TW300964B - The energy-accumulating method for manufacturing color filter - Google Patents

Abstract

An energy-accumulating method for manufacturing color filter includes following steps: coat a layer positive of photoresist with 3 different exposure amount on transparent conductive substrate; develop and remove on D1 area, then proceed electro-deposition on this area; totally illuminate the exposure amount with IEm to harden electro-deposition pixel and accumulate exposure amount of whole area; develop and remove on Dm+1 area as step (b) to expose conductive substrate then proceed electro-deposition on this area; repeat step (c) and (d) till the pixels of all color are arranged and hardened.

Description

A7 B7 Printed and Printed by the Beigong Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) Scope of the invention The present invention is a method for making a color filter. The materials used are positive photoresist and photohardening type Resin, this method only needs one accurate lithography process, the freedom of pattern arrangement is large, only a single developer is needed, the operation window (Process Window) is wide, and it can be enlarged in area. Background of the Invention With the development of information technology, the technology of displays has been continuously innovated and broken. Small-sized flat panel displays (F P D) have gradually replaced Futong cathode ray image tubes. The LCD has the advantages of light weight, thin thickness, low driving voltage and low current consumption, and it has rapidly attracted attention as a leader in flat panel displays. In recent years, due to the successful development of thin film transistors (Thin Film Transister, TFT), It also provides a commercial full-color display, and the future development of LCD is unlimited. Among them, color filter is the most important technology to control color. The structure of the color filter mainly includes three parts: a black matrix, a color filter layer, and an upper coat. There are currently five methods for making color filters commercially available: (I) Dyeing, (2) Etching, (3) Pigment dispersion, (4) Electro-authoring (Electro deposition), and (5) Printing method (Printing) ° Dyeing method and etching method is based on dye as the main technology, dye has a variety of

(Please read the notes on the back before filling in this page)

The size of this paper is based on the Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3. 10,000 The Ministry of Economic Affairs, Central Bureau of Samples and Printing Consumer Cooperatives A7 _B7_ V. Description of invention (2) Many types, uniform hue 1. The advantages of high dyeing power, good color density and penetration with resin are traditionally used as the main force of coloring materials for making color filters, as disclosed in US Patent Nos. 4820619 and 4837098. However, due to the poor light resistance of the dyes, the heat resistance has been gradually replaced by the pigment dispersion method and the electro-authoring method that use pigments as the main technology. Because the pigment has better heat resistance and the particle size is controlled below 0.2 μm Then, the particles can be uniformly dispersed in the resin and have excellent color rendering and light penetration. Therefore, the two technologies of pigment dispersion and electroporation have become the most popular technologies. The pigment dispersion method, as disclosed in US Patent Nos. 5,085973 and 4,786,148 and Japanese Patent Sho 6 0-1 2 9 7 3 9, uses a photosensitive photocurable resin and uses the lithography method to achieve high resolution. The purpose of flexible and flexible pattern arrangement can be used to make color filters for thin-film transistor LCDs, but the process is cumbersome, requires at least three masks, and must be repeated and accurately aligned. The main factor affecting yield is the production of color filters. Radiation reaction hardens resin during light film, it must be covered with a protective film to isolate oxygen is its shortcomings. The electro-authoring method. * As disclosed in US Patent 4 8 1 2 3 8 7, it is a polymer dispersed in water and Pigments and other materials are attached to the patterned indium tin oxide transparent electrode by electrophoresis, which can obtain the advantages of uniform film thickness, good flatness, and very fine thin circuits; however, due to the electronic method The design of the electrode plate is generally only used on the stripe (Stripe) patterned indium tin oxide transparent electrode, therefore, it is only suitable for making colored twisted light sheets for super twisted nematic (STN) LCD. As for the printing method, although it is the cheapest among all processes, it has poor dimensional accuracy, poor flatness, and poor reliability. It is suitable for the standard electronic standard paper standard (CNS > Μ 说 格 ( 210X297mm) 83.3.10,000 (please read the precautions on the back before filling in this page) Stranding 4- 0do4 A7 B7 Fifth Ministry of Economic Affairs Central Sample Bureau Employee Consumer Cooperative Printed Invention Instructions (3) Acceptance of Products In view of the advantages and disadvantages