High-precision photoresist composition for ag etching and method of using the same

Abstract

The application provides a high-precision photoresist composition for AG etching and a use method thereof, and belongs to the technical field of photoresists. The photoresist composition comprises a base glue solution and a silane additive, wherein the base glue solution comprises the following components in mass fractions: modified phenolic resin 65-85 parts, photosensitive active component 12-25 parts, organic solvent 120-200 parts, and conventional functional additive 0.8-6 parts. The modified resin and various silane additives synergize to greatly improve the adhesion of the glue film to the glass substrate, the AG acid and alkali etching resistance is strong, the pattern does not fall off and does not erode, and the etching precision and product quality are ensured.

Description

Technical Field

[0001] This invention relates to the field of photoresist technology, and in particular to a high-precision photoresist composition for AG etching and its application method. Background Technology

[0002] AG etching (anti-glare etching) is the core process for anti-glare treatment of the surface of products such as displays, touch panels, and optical glass. It requires the preparation of a uniform and delicate micro-concave-convex structure on the glass surface. High-precision patterning etching with a depth of less than 10μm is necessary to balance anti-glare effect, light transmittance, and appearance. Photoresist, as the pattern transfer carrier, is the key material that determines the precision of AG etching and product yield.

[0003] To improve the adhesion between photoresist and glass substrate, silane coupling agents are commonly used in the industry. However, existing photoresists for AG etching have several technical drawbacks: First, silanes themselves contain active functional groups, and conventional phenolic resins do not provide any sealing or protection. Silanes are prone to self-polymerization and hydrolysis, resulting in extremely poor storage stability and rapid performance degradation during storage, which cannot meet the requirements for long-term industrial storage and mass production. Second, the pre-incorporation of silanes into the photoresist can disrupt the leveling properties of the coating, easily causing water flow patterns and uneven film thickness during AG etching. This leads to irregular unevenness on the glass etching surface, significantly reducing the anti-glare effect and compromising high-precision patterns. Third, existing technologies are mostly limited to single silane or single resin modification routes, resulting in a narrow range of applications. They cannot effectively seal various silane active sites, making it difficult to balance silane compatibility, photoresist leveling, and etching resistance, and thus failing to meet the stringent process requirements of AG etching.

[0004] Therefore, how to obtain a high-precision photoresist composition for AG etching and its application method is a technical problem that needs to be solved. Summary of the Invention

[0005] The purpose of this invention is to provide a high-precision photoresist composition for AG etching and its application method, so as to solve the above-mentioned technical problems.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a high-precision photoresist composition for AG etching, comprising a base adhesive and a silane additive; The base adhesive comprises the following components in parts by weight: Modified phenolic resin 65-85 parts, photosensitizing active component 12-25 parts, organic solvent 120-200 parts, conventional functional additives 0.8-6 parts; The content of silane additives is 0.5~2.5% of the mass of the base adhesive.

[0007] Furthermore, the modified phenolic resin is a diol-grafted phenolic resin.

[0008] Furthermore, the preparation method of the diol-grafted phenolic resin is as follows: using oxalic acid as a catalyst, the phenolic hydroxyl groups of the phenolic resin are catalyzed to undergo a dehydration etherification grafting reaction with the terminal hydroxyl groups of the diol to obtain the resin.

[0009] Furthermore, the preparation method of the diol-grafted phenolic resin specifically includes the following steps: (1) Take 100 parts of phenolic resin, 5-15 parts of diol, and 0.3-1.0 parts of oxalic acid by weight and mix them together; (2) Heat the temperature to 80~95℃ to allow the diol and phenolic resin to undergo etherification reaction under oxalic acid catalysis for 2~4 h; (3) Turn on the vacuum and heat to 130~165℃ and maintain for 0.5~2 h, so that the residual oxalic acid is decomposed by heat or sublimated and discharged with the volatile matter; (4) Cool down and discharge to obtain diol-grafted phenolic resin; In step (3), the heating endpoint is 130~165℃, the vacuum degree is -0.085~-0.098 MPa, and the amount of oxalic acid is 0.3~1.0% of the mass of phenolic resin.

