OC photoresist and application thereof

Abstract

The invention provides an OC photoresist and application thereof. The OC photoresist comprises the following components in parts by mass: (A) 3-15 parts of nanoparticles; (B) 5-80 parts by mass of a curable monomer; (C) 0.1-5 parts of an initiator; (D) 0.1 to 0.5 part of a surfactant; (E) 1-100 parts by mass of a solvent, wherein the initiator has a structure as shown in a formula I in the specification. The OC photoresist has high transmissivity, high sensitivity and high heat-resistant stability, a photocuring pattern formed by using the OC photoresist has a good developing effect and high resolution, excellent sensitivity is shown, the cost for forming the photolithography pattern is reduced, and the OC photoresist has a wide application prospect.

Description

Technical Field

[0001] The invention belongs to the field of photoresist materials, and in particular relates to OC photoresist and application thereof. Background Art

[0002] In the application of photoresist, the problem encountered is that the yellowing property of the photoinitiator causes color difference in the composition. Especially in the application of color glue and OC glue, finding new active compounds with high sensitivity and low yellowing property has become the focus of technical research in this industry. Even a slight reduction in yellowing property is regarded as a significant technological advancement by users.

[0003] To this end, photoinitiators with different structures have been developed. For example, the photoinitiators disclosed in CN117510396A and CN116135888A have addressed these issues to some extent. However, the transmittance of the cured film after curing under long-wavelength conditions and the stability of the transmittance before and after curing require further consideration. Furthermore, photoresists must exhibit good thermal stability. Therefore, further development of initiators remains crucial to meet the performance requirements of photoresist applications. Summary of the Invention

[0004] In view of the deficiencies in the prior art, the object of the present invention is to provide an OC photoresist and its application. The OC photoresist of the present invention has high transmittance, high sensitivity and high heat stability.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In one aspect, the present invention provides an OC photoresist, comprising the following components in parts by weight:

[0007] (A) 3-15 parts by mass of nanoparticles; (B) 5-80 parts by mass of curable monomer; (C) 0.1-5 parts by mass of initiator; (D) 0.1-0.5 parts by mass of surfactant; (E) 1-100 parts by mass of solvent;

[0008] The initiator has a structure shown in the following formula I:

[0009]

[0010] Here, m is 1 or 2.

[0011] In the OC photoresist of the present invention, the content of the nanoparticles can be 3 parts by mass, 5 parts by mass, 8 parts by mass, 10 parts by mass, 13 parts by mass or 15 parts by mass, the content of the curable monomer can be 5 parts by mass, 8 parts by mass, 10 parts by mass, 15 parts by mass, 20 parts by mass, 30 parts by mass, 40 parts by mass, 50 parts by mass, 60 parts by mass, 70 parts by mass or 80 parts by mass; the content of the initiator can be 1 part by mass, 2 parts by mass, 3 parts by mass, 4 parts by mass or 5 parts by mass; the content of the surfactant can be 0.1 part by mass, 0.2 parts by mass, 0.3 parts by mass, 0.4 parts by mass or 0.5 parts by mass, and the content of the solvent is 1 part by mass, 3 parts by mass, 5 parts by mass, 10 parts by mass, 20 parts by mass, 30 parts by mass, 40 parts by mass, 50 parts by mass, 60 parts by mass, 70 parts by mass, 80 parts by mass, 90 parts by mass or 100 parts by mass.

[0012] Preferably, the nanoparticles are selected from one or a combination of at least two of ZrO2, TiO2, Al2O3, In2O3, ZnO or SnO2.

[0013] Preferably, the curable monomer is selected from (meth)acrylate compounds and / or alkenyl ether compounds.

[0014] Preferably, the (meth)acrylate compound is any one of (meth)acrylate alkyl esters, (meth)acrylate hydroxy esters, (meth)acrylates of alkylene glycols, (meth)acrylates of polyalkylene glycols, (meth)acrylates of trivalent or higher polyols or dicarboxylic acid modifications thereof, epoxy acrylates, polyurethane (meth)acrylates, polyester acrylates, (meth)acrylates of terminal hydroxylated polymers, urethane resins, silicone resins, (meth)acrylates of oligomeric resins (such as spirane resins, etc.), epoxy acrylates, and oxygen-containing acrylates, or a combination of at least two thereof.

