cyclohexenic acid (such as 3-cyclohexene-1-carboxylic acid), maleic acid, and any combination thereof.

[0039] In a preferred embodiment, the relative molecular weight of the olefinic unsaturated carboxylic acid may be 60-500, preferably 70-200, and more preferably 72-150.

[0040] In a preferred embodiment, the olefinic unsaturated carboxylic acid may contain one or more (e.g., two) unsaturated double bonds and / or carboxyl groups, preferably only one unsaturated double bond (C=C) and a carboxyl group (COOH).

[0041] According to the present invention, unless otherwise defined, the term "alkenyl" on its own or in combination with other terms shall be understood to refer to a straight-chain or branched C2-C8 alkenyl group having at least one double bond, such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1,3-pentadienyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, and 1,4-hexadienyl; wherein C2-C6 alkenyl or C2-C4 alkenyl are preferred.

[0042] In this invention, the unsaturated epoxide is an epoxy compound containing unsaturated groups (e.g., unsaturated double or triple bonds).

[0043] In a preferred embodiment, the relative molecular weight of the unsaturated epoxide may be 80-500, preferably 90-400, more preferably 100-300, and even more preferably 110-200.

[0044] Preferably, the unsaturated epoxide may be selected from glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and any combination thereof.

[0045] In this invention, it should be understood that the alkaline water-soluble photocurable resin refers to a resin containing carboxyl groups and polymerizable double bonds.

[0046] In this invention, unless otherwise stated, the terms "alkali-soluble UV-curable resin" and "solid components of alkali-soluble UV-curable resin" are used synonymously. This is because in use, "alkali-soluble UV-curable resin" typically contains solvent components (e.g., for reducing viscosity and facilitating handling); however, when it comes to, for example, calculating material ratios or determining acid values, only solvent-free components are usually considered, as is well known to those skilled in the art.

[0047] In a preferred embodiment, the alkaline water-soluble photocurable resin is prepared by reacting (i) at least partially capped diisocyanate and (ii) olefinic unsaturated carboxylic acid in a solvent in the presence of a catalyst, followed by reaction with (iii) an unsaturated epoxide.

[0048] In a preferred embodiment, the catalyst may be selected from dibutyltin dilaurate, stannous octanoate, dibutyltin dineodecanate, dibutyltin maleate, dibutylbismuth dilaurate, and any combination thereof; preferably, the solvent may be selected from ethyl acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and any combination thereof. In a more preferred embodiment, the catalyst is dibutyltin dilaurate, and the solvent is ethyl acetate.

[0049] In a preferred embodiment, the amount of catalyst used is the amount conventionally used in the art, for example, it may be 0.1 to 5% by weight, preferably 0.2 to 3% by weight, more preferably 0.3 to 2% by weight, and even more preferably 0.4 to 1% by weight, based on the weight of the uncapped diisocyanate used. In a preferred embodiment, the catalyst may be added all at once during the preparation of the capped isocyanate, or it may be added in multiple stages, for example, adding the remaining catalyst while adding the olefinic unsaturated carboxylic acid.

[0050] Preferably, the at least partially capped diisocyanate can be prepared in situ within the above reaction system, i.e., without separating the prepared at least partially capped diisocyanate, and can be directly used in the next reaction step. The reaction for isocyanate capping is well known to those skilled in the art. For example, in the presence of a solvent and a catalyst (the solvent here can be the same as that used in the subsequent reaction system), the diisocyanate is reacted with a capping agent at a temperature of 50-80°C (preferably 60-75°C), for example, for 1-8 hours, preferably 2 to 6 hours, more preferably 3 to 5 hours; preferably, the capping agent is added dropwise to the diisocyanate. The degree of capping can be adjusted by the amount of capping agent added. In this invention, the degree of capping is as described above.

[0051] In a preferred embodiment, the reaction of at least partially capped diisocyanate and olefinic unsaturated carboxylic acid can be carried out at a temperature of 55-80°C, preferably 65-75°C, for 2-6 hours, preferably 3-5 hours.

[0052] In a preferred embodiment, the reaction of at least partially capped diisocyanate and olefinically unsaturated carboxylic acid followed by reaction with unsaturated epoxide can be carried out at a temperature of 60-80°C, preferably 65-75°C, for 1-4 hours, preferably 1.5-3 hours.

[0053] In this invention, during the preparation of the alkaline water-soluble photocurable resin, there is no need to separate intermediate products; that is, there is no intermediate product separation process during the preparation of the alkaline water-soluble photocurable resin.

[0054] Therefore, in a preferred embodiment, the method for preparing the alkaline water-soluble photocurable resin comprises the following steps: (1) reacting a capping agent with a diisocyanate at a temperature of 50-80°C in the presence of a solvent and a catalyst; (2) adding an olefinic unsaturated carboxylic acid to the mixture obtained in step (1) and reacting it; and (3) adding an unsaturated epoxide to the mixture obtained in step (2) and reacting it.

[0055] In a preferred embodiment, the at least partially capped diisocyanate has a capping rate of 20-99.5%, preferably 30-99%.

[0056] In this invention, the capping rate can be calculated by the molar amount of diisocyanate and the amount of capping agent added, as is well known to those skilled in the art.

[0057] In a preferred embodiment, when preparing the alkaline water-soluble photocurable resin, the molar ratio of the diisocyanate (calculated as uncapped diisocyanate) to the olefinic unsaturated carboxylic acid can be 1:(1.3-5), preferably 1:(1.4-4), more preferably 1:(1.5-3), and even more preferably 1:(1.6-2.5).

[0058] In a preferred embodiment, when preparing the alkaline water-soluble photocurable resin, the weight ratio of the diisocyanate (calculated as uncapped diisocyanate) to the olefinic unsaturated carboxylic acid can be 1:(0.6-2), preferably 1:(0.7-1.8), more preferably 1:(0.8-1.6), and even more preferably 1:(0.9-1.4).