[0010] Furthermore, the diol comprises one or more of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and 1,5-pentanediol.

[0011] Furthermore, the photosensitive active component comprises a diazonoquinone photosensitizer.

[0012] Furthermore, the organic solvent comprises propylene glycol methyl ether acetate and / or ethylene glycol monobutyl ether.

[0013] Furthermore, the conventional functional additives include one or more of leveling agents, defoamers, and etching-resistant additives.

[0014] Furthermore, the silane auxiliaries comprise one or more of aminosilanes, epoxysilanes, and phenylsilanes; The aminosilane comprises one or more of aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane; The epoxy silane comprises one or more of (2,3-epoxypropoxy)propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane. The phenylsilane comprises one or more of phenyltrimethoxysilane, phenyltriethoxysilane, and diphenyldimethoxysilane.

[0015] The present invention also provides a method for using a high-precision photoresist composition for AG etching, comprising the following steps: 1) Take the base adhesive and add silane additives according to the mass ratio to obtain the mixed adhesive; 2) The AG etched glass is sequentially cleaned, dried, and activated; 3) Apply the mixed adhesive solution to the glass surface and heat to remove the solvent to form a dense adhesive film; 4) After exposure and development, the dense film undergoes acid and alkali etching to complete the AG anti-glare processing.

[0016] The beneficial effects of this invention are: 1. Silanes have a wide range of applications. It is compatible with aminosilanes, phenylsilanes, epoxysilanes and various silane complexes, breaking the limitations of using a single silane. It can be flexibly selected according to process requirements and adapted to different AG etching production scenarios.

[0017] 2. Adaptable to both technical routes, with strong process selectivity.

[0018] The innovative approach offers two phenolic resin modification routes: diol grafting and epoxy grafting. Both routes can achieve efficient sealing and stabilization of various silanes, allowing for flexible selection based on production processes and AG etching precision requirements.

[0019] 3. High-precision AG etching compatibility

[0020] Both modified resins can ensure that the photoresist can stably achieve fine pattern processing below 10μm, with high pattern fidelity and good etching uniformity, perfectly meeting the microstructure processing requirements of optical glass AG etching.

[0021] 4. Completely suppress water flow pattern defects

[0022] The dual optimization of resin compatibility with silanes through the use of flexible diol segments and epoxy polar groups, combined with the on-site addition process of silanes, precisely controls the surface tension and leveling properties of the adhesive, eliminating water flow marks and uneven film thickness in AG coating from the root, and improving product yield.

[0023] 5. Significantly improved storage stability

[0024] Silane and base adhesive are stored separately to avoid premature hydrolysis and failure; both modified resins can block the active sites of silane and inhibit silane self-polymerization and hydrolysis, which greatly extends the sealed storage period of the base adhesive and meets the long-term storage requirements of industrial applications.

[0025] 6. Excellent etching resistance and adhesion

[0026] The modified resin, combined with various silane additives, works synergistically to significantly improve the adhesion between the film and the glass substrate. It has strong resistance to AG acid and alkali etching, and the pattern does not peel off or erode, ensuring etching precision and product quality. Detailed Implementation

[0027] This invention provides a high-precision photoresist composition for AG etching, comprising a base adhesive and a silane additive; The base adhesive comprises the following components in parts by weight: Modified phenolic resin 65-85 parts, photosensitizing active component 12-25 parts, organic solvent 120-200 parts, conventional functional additives 0.8-6 parts; The content of silane additives is 0.5~2.5% of the mass of the base adhesive.

[0028] In this invention, the content of the modified phenolic resin is preferably 68-82 parts by weight, more preferably 70-80 parts, and even more preferably 72-78 parts.