[0015] Considering the effects of the compatibility, such as curing efficiency, developability, film hardness, substrate adhesion and the like, the (meth)acrylate compound is preferably one or a combination of two or more of alkyl (meth)acrylates, (meth)acrylates of alkylene glycols, (meth)acrylates of polyalkylene glycols, (meth)acrylates of trivalent or higher polyols, epoxy acrylates, and polyurethane (meth)acrylates.

[0016] Without limitation, the (meth)acrylate compound can be selected from one or a combination of two or more of the following compounds: methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, bisphenol A epoxy acrylate resin, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, etc.

[0017] Preferably, the alkenyl ether compound can be any one or a combination of at least two of vinyl ether, 1-propenyl ether, 1-butenyl ether, or 1-pentenyl ether compounds, preferably a vinyl ether compound. More preferably, the vinyl ether compound can be selected from one or a combination of two or more of triethylene glycol divinyl ether, 1,4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, glycerol carbonate vinyl ether, or dodecyl vinyl ether.

[0018] Preferably, the surfactant is selected from fluorine-based surfactants and / or silicone-based surfactants to improve coating characteristics and leveling properties, prevent or reduce the occurrence of stains during coating, and generate relatively few bubbles and film defects.

[0019] Preferably, the solvent is any one of alcohols, terpenes, ketones, aromatic hydrocarbons, glycol ethers or esters, or a combination of at least two of them.

[0020] Preferably, the alcohol solvent is selected from any one or a combination of at least two of methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone or diacetone alcohol.

[0021] Preferably, the terpene solvent is any one of α-terpene alcohol and β-terpene alcohol, or a combination of at least two of them.

[0022] Preferably, the ketone solvent is selected from any one of acetone, methyl ethyl ketone, cyclohexanone or N-methyl-2-pyrrolidone, or a combination of at least two thereof.

[0023] Preferably, the aromatic hydrocarbon solvent is selected from any one of toluene, xylene or tetramethylbenzene, or a combination of at least two thereof.

[0024] Preferably, the glycol ether solvent is selected from any one of methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether, or a combination of at least two thereof.

[0025] Preferably, the ester solvent is selected from any one of ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate or propylene glycol monoethyl ether acetate, or a combination of at least two thereof.

[0026] In the present invention, by using the above-mentioned solvents, the components of the OC photoresist can be dissolved and mixed to form a uniform solution-like composition.

[0027] In addition to the aforementioned components, the OC photoresist of the present invention may optionally contain organic and / or inorganic additives commonly used in the art, including but not limited to pigments, leveling agents, dispersants, or curing agents, depending on the product application requirements. This will be readily apparent to those skilled in the art. Furthermore, other sensitizers and / or photoinitiators may also be added to the composition for compounding, provided that they do not negatively impact the composition's performance.

[0028] According to the application requirements of the product, one or more macromolecules or polymer compounds can be selectively added to the composition to improve the application performance of the composition during use. Such macromolecules or polymer compounds can be polyols or polyester polyols; polymers that do not contain reactive functional groups can also be selectively added. These polymers are usually resins containing acidic functional groups such as phenolic hydroxyl groups and carboxyl groups.

[0029] On the other hand, the present invention further provides a photocurable pattern, wherein the photocurable pattern is formed by the above-mentioned OC photoresist.

[0030] In the present invention, the photocurable pattern can be used for a microlens array, an array planarization film pattern, a protective film pattern, an insulating film pattern, and the like.

[0031] In the present invention, the photocurable pattern is prepared by coating the OC photoresist on a substrate and then performing exposure and development.