[0059] In a preferred embodiment, when preparing the alkaline water-soluble photocurable resin, the molar ratio of the olefinic unsaturated carboxylic acid to the unsaturated epoxide used can be 1:(0.5-1.2), preferably 1:(0.6-1.1), more preferably 1:(0.7-1.0), and even more preferably 1:(0.8-1.0).

[0060] In a preferred embodiment, when preparing the alkaline water-soluble photocurable resin, the weight ratio of the olefinic unsaturated carboxylic acid to the unsaturated epoxide used can be 1:(0.7-2.5), preferably 1:(0.8-2.0), more preferably 1:(0.9-1.5), and even more preferably 1:(1.0-1.3).

[0061] In a preferred embodiment, when preparing the alkaline water-soluble photocurable resin, the molar ratio of the diisocyanate (calculated as uncapped diisocyanate) to the unsaturated epoxide can be 1:(1.0-3), preferably 1:(1.1-2.5), more preferably 1:(1.2-2.4), and even more preferably 1:(1.3-2.2).

[0062] In a preferred embodiment, when preparing the alkaline water-soluble photocurable resin, the molar amount of diisocyanate used is a moles, the amount of end-capping agent used is b moles, the amount of olefinic unsaturated carboxylic acid used is c moles, and the amount of unsaturated epoxide used is d moles, which satisfy the following relationship: 0.50≤c / (2a+db)≤1.40, preferably 0.55≤c / (2a+db)≤1.30, more preferably 0.60≤c / (2a+db)≤1.25, more preferably 0.65≤c / (2a+db)≤1.20, and even more preferably 0.66≤c / (2a+db)≤1.15.

[0063] Surprisingly, when the amounts of diisocyanate, end-capping agent, olefinic unsaturated carboxylic acid, and unsaturated epoxide are controlled within the above range during the preparation of alkaline water-soluble photocurable resin, the resulting cured film exhibits better performance, particularly in terms of resolution and chemical resistance.

[0064] In a preferred embodiment, the weight-average molecular weight of the alkaline water-soluble photocurable resin is 10,000 to 50,000, preferably 11,000 to 40,000, more preferably 11,100 to 20,000, and even more preferably 11,200 to 15,000.

[0065] In a preferred embodiment, the acid value of the alkaline water-soluble photocurable resin is 80 to 200 mg KOH / g, preferably 90 to 150 mg KOH / g, more preferably 100 to 130 mg KOH / g, and even more preferably 105 to 125 KOH / g.

[0066] In a preferred embodiment, the solid content of the alkaline water-soluble photocurable resin may be 20 to 60%, preferably 25 to 50%, and more preferably 30 to 40%.

[0067] In a preferred embodiment, the amount of the alkaline water-soluble photocurable resin may be 35 to 76% by weight, preferably 45 to 74% by weight, more preferably 50 to 72% by weight, and even more preferably 60 to 70% by weight or 62 to 68% by weight, based on the total solid content of the composition of 100% by weight.

[0068] In a preferred embodiment, the reaction in the preparation of the alkali-soluble photocurable resin can be carried out in an inert gas atmosphere and in a light-protected environment, wherein the inert gas used includes nitrogen, argon, helium and any combination thereof.

[0069] In a preferred embodiment, the low-temperature curing photosensitive resin composition does not contain curing agents conventionally used in the art, such as anhydride curing agents or amine curing agents.

[0070] Photopolymer monomers Photopolymerizable monomers are also known as reactive diluents. These monomers can be selected from β-carboxyethyl acrylate, bisphenol A dimethacrylate, 2-phenylphenoxyethyl acrylate, diphenyl polyoxyethylene ether acrylate, bis-trimethylolpropane tetraacrylate, dipropylene glycol diacrylate, dipentaerythritol hexaacrylate, ethoxyethoxyethyl acrylate, propanetriol triacrylate, 1,6-hexanediol diacrylate, isobornyl acrylate, propoxylated neopentyl glycol diacrylate, 2-phenylthioethyl acrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaethoxypentaerythritol tetraacrylate, 2-phenoxyethyl acrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane trimethacrylate, and trimethylolpropane triacrylate. One or more of the following: methyl propane triacrylate, triethoxytrimethylolpropane triacrylate, pentadecylethoxytrimethylolpropane triacrylate, 2-isopropylphenylphenoxyhexyl acrylate, tripropylene glycol diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, aliphatic hexaacrylate, aliphatic polyurethane acrylate, o-phenylphenoxyethyl acrylate, aliphatic polyurethane dimethacrylate, aliphatic polyurethane acrylate, aliphatic polyurethane diacrylate, aliphatic polyurethane hexaacrylate, 2-hydroxy-3-phenoxypropyl acrylate, aliphatic hexaacrylate, aromatic polyurethane hexaacrylate, aromatic polyurethane dimethacrylate, 2-hydroxy-3-phenylphenoxypropyl acrylate, ethoxylated bisphenol fluorene diacrylate and their phosphate esters.

[0071] In a preferred embodiment, the photopolymerizable monomer comprises dipentaerythritol hexaacrylate.

[0072] In a preferred embodiment, the weight ratio of the photopolymerizable monomer to the alkaline water-soluble photocurable resin may be 1:(1.0-5), preferably 1:(1.2-4), more preferably 1:(1.6-3), and even more preferably 1:(1.8-2.5).

[0073] In a preferred embodiment, the amount of the photopolymerizable monomer may be 10 to 60% by weight, preferably 15 to 50% by weight, more preferably 20 to 40% by weight, and even more preferably 25 to 30% by weight, based on the total solid content of the composition of 100% by weight.