of the pigment dispersion method and the electro-authoring method, Nippon Oil first proposed the electro-lithographic method (ED-litho), such as the US patent 5 2 1 4 5 4 1, 5 2 1 4 5 4 It is revealed by this technique that this technique combines electrography and lithography, using a photomask with three or more different light transmittance areas, only one exposure can get different exposure areas, and then use different development The photoresist is stripped off by the liquid, and the red, green, and blue pixels are sequentially printed on the transparent conductive substrate during the process. The advantages of this method can be summarized as follows: (1) Combined with the photoresist method, it can get more electricity. Move to higher-definition patterns; (2 ) The degree of freedom of pattern arrangement is large, and both stripes and non-stripes can be produced; (3) Using the characteristics of electrography, a uniform film thickness and good flatness can be obtained. However, more than three different concentrations must be used to remove the photoresist The tolerance of the operating conditions of the developer is relatively narrow. In addition, the actual use of photoresist and electro-hydraulic liquid is more limited, especially positive photoresist can only be used with cationic electro-resin resin and anion cannot be used. Type electro-resin, if anionic electro-resin is used, the alkaline developer will peel off the electro-resin containing but not hardened acid-containing electro-resin, and the electro-resin cannot be hardened by light or It is hardened by thermal hardening; therefore, the combination of photolithography and photoresist must be positive photoresist with cationic electroresin, or negative photoresist with anionic electroresin. " The characteristics of anionic electro-resin, regardless of the stability of the resin (not yellowing), the ease of emulsification, the dispersion of pigments (especially the dispersion of high pigment concentration), and the cost of materials are far from the sun Sub-type electro-resin resin is better, so electro-photolithography is not a good choice for positive photoresist with cationic electro-resin resin, and even more (please read the precautions on the back before filling this page). The standard is applicable to Zhongjiaojia Biaoping (CNS) A4 specification (210X297 mm) 81 3 · 1 ^ 〇〇〇 ^ ~ B7 V. Description of invention (4) Printed by the Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs The negative photoresist with poor resolution affects the yield of the product. The purpose of the present invention is to improve the shortcomings of the electrophotographic lithography method, abandon the negative photoresist with poor dimensional accuracy and adopt a positive photoresist, and use positive Type photoresist has the characteristics of energy accumulation, and the process method of the present invention was developed. First, the photoresist has three or more regions with different exposures, one of which has reached the exposure that can be developed, and the other regions have not reached The amount of exposure that can be developed, the developer removes the area that can be developed, and the pixels are electrically loaded. After the pixels are configured, a full exposure without precise alignment is required to harden the pixels, so that the configured pixels are not As for receiving The developer in this step attacks and accumulates the exposure of each area that has not been developed, so that the second area has reached the exposure that can be developed. Afterwards, it is developed and arranged in sequence with pixels of various colors. In the exposure step after the pixel configuration, the present invention breaks through the limitations of the previous electrophotographic lithography method, so that both negative and cationic electrophotographic resins can be used in the photolithography process of positive photoresist. The manufacturing method of the color filter of the present invention not only has all the advantages of electrolithography, but also has the advantage that the electroporation resin can be hardened in the middle of the process, and it is accompanied by multiple comprehensive exposure steps in the process. Hardening is more complete. In addition, the use of a single developer, a wider operating tolerance, and general commercial positive photoresists can be used, which greatly improves the yield. The detailed description of the present invention is as follows, with the embodiments of the present invention in conjunction with the drawings To explain the details of the present invention. (Please read the precautions on the back before filling in this page),-= 9