[0032] Preferably, the photocurable pattern preparation method comprises the following steps:

[0033] (1) mixing and stirring the above-mentioned OC photoresist composition, and coating it on a substrate;

[0034] (2) After coating, the film is heated and dried to remove volatile components to form a film with a thickness of 2 to 10 μm;

[0035] (3) The substrate with the coating film is cooled to room temperature, a mask is attached, and the substrate is exposed to ultraviolet light, and then cleaned and developed with a developer to obtain the desired photocured pattern.

[0036] Preferably, the developer is an aqueous solution containing alkali or a mixed aqueous solution of alkali and surfactant.

[0037] The method for forming a photocured pattern using the photoresist provided in the present application adopts the above-mentioned photoresist with excellent transmittance, high sensitivity and heat resistance stability. The obtained photocured pattern has good development effect and high resolution, shows excellent sensitivity, reduces the cost of forming the photolithographic pattern, and has broad application prospects.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] The OC photoresist of the present invention has high transmittance, high sensitivity and high heat stability. The photocurable pattern formed using the OC photoresist has good development effect and high resolution, shows excellent sensitivity, reduces the cost of forming the photolithographic pattern, and has broad application prospects. DETAILED DESCRIPTION

[0040] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0041] Examples 1-10 and Comparative Examples 1-5

[0042] Preparation of OC photoresist

[0043] OC photoresist was prepared according to the formula shown in Table 1 below.

[0044] Table 1

[0045]

[0046] Nanoparticle A: ZrO2

[0047] Nanoparticle B: Al2O3

[0048] HDDA: 1,6-Hexanediol diacrylate (SR238)

[0049] TPGDA: Tripropylene glycol diacrylate (SR306)

[0050] TMPTA: Trimethylolpropane triacrylate (SR351)

[0051] Initiator A: Initiator B: Initiator C: Initiator D: Initiator E: Initiator F: BYK300: Leveling agent

[0052] Sensitivity test

[0053] The above composition was stirred in the dark and coated on a 21-step gradient ruler using a 6# wire rod to form a coating with a thickness of about 15 μm. The coating was exposed to an LED light (385 nm) at 191 mJ / cm 2 The film was developed with 2% NaOH aqueous solution for 2 minutes after curing, and then rinsed with tap water for 1 minute. Table 2 below shows the test results of the observation gradient ruler measured under a 365nm light source. The larger the value, the higher the sensitivity.

[0054] Table 2

[0055]

[0056] Application performance testing

[0057] Under the same conditions, the prepared OC photoresist was spin-coated on a silicon nitride substrate according to the weight parts described in Table 1, dried in a vacuum drying oven, and then baked. The photosensitive resin composition coated on the surface of the glass substrate was exposed to 365nm ultraviolet light using a mask with a 10μm line / space pattern. The photosensitive resin composition was then developed using a 0.5% sodium hydroxide aqueous solution and washed with deionized water to remove the residual developer. Finally, the developed silicon nitride substrate was baked at 100°C for 30 minutes to obtain a sample for evaluation.

[0058] 1. Transmittance

[0059] Except for not using a mask, the rest of the samples were prepared according to the method for forming the cured pattern. The transmittance of the cured film under different conditions in the visible light range of 400nm and 500nm was measured by an ultraviolet-visible spectrophotometer (UV-2600, Shimadzu), and the results are shown in Table 3.

[0060] 2. <Heat resistance test>

[0061] After the test piece was placed in a constant temperature and humidity chamber at 100°C for 360 hours, its transmittance at 500 nm was measured using the same method as above. The results are shown in Table 3 and evaluated based on the following criteria:

[0062] ○: No peeling, no adhesive layer leaching, no bubbles or damage;

[0063] ×: There is peeling, adhesive layer leaching, bubbles, and damage.

[0064] 3. <Humidity and heat resistance test>

[0065] In the heat and humidity resistance test, the test piece was placed in a constant temperature and humidity chamber at 100° C. and 85% humidity for 360 hours, and then its transmittance under 500 nm absorbed light was measured in the same manner as above.

[0066] The results are shown in Table 3. Durability was evaluated based on the following criteria:

[0067] ○: No peeling, no adhesive layer leaching, no bubbles or damage;

[0068] ×: There is peeling, adhesive layer leaching, bubbles, and damage.