[0074] Photoinitiator In the low-temperature curable photosensitive resin composition of the present invention, the photoinitiator used can rapidly initiate a chemical reaction after absorbing light energy. The photoinitiator may include free radical photoinitiators and cationic photoinitiators. Free radical photoinitiators can be selected from benzoin ether, phenyl dimethoxyacetophenone, 2-hydroxy-2-methylphenyl-1-propanone, hydroxycyclohexylphenyl ketone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)benzene]-2-morpholinopropanone, 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)butanone, 2,4,6-trimethylbenzoyl oxide diphenylphosphine oxide, di(2,6-dimethoxybenzoyl)-(2-methylpropyl)phosphine oxide, hexaarylimidazolium, α-chloroacetophenone, sulfonylacetophenone, sulfonyloxyacetophenone, benzophenone, michidone, thioxanthraquinone, isopropylthioxanthraquinone, chloropropoxythioxanthraquinone, anthraquinone, 2-ethylanthraquinone, 2-isobutylanthraquinone and anthraquinone sulfonates, camphorquinone, coumarinone, 3- Coumarinone, bis-coumarin, 9-phenylacridine, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, N-alkyl / aliphatic maleimide, and N-aryl maleimide may be selected from one or more of these; the cationic initiator may be selected from 4,4'-dimethyldiphenyliodohexafluorophosphate, 5-p-toluenesulfonyloxyimide-5H-thiophene-2-ylide-(4-methoxyphenyl)acetonitrile, bis(4-dodecylbenzene)iodohexafluoroantimonate, (4-octaneoxyphenyl)phenyliodohexafluoroantimonate, bis(4-tert-butylphenyl)iodohexafluorophosphate, 4-[(2-hydroxytetradecyl)phenyl]phenyliodohexafluoroantimonate, 4-[(2-hydroxytetradecyl)phenyl]p-tolueneiodohexafluoroantimonate, (4-octaneoxyphenyl)phenyliodo Hexafluoroantimonate, (4-octyloxyphenyl)-p-tolyliodohexafluoroantimonate, 4-isobutylphenyl-4-methylphenyliodohexafluoroantimonate, triphenylsulfonate Fluoroborate, triphenylsulfonate hexafluorophosphate, triphenyl sulfide Hexafluoroantimonate, 4-Tolyldiphenylsulfonate Hexafluorophosphate, 4-chlorophenyldiphenylsulfonate Hexafluorophosphate, 3-nitrophenyl diphenyl sulfide Hexafluorophosphate, 4-acetamidophenyldiphenylthiohexafluorophosphate, 3-benzoylphenyldiphenylthiohexafluorophosphate Hexafluorophosphate, (cyclopentadienyl-iron-benzene)hexafluorophosphate, (cyclopentadienyl-iron-toluene)hexafluorophosphate, (cyclopentadienyl-iron-p-xylene)hexafluorophosphate, cyclopentadienyl(fluorene)iron(II)hexafluorophosphate, (cyclopentadienyl-iron-biphenyl)hexafluorophosphate, (cyclopentadienyl-iron-2,5-dimethylacetophenone)hexafluorophosphate, (acetylcyclopentadienyl-iron-p-xylene)hexafluorophosphate, (cyclo... One or more of the following: (cyclopentadienyl-iron-anisole) hexafluorophosphate, (cyclopentadienyl-iron-diphenyl ether) hexafluorophosphate, (cyclopentadienyl-iron-2,4-diethoxybenzene) hexafluorophosphate, (dicyclopentadienyl-iron-carbazole) hexafluorophosphate, (dicyclopentadienyl-iron-diphenyl ether) hexafluorophosphate, (dicyclopentadienyl-iron-ethylcarbazole) hexafluorophosphate, and (dicyclopentadienyl-iron-biphenyl) hexafluorophosphate.

[0075] In a preferred embodiment, the photoinitiator comprises 2-methyl-1-[4-(methylthio)benzene]-2-morpholinoacetone (e.g., trade name IRGACURE 907, available from BASF, Germany).

[0076] In a preferred embodiment, the amount of the photoinitiator may be 0.1 to 10% by weight, preferably 0.5 to 8% by weight, more preferably 1 to 7% by weight, and even more preferably 3 to 6% by weight, based on the total solid content of the composition of 100% by weight.

[0077] Coupling agent The coupling agent is used to improve the adhesion between the cured product of the composition of the present invention and the substrate, thereby improving the applicability of the composition. The coupling agent includes, but is not limited to, silane-based coupling agents, examples of which include vinyltrimethoxysilane, tetrakis(2-methoxyethoxy)silane, 1,2-bis(triethoxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, methyltriethoxysilane, methyltrimethoxysilane, methylpropyldiethoxysilane, methylpropyldimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltriethoxysilane, isooctyltrimethoxysilane, octylmethyldimethoxysilane, etc. Octylmethyldiethoxysilane, dodecyltrimethoxysilane, dodecylmethyldiethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, octadecylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, acyloxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(methacryloyloxy) propyltriethoxysilane, 3-(methacryloyloxy)propylmethyldimethoxysilane, 3-(methacryloyloxy)propylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, 3-glycidyl etheroxypropylmethyldimethoxysilane, 3-glycidyl etheroxypropylmethyldiethoxysilane, 3-isocyanopropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, allyl isocyanurate Silyl esters, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-n-butyl-3-aminopropyltrimethoxysilane, N-n-butyl-3-aminopropyltriethoxysilane, 3-ureapropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 3-anilinepropyltrimethoxysilane, N,N-diethyl-3-aminopropyltrimethoxysilane, N,One or more of the following coupling agents may be used: N-dimethyl-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, tri-[3-(trimethoxy)silylpropyl]isocyanurate, cyclohexylaminomethyltriethoxysilane, 2-aminoethylaminomethyltriethoxysilane, alkoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropylmethyldipropoxysilane, trimethoxyhydrosilane, triethoxyhydrosilane, methyldimethoxyhydrosilane, and diethylaminomethyltriethoxysilane. Other types of coupling agents may also be used, such as titanate coupling agents of triisostearoyl titanate and isopropyltrioleyloxytitanate, and aluminate coupling agents such as distearate isopropyl aluminate.

[0078] In a preferred embodiment, the coupling agent comprises vinyltrimethoxysilane.

