Alkali-free glass substrate with high color photoresist adhesive force as well as preparation method and application of alkali-free glass substrate
By hydroxylation of the surface of the glass substrate, the problem of poor adhesion of color photoresist is solved, significantly improves adhesion and reduces peeling, providing more reliable and efficient manufacturing of display devices. Solution.
Patent Information
- Application Number
- CN202411580417.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-07
- Publication Date
- 2025-02-18
AI Technical Summary
Existing colored photoresist has poor adhesion on glass substrates, resulting in peeling, affecting the quality and reliability of display devices.
By hydroxylation of the surface of the glass substrate, the adhesion of the colored photoresist is significantly improved. The method includes placing the glass substrate in an ethanol or acetone solution containing aminosiloxane, drying to remove residues, and forming a surface hydroxylated alkali-free glass substrate.
It significantly improves the adhesion of colored photoresist on the glass substrate, reduces the occurrence of light leakage caused by peeling, and provides a more reliable and efficient solution for the manufacturing of display devices.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of glass substrate production, and in particular to an alkali-free glass substrate with high color photoresist adhesion, a preparation method and application thereof. Background Art
[0002] In the manufacturing process of display devices, color filters are key components, and their performance directly affects the color performance and clarity of display devices. However, in the preparation process of existing color filters, the problem of poor adhesion of color photoresists on glass substrates is often encountered, resulting in color photoresist peeling, affecting product quality and reliability. Traditional optimization methods include adjusting the acid value of the polymer coated on the periphery of the color photoresist color dye crystal particles, the functional groups of the monomers, and the degree of branching of the resin, but these methods often affect other related characteristic values in the process, requiring re-evaluation and optimization of the composition and proportion of the color photoresist, and a long cycle of improvement and verification, which brings serious quality problems to customer production.
[0003] Therefore, it is urgent to develop a method for improving the adhesion of color photoresist on a glass substrate to solve the above problems. Summary of the invention
[0004] The technical problem to be solved by the present invention is: to overcome the shortcomings of the prior art, to provide an alkali-free glass substrate with high color photoresist adhesion, and a preparation method and application thereof, by using aminosiloxane to hydroxylate the surface of the glass substrate, thereby significantly improving the adhesion of the color photoresist and reducing the occurrence of light leakage caused by peeling, thereby providing a more reliable and efficient solution for the manufacture of display devices.
[0005] The technical solution of the present invention is:
[0006] In a first aspect, the present invention provides a method for preparing an alkali-free glass substrate with high color photoresist adhesion, comprising the following steps:
[0007] S1. placing a glass substrate on or coating the surface of the glass substrate with an ethanol or acetone solution containing aminosilicone, wherein the solution contains 2-3 wt.% acid, 2-3 wt.% aminosilicone and 6-9 wt.% water;
[0008] S2 dries the glass substrate to remove residual moisture and unreacted aminosiloxane on the surface, thereby obtaining an alkali-free glass substrate with a hydroxylated surface.
[0009] By using aminosiloxane on the surface of the glass substrate to perform hydroxylation on the glass surface, the molecule contains both hydrolyzable alkoxy groups and active amino groups. In a weakly acidic environment, the silicon-oxygen bonds on the glass surface are broken, and the amino groups in the aminosiloxane are nucleophilic and combine with the silicon in the broken silicon-oxygen bonds, thereby grafting the aminosiloxane onto the glass surface; the alkoxy groups of the aminosiloxane are easily hydrolyzed in water or a humid environment to generate silicon hydroxyl groups (-Si(OH)3), thereby hydroxylating the glass surface, and significantly improving the adhesion of the color photoresist with strong binding force to the glass substrate.
[0010] Here’s how it works:
[0011]
[0012] Wherein, R is an alkyl group, such as methyl, ethyl, propyl, etc.
[0013] Preferably, in step S1, before placing the glass substrate on or coating the surface with the solution, the glass substrate is first cleaned to remove oil stains and impurities on the surface.
[0014] Preferably, in step S1, the acid is fluorosilicic acid or hydrofluoric acid.
[0015] In a second aspect, the present invention provides an alkali-free glass substrate with high color photoresist adhesion, which is prepared by the above-mentioned method for preparing an alkali-free glass substrate with high color photoresist adhesion.
[0016] Preferably, the alkali-free glass substrate comprises the following components in mass percentage: SiO2 60-65%, Al2O3 16-19%, B2O3 8-11%, MgO 2-4%, CaO 2-4%, BaO 1-3%, SrO 1-3%, ZnO 1-3%, ZrO2 0.1-0.5%, SnO2 0.1-0.5%.