Line chart paper scale standard Chinese national standard (CNS) A4 is now available (210X297mm) 83.3. 10,000 -6- A 7 B7 Printed by the Ministry of Economic Affairs, Central Bureau of Prejudication and Consumer Cooperatives V. Invention description (5) 1A (a) to 1A (f) are schematic cross-sectional views of the manufacturing process of the method for manufacturing a color filter that does not include a black shading matrix in the present invention. Figures IB (a) to IB (f) are schematic cross-sectional views of the manufacturing process of the method for manufacturing a color filter that does not include a black shading matrix in the present invention. 2 (a) ~ 2 (f) is a schematic cross-sectional view of the manufacturing process of the method for manufacturing a color lenticular sheet made of a black shading matrix in the present invention. Drawing number description 1. Glass plate 2. Conductive substrate 3. Shading matrix 4. Exposure D 1 area 5. Exposure D2 area 5 'Exposure D 2 + IE 1 area 6 Exposure D 3 area 6' Exposure D3 + IE1 area 6 "Exposure D3 + IE1 + IE2 area 7. First pixel 8. Second pixel 9. Third pixel 1 0. Protective film 1 1. Glass plate 1 2. Conductive substrate (Please read the notes on the back before filling this page)

Stranding. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3. 10,000 -7- Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Invention Instructions (6) 1 3. Shading matrix 1 4. Exposure D1 area 1 5. Exposure D2 area 15 '. Exposure D2 + IE1 area 16 6. Exposure D 3 area 16'. Exposure D3 + IE1 area 16 ". Exposure Volume D3 + IE1 + IE2 area 1 7. First pixel 1 8. Second pixel 1 9. Third pixel 20. Protective film 2 1. Glass plate 22. Exposure D1 area 23. Exposure D4 area 23 'Exposure D4 + IE1 area 23' '. Exposure D4 + IE1 + IE2 area 23' ''. Exposure. Amount D4 + IE1 + IE2 + IE3 area 24. Exposure D2 area 24 '. Exposure D2 + IE1 Area 2 5. Exposure D 3 area 25 '. Exposure D3 + IE1 area 25 ". Exposure D3 + IE1 + IE2 area 2 6. Conductive substrate 2 7. First pixel 2 8. Second pixel ( Please read the "Notes on the back and then fill out this page" IV. Set the standard for the Dongshushu, China National Standard (CNS) 8 4 grid (210X297 mm) 83. 3.10,000 8- 3ϋ0ί) 〇4 Α7 Β7 Ministry of Economy Printed by the Central Standard Falcon Bureau Beigong Consumer Investment Cooperative V. Description of the invention (7) 29. Third pixel 30. Shading matrix 3 1. Protective film The present invention is a method for making color filters by energy accumulation method, mainly provided A method for making color filters. The materials used are positive photoresist and photohardening electro-resin. It only needs one accurate lithography process, the pattern layout has a large degree of freedom, and only a single developer is used. The tolerance (process window) is very wide, and a large area of color filters can be made. 1A and 1B are manufacturing methods of a color filter that does not include a black shading matrix in the present invention, and includes the following steps: 1. A black shading matrix (3, 3) is pre-made on a transparent conductive substrate (2, 12) 13), wherein the material of the black shading matrix (3, 13) may be an alloy of chromium, nickel and other metals or their oxides, and mixtures thereof, or an organic polymer coating film with black coloring materials such as acrylic resin ' Charged materials such as epoxy resin (3), or non-charged materials (13), as shown in Figure 1A (a) and Figure IB (a) "2. In a black shading matrix (3, 13) A layer of positive photoresist is coated on the transparent conductive substrate (2, 12), and the photoresist is covered with a photomask for exposure, so that the photoresist is formed into areas with three different exposure levels, and their exposure amounts are ·· D1 (4, 14), D2 (5, 15), D 3 (6-16), and D1 (4, 14) > D 2 (5 15) > D 3 (6, 16), where D1 (4, 14) Represents the amount of exposure that allows the photoresist to be fully developed. See Figure 1A (b) and Figure 1B (b). This paper scale is applicable to China National Standard Falcon (CNS) A4 specification (210X297mm)

-Subscribe · Line 83. 3.10,000 9- Ministry of Economic Affairs Central Sample Bureau Beigong Consumer Cooperative Seal A7 B7 5. Description of the invention (8) 3. After development, it can be completely dissolved by the developer and the exposure is D1 (4 · 14) In the area where the conductive substrate is exposed, perform the electrowriting of the photocurable electrocure resin containing colorants, which is the configuration of the first pixel (7, 17), as shown in Figure 1A (c) and IB (c). 4. Total exposure energy IE1 exposure, IE1 is the energy difference between D1 and D2 (ie, 1E1 = (D1-D2)), harden the first pixel (7, 17), and increase the exposure of all areas , And the exposure in the original D2 area (5, 1 5) has accumulated to the amount that can be fully developed by the developer (D2 + IEl = Dl) (5, 15, 15), while the original D3 area (6, 16) The cumulative amount of exposure does not reach the level that can be developed, as shown in Figure 1A (c) and Figure IB (c). 5. Use the same developer in step 3 to accumulate the exposure to the original D 2 area (5 ', 1 5') that can be completely developed by the developer and completely dissolved. In the area where the conductive substrate is barely exposed, the second color of the electronic image is the purpose of the electronic image, that is, the configuration of the second pixel (8, 18), as shown in Figure 1 A (c) and Figure 1 B (c) Show. 6. Full exposure. The exposure of the energy IE2 hardens the second pixel and accumulates the exposure of the original D3 area (6, 16) to an amount that can be fully developed by the developer (D3 + IE1 + IE2 = D1) (6 '', 16 ''), as shown in Figure 1A (d) and Figure IB (d). 7. Use the same developer in step 3 to accumulate the exposure to the original D3 area (6 '', 16 '') that can be completely developed by the developer solution and completely dissolve it. The configuration of the three colors of electro-resin, namely the third pixel (9, 1 9), is shown in Figure 1 A (e) and Figure IB (e). (Please read the precautions on the back before filling in this page) Ordering Line Vermicelli Standard (CNS > A4 Said (210X297mm) 83. 3.10,000