[0079] In a preferred embodiment, the amount of the coupling agent may be 0.1 to 6 wt%, preferably 0.2 to 5 wt%, more preferably 0.5 to 4 wt%, and even more preferably 0.8 to 2 wt%, based on the total solid content of the composition in 100% by weight.

[0080] Other additives Leveling agent Leveling agents ensure film formation and uniformity of film thickness during the coating process. Examples include, but are not limited to, acrylic leveling agents, silicone leveling agents, fluorocarbon leveling agents, and high-boiling-point solvent-based leveling agents. Trade names include: Flow 425, Flow 300, Flow 370, Flow ATF 2, Glide 411, Glide 432, Glide 482, Glide 100, Glide 410, Glide 415, Glide 450, Glide 485, Glide A 115, Glide B 1484, Glide Rad 2100, Glide Rad 2200N, or Glide Rad 2300 from German company DIGIC; and SiFast K-362, SiFast SF-721, SiFast SF-725, and SiFast from Guangdong BiaoMei Silicon Fluorine New Materials Co., Ltd. SF-728, SiFastSF-729 / 729A, SiFastSF-732, SiFastSF-734, SiFastSF-9090, SiFastSF-719, SiFastSF-104 , SiFastSF-510, SiFastSF-5101, SiFastSF-5102, SiFastSF-5104 or SiFastSF-761C; Levaslip from Deqian (Shanghai) Chemical Co., Ltd. 407,Levaslip 410,Levaslip 432,Levaslip 435,Levaslip 455,Levaslip 466,Levaslip 495,Levaslip 810,Levelo l835,Levaslip 836,Levelo l839,Levelo l837,Levaslip 872,Levaslip 876,Levaslip 879.Levaslip 882, Levaslip 8629, Levelol TSP or SLIP-AYDFS 444; BYK-333, BYK-361N, BYK-320, BYK-392, BYK-399, BYK-3550, BYK-359, BYK-360P, BYK-364P, BYK-3900P or BYK-3902P from BYK Chemicals (Germany).

[0081] In a preferred embodiment, the leveling agent comprises BYK-333 from BYK Chemicals, Germany.

[0082] In a preferred embodiment, the leveling agent is used in an amount of 0.1 to 6 wt%, preferably 0.2 to 5 wt%, more preferably 0.5 to 4 wt%, and even more preferably 0.8 to 2 wt%, based on the total solids content of the composition in 100% by weight.

[0083] Pigment Depending on the specific application, the low-temperature curing photosensitive resin composition of the present invention can contain various different color pastes. Based on their different effects during panel manufacturing, the color pastes used in the resin composition of the present invention can be categorized into black, red, green, and blue color pastes. Black pigments, which may be mentioned as trade names, include Orion's FW200, SB6, SB4, SB4A, SB250, S160, 140U, 140V, 900L, 50L, 30L, P35, 600L, P60, P300, N305, N505, N600, N605, HIBLACK 10, L6, L6B, 5L, N510, F138, F80, F85, 20L, 40L, 930L, N510, 49L, XE2, FW255, 20BT, 40B2, 420B, XE2-B or XE2; Cabot's E2000, M1400, M1300, M1000, etc. M900, M880, M800, M570, M470, M460, M430, M120, E570, P280, R99R, R660R, R400R, R330R, R250R, R350R, MogulE, Mogul L, Mogul H, VXC-72, VXC-72R, VXC305, BP2000, BP7, CXS935, E570, E415, N660, M717, .M700, M580, N330, N550, N774, M120, BP3560, ME N234, VXC-72, VXC-72R, VXC305, BP200O; Evonik’s STOCKOSORB 660 MM, STOCKOSORB 660, Powder STOCKOSORB 660XL, FavorPac, SP1307, Favor-Pac 593, Favor-Pac 530 or Favor-Pac 300.

[0084] Red pigments that can be mentioned as trade names include BASF's D3430, D3540, D3656HD, D3773, D3780, D3865, D3890, D4450, K2915, K2920, K3580, K3693SQ, K3810, K3840, K3840SQ, and K3890. , K3911HD, K4535, K4035, K4060FP, K4104, K4165, K4170FP, K4180, K4270, K4270FP, K4430FP, K4535FP, L3550, L3 630, L3660HD, L3670HD, L3671HD, L3685HD, L3837, L3875, L3885, L3910HD, L3920, L4010, L4039, L4040,, L4100HD L4110HD, L4330B, L4382, L4540, L4700, 4BK, 4330K, RK 3430K, 4CK, 4410K, BRK, 3890K, 5BK, 4535K or BK3630K, Clariant’s D3G70Hostaperm, P2GL Hostaperm, E5B02 Hostaperm, ER02 Hostaperm, E02 Hostaperm, F3RK70CN, NovopermF5RK, NovopermHF48 Novoperm, HF4C Permanent, L5B01 Permanent, TDG PV FASTTD3G, HFR Graphtol, P2B Graphtol, HF2B Graphtol, 3RLP Graphtol, LGGraphtol, LC Graphtol, HFG Graphtol, F5RK Graphtol, HF3C Graphtol, F3RK70 Graphtol or 1102B.

[0085] Green pigments, which may be mentioned as trade names, include BASF's K8730, K8740, K8740LW, K9360, K9610, L8710, L8730 or L9361; Clariant's GK8750K, GNX Hostaperm, GNX PV FAST, B2G131CN or GG131CN; and Nubiola's Nubiflow, Nubiola CP-84, Nubiola EP-19, Nubiola EP-25, Nubiola EP-28, Nubiola EP-62, Nubiola F-36 (F36), Nubiola FG-75, Nubiola GP-58, Nubiola H-56, Nubiola RA-40 or Nubiola FP-64.