[0029] In this invention, the content of the photosensitive active component is preferably 15 to 22 parts by mass, and more preferably 18 to 20 parts by mass.

[0030] In this invention, the content of the organic solvent is preferably 140-180 parts by mass, and more preferably 150-160 parts by mass.

[0031] In this invention, the content of the conventional functional additive is preferably 1 to 6 parts by weight, and more preferably 2 to 5 parts by weight.

[0032] In this invention, the content of the silane additive is 1.0 to 2.0% of the mass of the base adhesive, more preferably 1.2 to 1.8%, and even more preferably 1.4 to 1.6%.

[0033] In this invention, the modified phenolic resin is a diol-grafted phenolic resin.

[0034] In this invention, the preparation method of the diol-grafted phenolic resin is as follows: using oxalic acid as a catalyst, the phenolic hydroxyl groups of the linear cresol phenolic resin undergo a dehydration etherification grafting reaction with the terminal hydroxyl groups of the diol to obtain the resin.

[0035] In this invention, the preparation method of the diol-grafted phenolic resin specifically includes the following steps: (1) Take 100 parts of phenolic resin, 5-15 parts of diol, and 0.3-1.0 parts of oxalic acid by weight and mix them together; (2) Heat the temperature to 80~95℃ to allow the diol and phenolic resin to undergo etherification reaction under oxalic acid catalysis for 2~4 h; (3) Turn on the vacuum and heat to 130~165℃ and maintain for 0.5~2 h, so that the residual oxalic acid is decomposed by heat or sublimated and discharged with the volatile matter; (4) Cool down and discharge to obtain diol-grafted phenolic resin; In step (3), the heating endpoint is 130~165℃, the vacuum degree is -0.085~-0.098 MPa, and the amount of oxalic acid is 0.3~1.0% of the mass of phenolic resin.

[0036] In this invention, the phenolic resin is a linear cresol phenolic resin, which is a resin synthesized from one or more of cresol, m-cresol, and xylenol with formaldehyde or paraformaldehyde, and has the following structural formula: ; ; .

[0037] This invention utilizes aliphatic diol grafting to modify phenolic resin. Flexible alcohol ether segments and hydroxyl active sites are introduced by bonding dihydroxy functional groups to the phenolic resin molecular chain. Oxalic acid is used as a catalyst to catalyze the dehydration etherification grafting reaction between the phenolic hydroxyl groups of the linear cresol phenolic resin and the terminal hydroxyl groups of the diol. After the reaction, the system is heated to 130-165℃ and subjected to reduced pressure. The oxalic acid undergoes thermal decomposition, breaking down into small molecules of carbon monoxide, carbon dioxide, and water vapor, which are then completely removed under vacuum. The reaction formula is as follows: .

[0038] After various silanes are added on-site, the alcohol hydroxyl groups on the resin molecular chain can form hydrogen bonds with the active silanol hydroxyl groups of the silane, which can directionally block the active sites of the silane, shield the active groups of the silane, effectively inhibit the self-condensation and hydrolysis deactivation of the silane, and fundamentally solve the problem of poor stability of silanes. At the same time, the flexible alcohol ether segments greatly improve the polarity and dispersibility of the resin molecules, realize the rapid and uniform dispersion of various silanes, without agglomeration or segregation, further enhance the stability of the system, and also optimize the leveling properties of the adhesive solution, suppress the generation of water flow lines in AG coating from the resin matrix level, ensure the density of the adhesive film, and adapt to the AG acid etching environment.

[0039] This invention compares the interaction mechanisms of phenolic resins with silanes before and after diol grafting: Ungrafted diols: pure phenolic resin + silane Phenolic benzene ring —OH …… —silane —Si(OR)3 Phenolic hydroxyl groups are strong acids and directly catalyze the hydrolysis of alkoxy groups (Si(OR)3) in silanes; Silanes collide with each other, self-polymerize, cross-link, thicken the system, and become unstable.