Printed bag A7 _B2____ of the employee consumer cooperative of the Central Falcon Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) 8. Fully re-irradiate to harden each pixel (7, 17, 8, 18, 9, 19) completely, that is, complete the pixel configuration , As shown in Figure 1Α (e) and Figure 1B (e). 9. Finally, apply a protective layer (1G, 20) to protect the color filter, as shown in Figure 1A (f) and Figure IB (f). 2 is a method for manufacturing a color filter made of a black shading matrix according to the present invention, including the following steps: 1. Coating a transparent conductive substrate (26) with a layer of positive photoresist and covering the photoresist with a photomask Exposure to make the photoresist form an area with four different exposure levels, the exposure amounts are: Dl (22), D2 (24), D 3 (25), D4 (23), and Dl (22) > D 2 (2 4) > D 3 (2 5) > D 4 (23), where Dl (22) represents the exposure level that allows the photoresist to be fully developed, as shown in Figure 2 (a). 2. The development removes the area that can be completely dissolved by the developer and the exposure is D1 (22), and exposes the conductive substrate, and then in this area, the light-hardening and electro-resin containing resin is used. The configuration of a pixel (27) is shown in Figure 2 (b). 3. The exposure amount of the total irradiation energy IE1, IE1 is the energy difference between D1 and D2 (ie, IE1 = (D1-D2)), One pixel (27) hardens and increases the exposure of all areas, while the exposure of the original D2 area (24) has accumulated to an amount that can be fully developed by the developer (D 2 + IE 1 = D 1) (24, ), And the cumulative exposures (2 5 ') and (2 3') in the original D3 and D4 areas are not as high as can be developed, as shown in Figure 2 (b). This paper? Good standard general Chinese standard (CNS & A4 specifications (210X297 mm) 83. 3. 10,000 -11-(please read the notes on the back first and then fill in two pages). A7 B7 printed by the Bureau ’s Consumer Cooperative. V. Description of the invention (10) 4. Use the same developer in step 3 to accumulate the exposure to the original D2 area (24 ') that can be completely developed by the developer. Out of the area of the conductive substrate, the electrochromic resin of the second color, that is, the configuration of the second pixel (28), is shown in Figure 2 (c). 5. Fully irradiate the exposure amount of the energy IE2, the second The pixels are hardened, and the exposure of the original D3 area (25) is accumulated to an amount that can be fully developed by the developer (D3 + IEl + IE2 = Dl) (25 ''), while the cumulative exposure of the original D4 area (23 ”), It has not reached the level that can be developed, as shown in Figure 2 (c). 6. Use the same developer in step 3 to accumulate the exposure energy has reached the original D3 area that can be completely developed by the developer (25 '') Completely developed and dissolved, in the area where the conductive substrate is exposed, the third color is written The configuration of the electro-resin, that is, the third pixel (29), as shown in Figure 2 (d). 7. Full exposure energy [E3 exposure, hardening the third pixel, and the original D4 area (23 ) The exposure is accumulated to the amount that can be fully developed by the developer (D4 + IEl + IE2 + IE3 = Dl) (23 '' '), as shown in Figure 2 (d). 8. Various colors of electro-resin are completed After disposing and developing and exposing the conductive substrate of the fourth area to expose, coat or electrocoat a layer of black resin on it, and irradiate ultraviolet light from below the conductive substrate, using the pixels of the completed electro-composition (27, 28, 29 ) As a shading barrier, the black resin in the hole can be hardened to complete the production of the black shading matrix (30). The black shading matrix can be made of the following three kinds of materials and production methods: (1) Use black coloring The heat-hardenable positive type photoresist, the least exposed part can be left as a black shading moment at the end. The paper standard is applicable to the Chinese National Standard (CNS) A4 wash grid (210X297mm) 83. 3. 10,000 one please Read the precautions on the back first and fill in this book. Ir line 12- A7 Central Ministry of Economic Affairs Printed by the quasi-bureau employee consumption cooperative _B7_ V. Description of the invention (11) 1 array, (2) using the same resin formula with the same pixel as the black electric tree, the black shading matrix is arranged like a pixel Placed on a conductive substrate, (3) Use a photo-hardening type photosensitive black electro-resin, and finally irradiate all pixels (27, 28, 29) and black shading matrix (30) completely, such as As shown in Figure 2 (e). 