[0086] Blue pigments, which can be mentioned as trade names, include BASF's D7079, D7088, D7110, D8730, Green D9360, K6310, K6850, K6902, K6907, K6911, K7079, K7090, K7090FP, K7096, K7097, K7104LW, L4045, L6480, L6700FL6900, L6905, L6905F, L6950, L7085, L7101F, A3BB, Blue 755, Blue 825, Blue 855 or Blue 807, and Clariant's 4GK7080K, A3RK6480K, A2R Hostaperm, A4R Hostaperm, B2GLHostaperm, A2RPVFAST, A4RPV FAST, BG PV FAST or A2R131CN, Nubilai's NUBICOAT HTS or Nubiperf AR.

[0087] The amount of each color paste used can be determined according to the required application scenario, and no particular limitation is made here. For example, for 100 parts by weight of the low-temperature curing photosensitive resin composition of the present invention, 10-50 parts by weight, preferably 10-30 parts by weight, and more preferably 10-20 parts by weight of the above color paste can be used.

[0088] solvent The low-temperature curable photosensitive resin composition of the present invention contains solvents that do not affect its use, and are generally solvents commonly used in the industry. Examples of such solvents include, but are not limited to: alcohol solvents such as methanol, ethanol, propylene glycol, dipropylene glycol, glycerol, diethylene glycol, triethylene glycol, isohexanediol, C8-10 alcohol, C12-14 alcohol, C16-18 alcohol, isodecyl alcohol, and isotridecyl alcohol; phenol solvents such as phenol, mixed cresols, and xylenol; propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, and propylene glycol. Ether solvents such as butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, propylene glycol phenyl ether, ethylene glycol phenyl ether, ethylene glycol propyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, and triethylene glycol butyl ether; ketone solvents such as N-methylpyrrolidone acetone, methyl ethyl ketone, cyclohexanone, and isophorone; methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, and formic acid. Ester solvents such as isoamyl ester, benzyl formate, methyl acetate, ethyl acetate, ethyl acetoacetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, methyl amyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, propyl propionate, n-butyl propionate, amyl propionate, methyl butyrate, ethyl butyrate, n-butyl butyrate, methyl lactate, ethyl lactate, n-butyl lactate, amyl lactate, ethyl oxalate, dibutyl oxalate, dipentyl oxalate, diethyl carbonate, tributyl phosphate, ethyl benzoate, isopropyl benzoate, ethyl salicylate, propylene glycol methyl ether acetate, dimethyl carbonate, ethylene glycol ethyl ether acetate, and ethylene glycol butyl ether acetate; carboxylic acid solvents such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, and benzoic acid. The solvent content mentioned above can be adjusted according to the composition requirements and its solid content.

[0089] In a preferred embodiment, the solvent is propylene glycol methyl ether acetate.

[0090] It should be noted that in this invention, the candidate substances of different components may overlap. In the case of overlapping selected substances, the substances that play different roles are measured separately to meet their respective content requirements.

[0091] In preparing the composition of the present invention, the alkaline water-soluble photocurable resin, photopolymerizable monomer, and various additives of the present invention are first compounded and mixed evenly in a certain proportion, and then stored for later use (e.g., at -15 to 0°C) or used directly. For example, the resulting composition is used as an insulating layer for Micro-LEDs, which can be cured at low temperatures and, after low-temperature curing, exhibits good resistance to chemical etching and heat resistance on the substrate material.

[0092] In this invention, the term "low-temperature curing" should be understood as curing at a temperature greater than 80°C to 120°C, preferably 85°C to 110°C.

[0093] When using the composition of the present invention to manufacture a display, the composition is applied to a substrate (such as a silicon wafer, flexible polymer substrate, or ultrathin glass) by methods such as spraying, roller coating, wire rod coating, spin coating, slot coating, or slot spin coating. Then, pre-drying is performed at a temperature of approximately 50°C to 80°C. Subsequently, selective exposure is performed (using an exposure device such as a projection UV or stepper exposure machine), with an exposure intensity of, for example, 50-300 mJ / cm². 2 The wavelength range can be 300-450 nm. After development in a dilute alkaline aqueous solution (e.g., 0.035-0.055% KOH aqueous solution, or other developer types such as 2.38% tetramethylammonium hydroxide aqueous solution, or 1% NaHCO3 aqueous solution) for 40-120 seconds, it is further cured in an oven at a temperature greater than 80°C to 120°C (preferably 90°C to 110°C) for 30-60 min, preferably 40-50 min, followed by subsequent process steps.

[0094] On the other hand, the present invention also relates to displays prepared using the low-temperature curing photosensitive resin composition of the present invention.

[0095] The compositions of this invention can be used on flexible polymer substrates and ultrathin glass substrates without affecting the substrate during curing, thus meeting the requirements of novel display panels such as OLEDs and Micro-LEDs. In particular, the compositions of this invention can undergo intramolecular crosslinking, achieving rapid crosslinking at lower temperatures without the need for a curing agent, and the resulting cured product exhibits excellent performance. Furthermore, they maintain stable performance at room temperature, greatly ensuring the safety of photoresist transportation and storage.

[0096] The present invention will be described in more detail below with reference to the following embodiments. These embodiments disclosed below are for illustrative purposes only and are not intended to limit the invention. Those skilled in the art can make various modifications, additions, and substitutions to the embodiments of the invention without departing from the scope and spirit of the invention.

[0097] Example Example 1: Synthesis of Alkali-Soluble Photocurable Resin 16.9 g of toluene-2,4-diisocyanate and 25 g of ethyl acetate were added to a 250 mL three-necked flask, followed by 0.030 g of dibutyltin dilaurate. The temperature was raised to 55 °C, and 10.5 g of 2-dimethylaminomethylphenol was slowly added dropwise to the three-necked flask through a dropping funnel under constant temperature conditions. After the addition was completed, the temperature was raised to 70 °C and the reaction was carried out for 4 h. Continue adding 15g of ethyl acetate, 0.025g of dibutyltin dilaurate and 18.9g of 2-ethylacrylic acid to the three-necked flask, stirring slowly and heating to 75℃ for 4h. Then, slowly add 20.5g of 2,3-epoxypropyl acrylate and 12.0g of ethyl acetate dropwise to the three-necked flask through a dropping funnel, heat to 80℃ and react for 2h, then distill under reduced pressure to obtain a low-temperature curing resin product with a weight-average molecular weight (Mw) of 11200, an acid value of 105.2 mg KOH / g, and a solid content of 33.4% by weight.