[0069] Table 3

[0070]

[0071] In summary, the OC photoresist described in the present invention has the characteristics of high transmittance, and after application, it not only has the advantages of high heat resistance and stability, but also has no change in transmittance (i.e., transmittance) under high temperature and high humidity environments, and has good application performance.

[0072] The applicant states that while the present invention uses the aforementioned embodiments to illustrate the application of the OC photoresist, the present invention is not limited to these embodiments, nor does it necessarily rely on these embodiments for implementation. Persons skilled in the art should understand that any improvements to the present invention, equivalent substitutions for various raw materials in the present invention's products, additions of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. An OC photoresist, characterized in that: The OC photoresist comprises the following components in parts by mass: (A) 3-15 parts by mass of nanoparticles; (B) 5-80 parts by mass of curable monomer; (C) 0.1-5 parts by mass of initiator; (D) 0.1-0.5 parts by mass of surfactant; (E) 1-100 parts by mass of solvent; The initiator has a structure shown in the following formula I: Here, m is 1 or 2.

2. The OC photoresist according to claim 1, characterized in that The nanoparticles are selected from one or a combination of at least two of ZrO2, TiO2, Al2O3, In2O3, ZnO or SnO2.

3. The OC photoresist according to claim 1 or 2, characterized in that: The curable monomer is selected from (meth)acrylate compounds and / or alkenyl ether compounds.

4. The OC photoresist according to claim 3, characterized in that The (meth)acrylate compound is any one or a combination of at least two of alkyl (meth)acrylate, hydroxyl (meth)acrylate, (meth)acrylate of alkylene glycol, (meth)acrylate of polyalkylene glycol, (meth)acrylate of trivalent or higher polyol or its dicarboxylic acid modified product, epoxy acrylate, polyurethane (meth)acrylate, polyester acrylate, (meth)acrylate of terminal hydroxylated polymer, urethane resin, silicone resin, (meth)acrylate of oligomeric resin (such as spirane resin, etc.), epoxy acrylate, and oxygen-containing acrylate.

5. The OC photoresist according to claim 3, characterized in that The (meth)acrylate compound can be selected from one or a combination of two or more of the following compounds: methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, bisphenol A epoxy acrylate resin, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate.

6. The OC photoresist according to claim 3, characterized in that The alkenyl ether compound can be any one or a combination of at least two of vinyl ether, 1-propenyl ether, 1-butenyl ether, or 1-pentenyl ether compounds, preferably a vinyl ether compound. More preferably, the vinyl ether compound can be selected from one or a combination of two or more of triethylene glycol divinyl ether, 1,4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, glycerol carbonate vinyl ether, or dodecyl vinyl ether.

7. The OC photoresist according to any one of claims 1 to 6, characterized in that The surfactant is selected from fluorine-based surfactants and / or silicone-based surfactants.

8. The OC photoresist according to any one of claims 1 to 7, characterized in that The solvent is any one of alcohols, terpenes, ketones, aromatic hydrocarbons, glycol ethers or esters, or a combination of at least two of them.

9. The OC photoresist according to any one of claims 1 to 8, characterized in that The alcohol solvent is selected from any one or a combination of at least two of methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone or diacetone alcohol; Preferably, the terpene solvent is any one of α-terpene alcohol or β-terpene alcohol or a combination of at least two; Preferably, the ketone solvent is selected from any one or a combination of at least two of acetone, methyl ethyl ketone, cyclohexanone or N-methyl-2-pyrrolidone; Preferably, the aromatic hydrocarbon solvent is selected from any one or a combination of at least two of toluene, xylene or tetramethylbenzene; Preferably, the glycol ether solvent is selected from any one of methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether, or a combination of at least two thereof; Preferably, the ester solvent is selected from any one of ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate or propylene glycol monoethyl ether acetate, or a combination of at least two thereof.

10. A photocurable pattern, characterized in that: The photocured pattern is formed by the OC photoresist according to any one of claims 1 to 9.

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