9. Finally, coat a protective layer (31) to protect the color filter, as shown in Figure 2 (f). The above-mentioned conductive substrate can be selected from oxides containing tin, indium, or antimony, such as indium tin oxide (I Τ Ο), or commercially available conductive Glass I is therefore not restricted here. The photoresist described in the present invention is a positive resist (PR). Using its energy accumulation, it can cause the exposed areas of different exposure levels to develop successively. The positive resist will cause solubility after exposure. It can be developed by alkaline solution or solvent, and the positive photoresist has high reliability and fine dimensional accuracy for the pattern. At the same time, in conjunction with the method of the present invention, the positive photoresist with high contrast (highcontrast) can be selected. The unexposed or underexposed areas are minimized in film thickness loss during development. The general positive photoresist is composed of Novolac resin and quinonediazide compound. The present invention utilizes the following three types of photoresist: (i) general positive photoresist; (2) positive electrical A positive photoposition (positive electrodeposition photoresist); (3) A thermosetting positive photoresist or positive electroresistance (colored; pigment dispered PR) containing a coloring material. (Please read the precautions on the back first and then fill in this book 1) -The paper size of the binding book is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 83.3.10,000 -13- V. Description of the invention (12) A7 B7 light The method of resist coating can be adapted to the type of photoresist. In addition to electroposition, photoresist must use electroposition (electrodeposition), the rest can be sprayed (dip coating), screen printing (screen printing), roller coating (Roll coating), spin coating (spincoating), etc., as for the coating film thickness is generally 1 ~ 1 〇μ m, the best is 2 ~ 5μιη. The photoresist process requires a complete exposure energy of 80 ~ 1500 2, this The multiple exposure method invented can be exposed to different degrees at a time by a photomask with a multi-transparency printed by the Consumer Cooperative of the Central Ministry of Economic Affairs of the Ministry of Economic Affairs, or using a light with partial area transmission After the mask has been finely shifted, the photoresist has been exposed to different exposures successively | the area where the photoresist has different exposure levels can also be replaced by multiple (three or four) photomasks to achieve different exposure levels of the photoresist Region, The area graphics can be st ripe or non-striped (such as mosaic, red, green, and blue triangle arrangement). The arrangement pattern, three areas with different exposure levels must be developed in sequence; this At the time, first apply the first color-containing photo-curable electro-resin resin (ie the first pixel) to the first exposed conductive substrate (that is, the area with the highest exposure, D 1), and then fully irradiate ( Overall exposure) Exposure amount IE 1 causes the first pixel to produce a hardening reaction, while increasing the exposure amount of each area, and the D2 energy is accumulated to an exposure amount that can be completely developed by the same developer for a second development, and the conductive substrate is exposed The second area, and the second photo-curable electro-resin (ie, the second pixel) is electro-discharged in the exposed second area; once again full exposure exposure IE2 hardens the second pixel, and the original The energy of the area of D3 is accumulated to an exposure amount that can be completely developed, and the third development is performed to expose the third area of the conductive substrate and expose the third photo-curable electro-resin (ie, the third pixel) to the bare area. Out The third area, the last is more comprehensive (please read the precautions on the back and then fill in the cornel). The paper size of the cup line is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3. 10,000 -14 A7 _B7___ _5. Description of the invention (13) Irradiation hardens each pixel completely to complete the configuration of the pixels. The above-mentioned areas that make the photoresist have different exposure levels, in which three areas with different exposure levels are made, three light transmissions can be used The photomask of the area of different degrees, the range of different light transmittance is 100 ~ 40%, 85 ~ 20%, 40% 0% printed by the Industrial and Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy; made four areas of different exposure levels, can be used Photomask with four areas of different light transmittance | The range of different light transmittances is 100 ~ 40%, 85% ~ 20%, 70% ~ 50%, 50% ~ 0%, preferably 10% 〇 ~ 80%, 80% ~ 50%, 50% ~ 30%, 30% ~ 0%. The positive photoresist developer is an alkaline solution such as sodium