[0017] If the content of hydroxyl groups inside the glass is high, the density and refractive index of the glass substrate will decrease, which will affect the transmission and refraction characteristics of the glass substrate for light. For TFT display devices that require high-precision optical performance, it will cause deviations in the display effect, such as color accuracy, brightness uniformity, etc. will be affected. In addition, the increase in the content of hydroxyl groups inside the glass will reduce the viscosity of the glass, which will affect the molding process of the glass substrate, and may cause problems such as uneven thickness and decreased surface flatness of the glass substrate. It will also cause bubbles to be generated: during the production process, the hydrogen permeation characteristics of the platinum channel will cause the hydroxyl groups in the glass to react with hydrogen to generate hydrogen, causing bubble defects in the glass substrate. The present invention optimizes the formula of the alkali-free glass substrate, reduces the generation of hydroxyl groups inside the glass substrate, reduces the generation of hydroxyl groups inside the glass substrate, can ensure product quality, and provides a good foundation for subsequent surface hydroxylation treatment.
[0018] In the third aspect, the present invention provides an application of an alkali-free glass substrate with high color photoresist adhesion, wherein a color photoresist is coated on the surface of the above-mentioned alkali-free glass substrate with high color photoresist adhesion to form a color photoresist layer, which is pre-baked in sequence to remove the solvent and promote the initial cross-linking of the curing resin, then exposed and developed to obtain a patterned color film, hard-baked to completely cure the color film to form a color filter layer, and further processed on the color filter layer to form a black matrix to obtain a color filter.
[0019] Preferably, the pre-baking temperature is 90° C. and the pre-baking time is 216 seconds.
[0020] Preferably, the i-line exposure energy is 200 mJ / cm 2 .
[0021] Preferably, the developer is 2.38% TMAH, and the developing time is 30 seconds.
[0022] Preferably, the hard baking temperature is 120° C. and the time is 30 minutes.
[0023] Compared with the prior art, the present invention has the following beneficial effects:
[0024] 1. The present invention uses aminosiloxane to perform hydroxylation on the surface of a glass substrate. The surface of the glass substrate after hydroxylation has better wettability and compatibility, which is beneficial to the uniform coating and curing of the color photoresist, significantly improves the adhesion of the color photoresist, reduces the occurrence of light leakage caused by peeling, and provides a more reliable and efficient solution for the manufacture of display devices.
[0025] 2. The method of the present invention is simple, easy to operate, and suitable for large-scale industrial production. The color filter prepared by the present invention has excellent color performance, high contrast, and good stability, and can meet the strict requirements of high-end liquid crystal displays (such as high temperature and high humidity), thereby improving user experience. DETAILED DESCRIPTION
[0026] In order to enable persons skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.
[0027] The color photoresist used in the embodiments and comparative examples of the present invention is a color photoresist produced by Fujifilm Electronic Materials Co., Ltd., and the model number is: Color RGB 6000.
[0028] Example 1
[0029] The alkali-free glass substrate with high color photoresist adhesion of this embodiment includes the following components in mass percentage: SiO2 62.5%, Al2O3 17.5%, B2O3 9.5%, MgO 3%, CaO 3%, BaO 2%, SrO 1%, ZnO 2%, ZrO2 0.3%, and SnO2 0.2%.
[0030] The method for preparing the alkali-free glass substrate with high color photoresist adhesion of the present embodiment comprises the following steps:
[0031] S1 Glass substrate cleaning: The alkali-free glass substrate is cleaned with acetone, isopropyl alcohol and deionized water in sequence to remove oil and impurities on the surface, and then blown dry with nitrogen;
[0032] S2 Surface hydroxylation treatment: The glass substrate was placed in an ethanol solution containing aminosiloxane, which contained 3wt.% hydrofluoric acid, 3wt.% aminotrimethoxysilane and 9wt.% water, and kept at room temperature for 15 minutes;
[0033] S3 Drying: The glass substrate after the surface hydroxylation treatment is taken out, rinsed with pure water, and then blown away with nitrogen to remove the pure water and unreacted aminosiloxane remaining on the surface, and dried to obtain an alkali-free glass substrate with a hydroxylated surface.