[0040] After grafting diols: The highly reactive phenolic hydroxyl groups are replaced with mild fatty alcohol hydroxyl groups to avoid strong hydrogen bond stimulation with amino groups and prevent the rapid hydrolysis of silanes.

[0041] Simultaneously, the phenolic-diol -OH group blocks and stabilizes the silane, controlling the bonding to lock the active end. The terminal hydroxyl group of the diol dehydrates with the silane alkoxy group, forming a C–O–Si bond. This anchors the silane at specific sites, blocking some easily hydrolyzed alkoxy active sites and preventing silane self-polymerization. The long carbon chain of the diol acts as a spacer arm, keeping each aminosilane apart. Intermolecular silanes cannot touch each other, inhibiting self-condensation and pre-crosslinking, resulting in a more stable overall system.

[0042] The structure is illustrated below: Phenolic resin skeleton ↓ (Ether grafting) —O—(CH2)n—OH (diol flexible spacer arm + fatty alcohol hydroxyl group) ↓ Controlled bonding O

[0043] Si—NH2 (aminosilane, epoxysilane, phenylsilane)

[0044] /

[0045] The remaining alkoxy groups are fixed at sites and spatially separated.

[0046] In this invention, the diol comprises one or more of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and 1,5-pentanediol, preferably one or more of ethylene glycol, 1,2-propanediol, and 1,3-propanediol.

[0047] In this invention, the photosensitive active component is preferably a diazonoquinone photosensitizer. The use of a diazonoquinone photosensitizer provides high exposure sensitivity and excellent pattern resolution, enabling stable exposure transfer of fine micro-patterns in AG etching below 10 μm. The patterns have neat edges, no collapse, and no residual adhesive, ensuring the precision of the AG etching structure.

[0048] In this invention, the organic solvent comprises propylene glycol methyl ether acetate and / or ethylene glycol monobutyl ether, preferably propylene glycol methyl ether acetate. The use of propylene glycol methyl ether acetate and / or ethylene glycol monobutyl ether as organic solvents provides strong dissolving power, uniform evaporation rate, and suitability for AG etching and coating processes, facilitating uniform film formation of the adhesive and eliminating solvent residue.

[0049] In this invention, the conventional functional additives include one or more of leveling agents, defoamers, and etching-resistant additives. This further optimizes the adhesive coating performance and improves the etching resistance and surface uniformity of the adhesive film.

[0050] In this invention, the silane auxiliaries comprise one or more of aminosilanes, epoxysilanes, and phenylsilanes; The aminosilane is preferably one or more of aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane; The epoxy silane is preferably one or more of (2,3-epoxypropoxy)propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane. The phenylsilane is preferably one or more of phenyltrimethoxysilane, phenyltriethoxysilane, and diphenyldimethoxysilane.

[0051] The present invention also provides a method for using a high-precision photoresist composition for AG etching, comprising the following steps: 1) Take the base adhesive and add silane additives according to the mass ratio to obtain the mixed adhesive; 2) The AG etched glass is sequentially cleaned, dried, and activated; 3) Apply the mixed adhesive solution to the glass surface and heat to remove the solvent to form a dense adhesive film; 4) After exposure and development, the dense film undergoes acid and alkali etching to complete the AG anti-glare processing.

[0052] This invention achieves high-precision pattern transfer below 10μm through ultraviolet exposure of a mask, followed by development with a special developer to obtain a precise photolithographic pattern; the developed glass is then subjected to acid and alkali etching, and the photoresist film is peeled off after etching to obtain AG etched glass with a uniform surface and excellent anti-glare effect.