carbonate, sodium bicarbonate, sodium silicate, sodium hydroxide, potassium hydroxide, and an aqueous solution of a tetraalkylamine compound or mixture thereof. The concentration of the developer is 0.2 ~ 4wt%, the developing condition is generally 10 ~ 70 ° C, the best is 15 ~ 40 ° C, and the developing time is 5 ~ 600 sec. The red, green, and blue three-pixel electro-resin used in the present invention is a composition of a photo-curable electro-resin and a coloring substance. The electro-resin can be divided into anionic electro-resin and cationic electro-resin. Anionic electro-resin consists of anionic resin, photoreactive monomer (usually unsaturated double bond monomer), photoinitiator (0.1 ~ 30 mole percentage), solvent and water. Among them, anionic resin Acrylic resins containing acid groups (carboxylic acid groups, sulfonic acid groups) and ammonia, ammonia, trimethylamine, diethylamine, dimethyl ethanol amine 、 Diethyl ethanol amine (diethyl ethanol amine) dreaming agent is composed of resin, anion-type electro-resin resin completely hardened energy is 20 ~ 500mj / Cm2, the best is 50 ~ 350mj / cm2; cationic resin It is composed of amine groups (level 3 (please read the precautions on the back before filling in this page)-order the color book. * People's legal standard is suitable for China National Standard Rate (CNS) grid (210X297mm) 83. 3. 10,000 -15- 0 ^ A7 B7 Central Bureau of Economics and Politics, Ministry of Economic Affairs Beigong Consumer Investment Ling Zuoshe Printing and Burning V. Description of the invention (14) Amine or quaternary amine) Acrylic resin and formic acid (Formicacid), Acetic acid (Acetic acid), propionic acid (Propionic acid), lactic acid (Lactic acid), etc. The resin composed of the agent, the energy required for complete curing of the cationic electro-resin resin is 20 ~ 800mj / cm2, and the best is 50 ~ 6 50 mj / cm2. In addition, thermosetting cationic resin and coloring materials can also be used. Composition | wherein this thermosetting cationic resin contains a composition of cationic resin, thermosetting agent, solvent and water | Electrical writing conditions are 30 ° C, 10 ~ 50 Volt, electrowriting time 30 ~ 180sec, resin is available The film thickness is 0.5 to 3 μm. However, the characteristics of anionic electro-resin, regardless of the stability of the resin (non-yellowing), ease of emulsification, and pigment dispersion, especially at high pigment concentration dispersibility | even the cost of materials is far higher than that of cationic The resin is better, so the positive combination of photoresist and anion electro-resin is the best combination in the present invention, which greatly helps to improve the yield. The coloring substance used in the red, green and blue pixels can be a composition of dyes, pigments or mixtures thereof. The amount of coloring substance added is 3 ~ 70wt% of the total solids, preferably 5 ~ 60wt%. The amount depends on the need for color saturation. The types of dyes include: azo dyes, anthraquinone dyes, benzodiforanone dyes, condensed methine dyes, or mixtures thereof. The types of pigments include: azo lake organic pigments, quinacridone organic pigments, phthalocyanine organic pigments, isoindolinone organic pigments ), Anthraquinone organic pigments, thioindigo organic pigments, chrome oxide, chrome vermilion, chrome green, chrome green (please first Read the precautions on the back and fill out this page)-β-line paper paper scales are used in China National Standard Falcon (CNS) A4 wash grid (210X297 mm) 83. 3.10,000 -16- Ministry of Economic Affairs, Ministry of Economic Affairs Consumer Cooperative Printed A7 B7 V. Description of invention (15) (utramarine), prussian blue, cobalt green, emerald green, titanium white, carbon black ( carbon black) or its mixture. Dyes have no problem of dispersion because they are completely dissolved in the resin; pigments can only be dispersed in the resin, and the general particle size does not exceed 0.2 The positive photoresist containing the shading material, the shading material can be shading color or shading filler, the shading color is carbon black (Carbon black); the shading filler is carbon dioxide ( T i 0 2, titanium oxide). When using anionic resin electrolysis resin • Unhardened acid groups on the surface will dissolve in the alkaline development solution of the photoresist, and the next area of the photoresist pattern is developed at the same time. It is easy to peel off the resin that has been electrolyzed. The solution is to harden the resin first so that it will not be attacked by the developer. In addition, if the positive photoresist is heated, the development process can no longer be carried out, so the thermosetting method cannot be used; based on the above two items For the reason, the electro-resin resin of the anionic resin of the present invention must be selected as the photo-curable type. The relationship between the fully developable exposure energy E of the positive type photoresist and the electro-resin resin's chemical energy R is different if the N region is to be produced Area of the exposure level, the exposure energy E of the photoresist can be fully