[0098] Example 2 of the synthesis of alkaline water-soluble photocurable resin 18.6 g of isophorone diisocyanate and 25 g of ethyl acetate were added to a 250 mL three-necked flask, followed by 0.035 g of dibutyltin dilaurate. The temperature was raised to 55 °C, and 13.8 g of 2,2,6,6-tetramethyl-4-piperidinone was slowly added dropwise to the three-necked flask under constant temperature conditions through a dropping funnel. After the addition was completed, the temperature was raised to 70 °C and the reaction was carried out for 4 h. Continue adding 15g of ethyl acetate, 0.030g of dibutyltin dilaurate and 18.9g of 2-ethylacrylic acid to the three-necked flask, stirring slowly and heating to 75℃ for 4h. Then, slowly add 22.8g of 2,3-epoxypropyl acrylate and 12.0g of ethyl acetate dropwise to the three-necked flask through a dropping funnel, heat to 80℃ and react for 2h, then distill under reduced pressure to obtain a low-temperature curing resin product with a weight-average molecular weight (Mw) of 11800, an acid value of 114.5 mg KOH / g, and a solid content of 32.8% by weight.

[0099] Example 3: Synthesis of Alkali-Soluble Photocurable Resin 19.8 g of isophorone diisocyanate and 25 g of ethyl acetate were added to a 250 mL three-necked flask, followed by 0.048 g of dibutyltin dilaurate. The temperature was raised to 55 °C, and 15.0 g of 3-pentadecanylphenol was slowly added dropwise to the three-necked flask through a dropping funnel under constant temperature conditions. After the addition was completed, the temperature was raised to 70 °C and the reaction was carried out for 4 h. Continue adding 15g of ethyl acetate, 0.045g of dibutyltin dilaurate and 19.5g of 2-ethylacrylic acid to the three-necked flask, stirring slowly and heating to 75℃ for 4h. Then, slowly add 21.8g of 2,3-epoxypropyl acrylate and 12.0g of ethyl acetate dropwise to the three-necked flask through a dropping funnel, heat to 80℃ and react for 2h, then distill under reduced pressure to obtain a low-temperature curing resin product with a weight-average molecular weight (Mw) of 12300, an acid value of 109.2 mg KOH / g, and a solid content of 35.0% by weight.

[0100] Example 4: Synthesis of alkaline water-soluble photocurable resin 17.2 g of hexamethylene diisocyanate and 25 g of ethyl acetate were added to a 250 mL three-necked flask, followed by 0.042 g of dibutyltin dilaurate. The temperature was raised to 55 °C, and 17.6 g of butanone oxime was slowly added dropwise to the three-necked flask through a dropping funnel under constant temperature conditions. After the addition was completed, the temperature was raised to 70 °C and the reaction was carried out for 4 h. Continue adding 15g of ethyl acetate, 0.048g of dibutyltin dilaurate, and 18.5g of 2-ethylacrylic acid to the three-necked flask. Stir slowly and heat to 75℃ for 4 hours. Then, slowly add 20.7g of 2,3-epoxypropyl acrylate and 12.0g of ethyl acetate dropwise to the three-necked flask through a dropping funnel. Heat to 80℃ and react for 2 hours. After vacuum distillation, obtain the low-temperature curing resin product with a weight-average molecular weight (Mw) of 12500, an acid value of 111.2 mg KOH / g, and a solid content of 32.8% by weight.

[0101] Example 5: Synthesis of alkaline water-soluble photocurable resin 19.4 g of hexamethylene diisocyanate and 25 g of ethyl acetate were added to a 250 mL three-necked flask, followed by 0.050 g of dibutyltin dilaurate. The temperature was raised to 55 °C, and 18.8 g of 3-hydroxy-3-methyl-2-butanone oxime was slowly added dropwise to the three-necked flask through a dropping funnel under constant temperature conditions. After the addition was completed, the temperature was raised to 70 °C and the reaction was carried out for 4 h. Continue adding 15g of ethyl acetate, 0.050g of dibutyltin dilaurate and 18.5g of 2-ethylacrylic acid to the three-necked flask, stirring slowly and heating to 75℃ for 4h. Then, slowly add 20.2g of 2,3-epoxypropyl acrylate and 12.0g of ethyl acetate dropwise to the three-necked flask through a dropping funnel, heat to 80℃ and react for 2h, then distill under reduced pressure to obtain a low-temperature curing resin product with a weight-average molecular weight (Mw) of 11800, an acid value of 120.5 mg KOH / g, and a solid content of 35.4% by weight.

[0102] Example 6: Synthesis of Alkali-Soluble Photocurable Resin 18.4 g of isophorone diisocyanate and 25 g of ethyl acetate were added to a 250 mL three-necked flask, followed by 0.052 g of dibutyltin dilaurate. The temperature was raised to 55 °C, and 18.2 g of 4,4-dimethylcyclohexanone oxime was slowly added dropwise to the three-necked flask through a dropping funnel under constant temperature conditions. After the addition was completed, the temperature was raised to 70 °C and the reaction was carried out for 4 h. Continue adding 15g of ethyl acetate, 0.048g of dibutyltin dilaurate, and 18.5g of 2-ethylacrylic acid to the three-necked flask. Stir slowly and heat to 75℃ for 4 hours. Then, slowly add 20.6g of 2,3-epoxypropyl acrylate and 12.0g of ethyl acetate dropwise to the three-necked flask through a dropping funnel. Heat to 80℃ and react for 2 hours. After vacuum distillation, obtain the low-temperature curing resin product with a weight-average molecular weight (Mw) of 12400, an acid value of 110.2 mg KOH / g, and a solid content of 34.1% by weight.