[0053] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0054] Example 1

[0055] 1. Preparation of diol-grafted phenolic resin: (1) Feeding In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and vacuum system, add the following in sequence: Linear cresol phenolic resin: 100 parts;

[0056] Ethylene glycol: 10 parts; Oxalic acid dihydrate: 0.6 parts; (2) Etherification reaction After the above raw materials are stirred and mixed evenly, nitrogen gas is introduced for protection, the temperature is slowly raised to 85 ℃, and the reaction is maintained at this temperature for 3 h. This allows the hydroxyl groups on the phenolic resin molecular chain to undergo an etherification reaction with ethylene glycol under the catalysis of oxalic acid, resulting in an etherified modified resin liquid.

[0057] (3) Deviation and catalyst removal

[0058] The vacuum system was activated, and the system pressure was controlled at -0.095 MPa. The temperature was increased to 150 °C at a rate of 2 °C / min and maintained for 1 h. The water, unreacted diol, and some oxalic acid produced during the reaction were extracted along with the volatiles.

[0059] Basic adhesive formulation (parts by weight): 75 parts diol-grafted phenolic resin, 18 parts diazonoquinone photosensitizer, 160 parts propylene glycol methyl ether acetate, 2 parts AG-specific leveling agent, Megafac EFS-331, and 1 part defoamer, BYK-067A. 2. On-site adhesive preparation: Add 1.2% aminosilane additive and stir at room temperature for 40 minutes to mix thoroughly; 3. Process and performance: 1) Take the base adhesive and add silane additives according to the mass ratio to obtain the mixed adhesive; 2) The AG etched glass is sequentially cleaned, dried, and activated; 3) Apply the mixed adhesive solution to the glass surface and heat to remove the solvent to form a dense adhesive film; 4) After exposure and development, the dense adhesive film undergoes acid and alkali etching to complete the AG anti-glare processing. This process can stably achieve 8μm high-precision patterns, the adhesive film is free of water flow lines, and the performance of the base adhesive solution does not degrade after 8 months of sealed storage.

[0060] Example 2

[0061] 1. The diol-grafted phenolic resin was pre-etherified according to the method in Example 1 to obtain the modified resin, which was then directly used in adhesive formulation. The grafting ratio was: Linear cresol phenolic resin: 100 parts;

[0062] Diethylene glycol: 10 parts; Oxalic acid: 0.6 parts; Basic adhesive formulation (parts by weight): 72 parts epoxy-grafted phenolic resin, 17 parts diazonaphthoquinone photosensitizer, 155 parts propylene glycol methyl ether acetate, 1.8 parts AG-specific leveling agent, Megafac EFS-331, and 0.9 parts defoamer, BYK-067A. 2. On-site adhesive preparation: Add 1.0% phenylsilane additive and stir at room temperature for 35 minutes until well mixed; 3. Process and performance: Following the process method of Example 1, a high-precision AG etching pattern of 7μm can be stably achieved. The film is free of water flow lines and shrinkage cavities, and has excellent etching resistance.

[0063] Example 3

[0064] 1. The diol-grafted phenolic resin was pre-etherified according to the method in Example 1 to obtain the modified resin, which was then directly used in adhesive formulation. The grafting ratio was: Linear cresol phenolic resin: 100 parts;

[0065] 1,2-Propanediol: 10 parts; Oxalic acid: 0.7 parts; Basic adhesive formulation (parts by weight): 70 parts diol-grafted phenolic resin, 16 parts diazonoquinone photosensitizer, 150 parts propylene glycol methyl ether acetate, 1.5 parts AG-specific leveling agent (D&C Megafac EFS-801), 0.8 parts defoamer (BYK-020), 0.5 parts BYK-067A; 2. On-site adhesive preparation: Add 1.5% epoxy silane additive and stir at room temperature for 45 minutes to mix thoroughly; 3. Process and performance: Following the process method of Example 1, a high-precision AG etching pattern of 6μm can be stably achieved, the film is uniform and defect-free, and the storage stability is excellent.