developed must be at least greater than or equal to (N-1) times the hardening energy R of the electro-resin, that is to say, if you want to make 3 exposure zones The area where the photoresist can be fully developed must be at least greater than or equal to 2 times the curing energy R of the electro-resin; if you want to make 4 areas with different exposure levels | then E must be at least 3 or greater than R Times, the energy difference Ιηη of the regions exposed by the photoresist does not have to be the same, but it must be greater than the hardening energy R of the electro-resin to ensure that the electro-resin can be completely hardened while accumulating full exposure energy Will be affected by subsequent development steps. This paper scale is applicable to the national rate in China (CNS> Α4 said grid (210X297mm) 83. 3.10,000 ----------------- tr ------ -线 "->, (please read the precautions on the back before filling in this page) -17- A7 B7_printed by the Consumer Cooperative of Central Central Bureau of Economics of the Ministry of Economic Affairs 5. Description of the invention (4 impact, use in the invention The above is different from the electro-resin resin of anionic resin, and its curing is not necessarily in the process of electro-development, so the curing mode can be selected from photo-hardening or thermo-hardening; the former can accumulate energy with the photoresist in the middle of the electro-development process Hardening at the same time • or partly hardened in the electrographic development process, one exposure hardening after the electrographic development process is completed; the latter considers that the positive type photoresist is affected by temperature and can be baked once after the electrographic development process is completed In addition, when accumulating exposure energy with photoresist, the total accumulated exposure energy IE n must make the exposed photoresist develop discrimination, for example, the energy of IE 1 can only increase D 2 The cumulative exposure of the area reaches the amount that can be fully developed, The cumulative exposure of the D3 area cannot be developed; the energy of IE2 can only increase the cumulative exposure of the D3 area to the amount that can be fully developed, and the cumulative exposure of the D4 area cannot be developed. Next, give the invention In the third embodiment, I believe that other objects, features, and advantages of the present invention can be obtained from it to obtain a more clear and specific understanding. (Example 1) In a pre-completed black light-shielding matrix, a 1.1 mm thick transparent conductive A layer of positive photoresist A is coated on the glass (see Table 1 for composition), the film thickness is 2.2 μιη, and a photomask with only one-third part of the light transmittance domain is used, and the photomask is carefully shifted , Respectively, the energy is 3 0 0, 1 6 5, 3 0 mj / cm 2 (100%, 55%, 10%) exposure, can make the photoresist in three different exposure areas of the whole area (Please read the precautions on the back and then fill out this page) The paper size of the binding book is applicable to China National Standard Car (CNS > Μ 洗 格 (210X297mm) 83.3. 10,000 18 · Printed by the Central Committee of the Ministry of Economic Affairs Staff Consumer Cooperative Α7 Β7 5. Description of the invention (17) Development with 0.5% Na2Si〇3 The solution is developed to remove the part with an exposure amount of 300 m / cm 2 (100% exposure), and the red-light-curable electro-resin resin is used; the electro-authoring conditions are 30 ° c, 20Volt. 9 0 sec ° full exposure of 135m] / cm2 of energy, the second area, the original exposure I65mj / cm2 can be "300〇 ^ / (: 1112 (energy has been accumulated to 100% exposure), and the original exposure and the amount of 3 Ο / cm The third area of 2 (1 Ο% exposure area) also accumulates an exposure of 1 6 5 m〗 / cm 2 (5 5% exposure area). At this time, the red photo-curable electro-resin has been completely cured by exposure . Similarly, 0.5% / 〇 Na2Si〇3 developer solution was used to develop and remove the fully exposed part (100% exposed area), and the electrophotographic work of the green photo-curable electro-resin was performed under the same conditions. . Then fully expose the energy of 135mj / cm2. At this time, the green photo-curable electro-resin will be cured by ultraviolet light, and at the same time, the energy of the third zone 165mj / cm2 (55% exposure zone) will be accumulated to the full exposure of 3 0 0 mj / cm 2 ('energy has accumulated to 100〇 / 〇 exposure), and can be developed in 0.5% Na2Si〇3 developer, followed by blue light-curable electro-resin electro-resin. Finally, the electro-resin is hardened with ultraviolet light with an exposure of 1 3 5 m j / cm 2 and then completely cured at 200 ° C for 1 h r. The production of red, green and blue pixels is completed. (Example 2) A layer of positive photoresist B (see Table 1 for composition) is coated on a transparent conductive glass with a thickness of 1.1 mm, and the film thickness is 2.2 μm. Use a paper-only standard for remote use Chinese National Standards (CNS) Α4 specification (2 丨 0Χ297 公 Jtl) 9 · 83. 