[0034] Preparation of color filters:
[0035] The colored photoresist was applied on the surface of the dried glass substrate by spin coating (350 rpm / 10 sec in the first stage and 1200 rpm / 1 sec in the second stage) to form a uniform colored photoresist layer. The colored photoresist layer was pre-baked (90°C, 216 s) and then exposed (200 mJ / cm 2 The color filter layer is further processed to form a black matrix, and finally a color filter is obtained by performing development (2.38% TMAH, 30s) and hard baking (120°C, 30min).
[0036] Example 2
[0037] The alkali-free glass substrate with high color photoresist adhesion of this embodiment includes the following components in mass percentage: SiO2 60%, Al2O3 18%, B2O3 9%, MgO 3%, CaO 3%, BaO 2%, SrO 2%, ZnO 2%, ZrO2 0.3%, and SnO2 0.7%.
[0038] The method for preparing the alkali-free glass substrate with high color photoresist adhesion of the present embodiment comprises the following steps:
[0039] S1 Glass substrate cleaning: The alkali-free glass substrate is cleaned with acetone, isopropyl alcohol and deionized water in sequence to remove oil and impurities on the surface, and then blown dry with nitrogen;
[0040] S2 Surface hydroxylation treatment: The glass substrate was placed in an acetone solution containing aminosiloxane, which contained 2wt.% hydrofluoric acid, 2wt.% aminotriethoxysilane and 8wt.% water, and kept at room temperature for 15 minutes;
[0041] S3 Drying: The glass substrate after the surface hydroxylation treatment is taken out, rinsed with pure water, and then blown away with nitrogen to remove the pure water and unreacted aminosiloxane remaining on the surface, and dried to obtain an alkali-free glass substrate with a hydroxylated surface.
[0042] Preparation of color filters:
[0043] The colored photoresist was applied on the surface of the dried glass substrate by spin coating (350 rpm / 10 sec in the first stage and 1200 rpm / 1 sec in the second stage) to form a uniform colored photoresist layer. The colored photoresist layer was pre-baked (90°C, 216 s) and then exposed (200 mJ / cm 2 The color filter layer is further processed to form a black matrix, and finally a color filter is obtained by performing development (2.38% TMAH, 30s) and hard baking (120°C, 30min).
[0044] Example 3
[0045] The alkali-free glass substrate with high color photoresist adhesion of this embodiment includes the following components in mass percentage: SiO2 65%, Al2O3 16%, B2O3 8%, MgO 4%, CaO 3.5%, BaO 1%, SrO 3%, ZnO 1%, ZrO2 0.4%, and SnO2 0.1%.
[0046] The method for preparing the alkali-free glass substrate with high color photoresist adhesion of the present embodiment comprises the following steps:
[0047] S1 Glass substrate cleaning: The alkali-free glass substrate is cleaned with acetone, isopropyl alcohol and deionized water in sequence to remove oil and impurities on the surface, and then blown dry with nitrogen;
[0048] S2 Surface hydroxylation treatment: The glass substrate was placed in an acetone solution containing aminosiloxane, which contained 3wt.% fluorosilicic acid, 3wt.% aminotri-n-propoxysilane and 6wt.% water, and kept at room temperature for 15 minutes;
[0049] S3 Drying: The glass substrate after the surface hydroxylation treatment is taken out, rinsed with pure water, and then blown away with nitrogen to remove the pure water and unreacted aminosiloxane remaining on the surface, and dried to obtain an alkali-free glass substrate with a hydroxylated surface.
[0050] Preparation of color filters:
[0051] The colored photoresist was applied on the surface of the dried glass substrate by spin coating (350 rpm / 10 sec in the first stage and 1200 rpm / 1 sec in the second stage) to form a uniform colored photoresist layer. The colored photoresist layer was pre-baked (90°C, 216 s) and then exposed (200 mJ / cm 2 The color filter layer is further processed to form a black matrix, and finally a color filter is obtained by performing development (2.38% TMAH, 30s) and hard baking (120°C, 30min).
[0052] Comparative Example 1
[0053] The difference from Example 1 is that when preparing an alkali-free glass substrate with high color photoresist adhesion, steps S1-S3 are not performed; when preparing a color filter, the color photoresist is directly coated on the surface of the glass substrate by spin coating.
[0054] Comparative Example 2
[0055] The difference from Example 1 is that in step S2, KH550 is used instead of aminotrimethoxysilane.
[0056] Comparative Example 3
[0057] The difference from Example 1 is that in step S2, hydrofluoric acid is not added to the ethanol solution.
[0058] Comparative Example 4
[0059] The difference from Example 1 is that in step S2, sulfuric acid is used instead of hydrofluoric acid.