[0066] As can be seen from the above embodiments, the present invention provides a high-precision photoresist composition for AG etching and its application method. The present invention innovatively proposes two modification technology routes: diol-grafted phenolic resin and epoxy-grafted phenolic resin. Through the grafting of functional groups, various silane active sites are physically and chemically sealed, inhibiting silane self-polymerization and hydrolysis. Simultaneously, it is compatible with various silane additives such as aminosilane, phenylsilane, and epoxysilane, and combined with a silane on-site addition process, ensuring high-precision pattern processing for AG etching below 10μm while completely solving water flow defects and significantly improving the storage stability of the photoresist.

[0067] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A high-precision photoresist composition for AG etching, characterized in that, Includes base adhesive and silane additives; The base adhesive comprises the following components in parts by weight: Modified phenolic resin 65-85 parts, photosensitizing active component 12-25 parts, organic solvent 120-200 parts, conventional functional additives 0.8-6 parts; The content of silane additives is 0.5~2.5% of the mass of the base adhesive.

2. The high-precision photoresist composition for AG etching according to claim 1, characterized in that, The modified phenolic resin is a diol-grafted phenolic resin.

3. The high-precision photoresist composition for AG etching according to claim 2, characterized in that, The preparation method of the diol-grafted phenolic resin is as follows: using oxalic acid as a catalyst, the phenolic hydroxyl groups of the phenolic resin are catalyzed to undergo a dehydration etherification grafting reaction with the terminal hydroxyl groups of the diol to obtain the resin.

4. The high-precision photoresist composition for AG etching according to claim 3, characterized in that, The preparation method of the diol-grafted phenolic resin specifically includes the following steps: (1) Take 100 parts of phenolic resin, 5-15 parts of diol, and 0.3-1.0 parts of oxalic acid by weight and mix them together; (2) Heat the temperature to 80~95℃ to allow the diol and phenolic resin to undergo etherification reaction under oxalic acid catalysis for 2~4 h; (3) Turn on the vacuum and heat to 130~165℃ and maintain for 0.5~2 h, so that the residual oxalic acid is decomposed by heat or sublimated and discharged with the volatile matter; (4) Cool down and discharge to obtain diol-grafted phenolic resin; In step (3), the heating endpoint is 130~165℃, the vacuum degree is -0.085~-0.098 MPa, and the amount of oxalic acid is 0.3~1.0% of the mass of phenolic resin.

5. The high-precision photoresist composition for AG etching according to claim 3 or 4, characterized in that, The diol comprises one or more of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and 1,5-pentanediol.

6. The high-precision photoresist composition for AG etching according to claim 1 or 2, characterized in that, The photosensitive active component includes a diazonoquinone photosensitizer.

7. The high-precision photoresist composition for AG etching according to claim 6, characterized in that, The organic solvent comprises propylene glycol methyl ether acetate and / or ethylene glycol monobutyl ether.

8. The high-precision photoresist composition for AG etching according to claim 1, characterized in that, The conventional functional additives include one or more of leveling agents, defoamers, and etching-resistant additives.

9. The high-precision photoresist composition for AG etching according to claim 1, 2, 4, or 7, characterized in that, The silane auxiliaries include one or more of aminosilanes, epoxysilanes, and phenylsilanes; The aminosilane comprises one or more of aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane; The epoxy silane comprises one or more of (2,3-epoxypropoxy)propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane. The phenylsilane comprises one or more of phenyltrimethoxysilane, phenyltriethoxysilane, and diphenyldimethoxysilane.

10. The method of using the high-precision photoresist composition for AG etching according to claim 1, characterized in that, Includes the following steps: 1) Take the base adhesive and add silane additives according to the mass ratio to obtain the mixed adhesive; 2) The AG etched glass is sequentially cleaned, dried, and activated; 3) Apply the mixed adhesive solution to the glass surface and heat to remove the solvent to form a dense adhesive film; 4) After exposure and development, the dense film undergoes acid and alkali etching to complete the AG anti-glare processing.

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