[0103] Example 7: Synthesis of Alkali-Soluble Photocurable Resin 25g of ethyl acetate, 0.045g of dibutyltin dilaurate, and 20.5g of 2-ethylacrylic acid were added to a 250mL three-necked flask. The mixture was slowly stirred and heated to 75℃ for 4 hours. Then, 25.5g of 2,3-epoxypropyl acrylate and 15.0g of ethyl acetate were slowly added dropwise to the three-necked flask through a dropping funnel. The mixture was heated to 80℃ and reacted for 2 hours. After vacuum distillation, a resin product without blocked isocyanate groups was obtained. The weight-average molecular weight (Mw) was 10200, the acid value was 102.5 mg KOH / g, and the solid content was 30.4% by weight.

[0104] Example 1 The alkaline water-soluble photocurable resin of Synthesis Example 1 was added to a 30 mL brown bottle. Based on the total solid content of the final composition of 100% by weight, the amount added was 65% by weight (calculated based on the solid content of the obtained alkaline water-soluble photocurable resin). Then, dipentaerythritol hexaacrylate monomer (manufactured by Chang Hsing Chemical Industry Co., Ltd., Taiwan) was added, with an amount of 28% by weight of the total solid content. Then, IRGACURE 907 photoinitiator (manufactured by BASF, Germany) was added, with an amount of 5% by weight of the total solid content. Then, vinyltrimethoxysilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., Japan) was added, with an amount of 1% by weight of the total solid content. Then, BYK-333 (manufactured by BYK Chemicals GmbH, Germany) was added, with an amount of 1% by weight of the total solid content. Finally, propylene glycol methyl ether acetate solvent was added to adjust the solid content of the resin composition so that the total solid content of the final composition was 25% by weight.

[0105] Example 2 The low-temperature curable photosensitive resin composition was prepared in the same manner as in Example 1, except that the alkaline water-soluble photocurable resin of Synthesis Example 1 was replaced with the alkaline water-soluble photocurable resin of Synthesis Example 2.

[0106] Example 3 The low-temperature curable photosensitive resin composition was prepared in the same manner as in Example 1, except that the alkaline water-soluble photocurable resin of Synthesis Example 1 was replaced with the alkaline water-soluble photocurable resin of Synthesis Example 3.

[0107] Example 4 A low-temperature curable photosensitive resin composition was prepared in the same manner as in Example 1, except that the alkaline water-soluble photocurable resin of Synthesis Example 1 was replaced with the alkaline water-soluble photocurable resin of Synthesis Example 4.

[0108] Example 5 A low-temperature curable photosensitive resin composition was prepared in the same manner as in Example 1, except that the alkaline water-soluble photocurable resin of Synthesis Example 1 was replaced with the alkaline water-soluble photocurable resin of Synthesis Example 5.

[0109] Example 6 The low-temperature curable photosensitive resin composition was prepared in the same manner as in Example 1, except that the alkaline water-soluble photocurable resin of Synthesis Example 1 was replaced with the alkaline water-soluble photocurable resin of Synthesis Example 6.

[0110] Comparative Example 1 The low-temperature curable photosensitive resin composition was prepared in the same manner as in Example 1, except that the alkaline water-soluble photocurable resin of Synthesis Example 1 was replaced with the alkaline water-soluble photocurable resin of Synthesis Example 7.

[0111] Performance Evaluation The compositions obtained in Examples 1-6 and Comparative Example 1 were evaluated based on their developability, resistance to chemical etching, and heat resistance. The specific experimental procedures are as follows: First, the prepared resin composition was uniformly coated onto a silicon wafer by spin coating to obtain a 3 μm thick coating. Then, it was dried on a hot plate at 80°C for 150 seconds to remove the solvent. After placing the mask in the exposure machine, the distance between the coated film and the mask was set to 100 μm, and the exposure energy was selected to be 100 mJ / cm². 2 The exposure equipment was a projection-type ultraviolet exposure machine, and then a 0.043% KOH developer was used for spray development for 120 seconds. Finally, the film was baked in a 100℃ clean oven for 45 minutes to obtain a cured film.

[0112] 1. Development performance The developed photoresist was observed using an optical microscope to analyze the pattern resolution, morphology, and measure the line width. The ΔCD (photoresist line width - mask line width) was recorded, and the evaluation results are listed in the table below.

[0113] Analysis: Minimum resolution of the developed pattern Appearance: ○: No residue remains at the edges of the lines. Δ: The residual thickness at the edge of the line is less than 1 μm. ×: Line edge residue greater than 1 μm ΔCD: ○: 0≤ΔCD≤10, line CD dimension OK; ×: ΔCD > 10 CD, line CD size NG Figures 1 to 7 Microscopic magnifications of the low-temperature curable photosensitive resin compositions prepared in Examples 1-6 and Comparative Example 1 after development are shown.

[0114] Table 1

[0115] From Table 1 and Appendix Figure 1-7 It is evident that the composition prepared by this invention has excellent developing properties.

[0116] 2. Resistance to chemical etching The cured films, after being baked in a clean oven at 100℃ for 30 min, were immersed in 100% propylene glycol methyl ether acetate, 100% 3-methoxy-1-butanol, 100% 3-methoxybutyl acetate, 100% ethyl lactate, 100% propylene glycol methyl ether, 100% diethylene glycol dimethyl ether, 100% diethylene glycol methyl ethyl ether, 0.04% KOH, 2.38% TMAH, and 100% ethanol at 25℃ for 10 min respectively. After immersion, the films were removed and rinsed thoroughly in ultrapure water. The film thickness before and after immersion was measured using a step tester, and the adhesion was tested using the tape method (ASTM D 3359-2002, "Adhesion Determination by Tape Method"). Simultaneously, the transmittance before and after immersion was measured using a spectrophotometer. The evaluation results are listed in the table below.