[0060] Comparative Example 5
[0061] The difference from Example 1 is that in step S2, the concentration of hydrofluoric acid in the ethanol solution is 5 wt.%.
[0062] Comparative Example 6
[0063] The difference from Example 1 is that in step S2, the concentration of aminotrimethoxysilane in the ethanol solution is 5 wt.%.
[0064] The color filters of Examples 1-3 and Comparative Examples 1-6 were tested for performance:
[0065] Adhesion test: refer to "ASTM D3359-2017 Standard Test Method for Evaluating Adhesion by Tape Test" for testing;
[0066] Reliability test: Refer to "JESD22-A102-C Accelerated Cooking Test" to conduct PCT test on color filters to check whether there are defects such as cracks, pinholes, bubbles, peeling, etc. in the film layer, and evaluate its reliability;
[0067] Color saturation test: refer to GB / T 31370.1-2015 Flat Panel Display (FPD) Color Filter Test Method Part 1: Color and Transmittance for testing.
[0068] The performance test results of the color filters of Examples 1-3 and Comparative Examples 1-6 are shown in Table 1:
[0069] Table 1 Performance test results of color filters of Examples 1-3 and Comparative Examples 1-6
[0070]
[0071]
[0072] It can be seen from the test results in Table 1 that, compared with Comparative Examples 1-4, the adhesion of the color photoresist on the glass substrate of the color filter of Examples 1-3 is significantly improved, and no peeling or falling off occurs; and the uniformity and color saturation of the color filter layer meet the design requirements. In Comparative Example 5, due to the addition of too much hydrofluoric acid, the glass is corroded, resulting in an uneven and fragile glass surface. It can be seen from Comparative Example 6 that even if more aminosiloxane is added, the quality of the color filter cannot be further improved, and the production cost will increase. This shows that the present invention effectively improves the adhesion of the color photoresist on the glass substrate, providing reliable technical support for the manufacture of display devices.
Claims
1. A method for preparing an alkali-free glass substrate with high color photoresist adhesion, characterized in that: The following steps are involved: S1. placing a glass substrate on or coating the surface of the glass substrate with an ethanol or acetone solution containing aminosilicone, wherein the solution contains 2-3 wt.% acid, 2-3 wt.% aminosilicone and 6-9 wt.% water; S2 dries the glass substrate to remove residual moisture and unreacted aminosiloxane on the surface, thereby obtaining an alkali-free glass substrate with a hydroxylated surface.
2. The method for preparing an alkali-free glass substrate with high color photoresist adhesion as claimed in claim 1, characterized in that: In step S1, before placing the glass substrate or coating the surface of the glass substrate with the solution, the glass substrate is first cleaned.
3. The method for preparing an alkali-free glass substrate with high color photoresist adhesion as claimed in claim 1, characterized in that: In step S1, the acid is fluorosilicic acid or hydrofluoric acid.
4. Alkali-free glass substrate with high color photoresist adhesion, characterized in that: The substrate is prepared by the method for preparing an alkali-free glass substrate with high color photoresist adhesion as described in any one of claims 1 to 3.
5. The alkali-free glass substrate with high color photoresist adhesion as claimed in claim 4, characterized in that: The alkali-free glass substrate comprises the following components in mass percentage: SiO2 60-65%, Al2O3 16-19%, B2O3 8-11%, MgO 2-4%, CaO 2-4%, BaO 1-3%, SrO 1-3%, ZnO 1-3%, ZrO2 0.1-0.5%, and SnO2 0.1-0.5%.
6. Application of alkali-free glass substrate with high color photoresist adhesion, characterized in that: Color photoresist is coated on the surface of the alkali-free glass substrate with high color photoresist adhesion as claimed in claim 4 or 5 to form a color photoresist layer, which is then pre-baked, exposed, developed and hard-baked in sequence to obtain a color filter.
7. The use of the alkali-free glass substrate with high color photoresist adhesion as claimed in claim 6, characterized in that: The pre-baking temperature was 90°C and the time was 216s.
8. The use of the alkali-free glass substrate with high color photoresist adhesion as claimed in claim 6, characterized in that: i-line exposure energy is 200mJ / cm 2 .
9. The use of the alkali-free glass substrate with high color photoresist adhesion as claimed in claim 6, characterized in that: The developer was 2.38% TMAH, and the developing time was 30 s.
10. The use of the alkali-free glass substrate with high color photoresist adhesion as claimed in claim 6, characterized in that: The hard baking temperature is 120°C and the time is 30 minutes.