[0117] Film thickness change rate ((film thickness after immersion - film thickness before immersion) / film thickness before immersion): ○: Film thickness change rate ≤ 0.5% Δ: 0.5 < film thickness change rate ≤ 1% ×: Film thickness change rate > 1% Transmittance change rate: ((Transmittance after soaking - Transmittance before soaking) / Transmittance before soaking): ○: Transmittance change rate ≤ 0.5% Δ: 0.5 < transmittance change rate ≤ 1% ×: Transmittance change rate > 1% Table 2

[0118] As shown in Table 2, the cured film formed by the composition prepared in this invention has excellent resistance to chemical etching.

[0119] 3. Heat resistance The cured film, after being baked in a clean oven at 100°C for 30 minutes, was further baked in a clean oven at 150°C for 2 hours. After being removed and cooled to room temperature, the film thickness before and after baking at 150°C was measured using a step tester, and the adhesion was tested using the tape method (ASTM D 3359-2002, "Adhesion Determination by Tape Method"). Simultaneously, the transmittance and colorimetric changes before and after baking at 150°C were measured using a spectrophotometer. The evaluation results are listed in the table below.

[0120] Film thickness change rate ((film thickness after baking - film thickness before baking) / film thickness before baking): ○: Film thickness change rate ≤ 0.5% Δ: 0.5 < film thickness change rate ≤ 1% ×: Film thickness change rate > 1% Transmittance change: ((Transmittance after baking - Transmittance before baking) / Transmittance before baking): ○: Transmittance change rate ≤ 0.5% Δ: 0.5 < transmittance change rate ≤ 1% ×: Transmittance change rate > 1% Color variation: ○: No color difference before and after baking, ΔEab≤1 Δ: Slight color difference before and after baking, 1 < ΔEab ≤ 2 ×: Significant color difference before and after baking, ΔEab > 2 Table 3

[0121] As shown in Table 3, the cured film formed by the composition prepared in this invention has excellent heat resistance.

Claims

1. A low-temperature curing photosensitive resin composition comprising the following components: (a) Alkali-soluble light-curing resin, 30 to 80% by weight. (b) Photopolymerizable monomers, 10 to 60% by weight; (c) Photoinitiator, 0.1 to 10% by weight; (d) Coupling agent, 0.1 to 6% by weight; (e) Other additives, The content of each component is based on the total solid content of the composition, 100% by weight. The alkaline water-soluble photocurable resin is prepared by comprising: (i) at least partially capped diisocyanate; (ii) olefinic unsaturated carboxylic acid; and (iii) unsaturated epoxide, wherein the alkaline water-soluble photocurable resin has a weight-average molecular weight of 10,000 to 50,000 and an acid value of 80 to 200 mg KOH / g.

2. The resin composition according to claim 1, wherein in preparing the alkaline water-soluble photocurable resin, the molar ratio of the diisocyanate (calculated as uncapped diisocyanate) to the olefinic unsaturated carboxylic acid is 1:(1.3-5), preferably 1:(1.5-4), more preferably 1:(1.6-3), and even more preferably 1:(1.8-2.3).

3. The resin composition according to claim 1 or 2, wherein in preparing the alkaline water-soluble photocurable resin, the molar ratio of the olefinic unsaturated carboxylic acid to the unsaturated epoxide used is 1:(0.5-1.2), preferably 1:(0.6-1.1), more preferably 1:(0.7-1.0), and even more preferably 1:(0.8-1.0).

4. The resin composition according to any one of claims 1 to 3, wherein in preparing the alkaline water-soluble photocurable resin, the molar amount of diisocyanate used is a moles, the molar amount of end-capping agent used is b moles, the molar amount of olefinic unsaturated carboxylic acid used is c moles, and the molar amount of unsaturated epoxide used is d moles, and they satisfy the following relationship: 0.50≤c / (2a+db)≤1.40, preferably 0.55≤c / (2a+db)≤1.30, more preferably 0.60≤c / (2a+db)≤1.25, more preferably 0.65≤c / (2a+db)≤1.20, and even more preferably 0.66≤c / (2a+db)≤1.

15.

5. The resin composition according to any one of claims 1 to 3, wherein the diisocyanate is selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hydrogenated phenylmethane diisocyanate, hexamethylene diisocyanate, and any combination thereof.

6. The resin composition according to any one of claims 1 to 3, wherein the end-capping agent used is selected from acetanilides, such as acetanilide or N-methylacetamide; caprolactams, such as caprolactam or N-acetylcaprolactam; pyridines, such as 2-hydroxypyridine, 3-hydroxyquinoline, piperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine or 4-(dimethylamino)-2,2,6,6-tetramethylpiperidine; oximes, such as butanone oxime, 3-hydroxy-3-methyl-2-butanone oxime, 4,4-dimethylcyclohexanone oxime, cyclohexanone oxime, acetone oxime or acetaldehyde oxime; phenols, such as 2-dimethylaminomethylphenol or 3-pentadecanylphenol; piperidinones, such as 2,2,6,6-tetramethyl-4-piperidinone; or any combination thereof.

7. The resin composition according to any one of claims 1 to 3, wherein the olefinic unsaturated carboxylic acid is a compound containing an unsaturated double bond and a carboxylic acid group, preferably selected from C2-C8 alkenyl carboxylic acids, such as (meth)acrylic acid, 2-pentenoic acid, 3-hexenoic acid, butenoic acid, 2-ethylacrylic acid, cyclopentenic acid (such as 1-cyclopentenic acid), cyclohexenic acid (such as 3-cyclohexene-1-carboxylic acid), maleic acid, and any combination thereof.

8. The resin composition according to any one of claims 1 to 3, wherein the unsaturated epoxide is an epoxy compound containing unsaturated double bonds, preferably selected from glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and any combination thereof.

9. The resin composition according to any one of claims 1 to 3, wherein the amount of the alkaline water-soluble photocurable resin is 35 to 76% by weight, preferably 45 to 74% by weight, more preferably 50 to 72% by weight, even more preferably 60 to 70% by weight or 62 to 68% by weight, based on the total solid content of the composition of 100% by weight.

10. A display that uses the resin composition according to any one of claims 1 to 9.

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