3. 10,000 (Jing first read the notes on the back and then fill out this book) Order A7 B7 Ministry of Economic Affairs Printed by the Central Bureau of Standards' Staff Consumer Cooperative V. Invention Description (IB) A mask with a quarter of the light-transmitting area, the mask is carefully shifted, and the energy is 5 0 0, 3 5 0, 2 respectively 0 0, 5 0 mj / cm 2 (100%, 70%, 40%, 10%) exposure, you can get four different exposure areas of the whole area. A 0.5% Na 2 S i Ο 3 developer solution was used to develop and remove the portion exposed to 500 m / cm 2 (exposed area of 1000 / 〇), and the red photo-curable electro-resin ( For the composition, please refer to Table 2). The electrowriting condition is 30 ° C > 20Volt, 90sec. Fully expose the energy of ISOmj / cm2, and harden the red light-curable electro-resin, so that the second area, the part of the original exposure 3 5 0 Hi〗 / cm 2 (70% exposure area), the energy accumulation reaches 50. 111 " (: 〇12 (丨 〇〇% exposure); and the third area (40% exposure meter area) of the original exposure 200m〗 / cm2 also accumulates an exposure of 350m〗 / cm2; and the original exposure of 50mj / cm2 The energy accumulation of the fourth area (10% exposure area) is 20〇111】 / (: 1112. Similarly, 0.5% Na 2 S i 〇3 developer solution is used to develop and remove the fully exposed part (100 exposure ), Under the same conditions, the green photo-curable electro-resin resin is electro-resined. Then, the energy of the green photo-curable electro-resin resin is fully exposed to harden the green photo-curable electro-resin resin to make the third zone 3 50 mj / cm 2 (70% exposure area) energy accumulation reaches the full exposure energy 500〇1 ". 〇12 (100% exposure), and can be developed in 0.5% Na2Si〇3 developer, and the exposure amount is 20〇mi / Cm2 The energy accumulation of the four areas (40% exposure area) is 70% of the full exposure; then the blue light-curing electro-resin resin is used. Then the full exposure is 1 54 m The energy of j / cm 2 is used to develop the fourth zone, and at the same time, the blue light-curable electro-resin resin is hardened, and finally the black light-cured electro-resin resin is electrically set. CNS > A4 grid (210X297mm) -20 83.3.10,000 Printed by Abe Bong Consumer Cooperative of Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 _ .. V. Description of the invention (19)》》 Exposure with 15〇mj / cm2 The amount of UV light hardens the resin, and then the color filter is hardened at 200 ° C, 1 hr. The red, green and blue pixels are completed. (Example 3) In a thickness of 1.1 mm transparent conductive A layer of positive photoresist C (see Table 1 for the composition) coated with black resin is coated on the glass, and the film thickness is 2.2 μm. Use a photomask with only a quarter of the light-transmitting area. The photomask is carefully shifted to perform exposures with energies of 600, 4, 20, 2 40, and 60 mj / cm 2 (10 0%, 70%, 40%, 10%). Get four different exposure areas in the whole area. 'Develop with 0.5% Na 2 S i 0 3 developing solution to remove the part with the exposure amount of 600 mj / cm 2 (10000 / 〇 Exposure), the electrophotographic work of the red photo-curable electro-resin; the electro-poration conditions are 3 ° C, 20Volt, 90 sec · Full exposure of 180m〆cm2 of energy to harden the red photo-curable electro-resin. The second area, that is, the part of the original exposure 4 2 0 m] / cm 2 (70% exposure area), the energy accumulation reaches 600mjf / cm2 (100% exposure); and the third area of 240mj / cm2 (40% exposure area) is also Cumulative exposure of 70%; and the energy of the fourth area (10% exposure area) of the original exposure of 60mj / cm2 is 240m " cm2 exposure ❶ is also developed with 0.5% N a 2 S i Ο 3 The solution is developed to remove the fully exposed part (100% of the exposed area), and the green photo-curable electro-resin resin is used under the same conditions * and then fully exposed to the energy of lSOmycm2. Please read the precautions on the back and then fill out this page) The standard paper size is in accordance with the Chinese National Standard (CNS> A4 said grid (210X297mm & 83.3.10,000 printed bag A7 B7___5. Description of the invention (2〇) The resin is hardened so that the third zone can reach 420m / cm2 (70% exposure zone) Accumulated up to a full exposure energy of 600mj / cm2 'and can be developed in 0.5% Na2Si〇3 developer, and the fourth area 240mj / cm2 (40% exposure area) energy accumulated to 70% of the complete exposure; then proceed The blue light-curable electro-resin resin, because the fourth area is directly used as a black shading matrix in this embodiment, after the last exposure of 18〇mi / cm2 the resin is completely hardened by 2 0 0 ° C, 1 hr, the fourth zone is hardened, and the production of the color filter is completed. * The foregoing and other objects and features of the present invention will be more prominent through the above description of the comparative example, the description It is only used to illustrate the operation results of the present invention in a better situation, and is not intended to limit the scope of the invention. Other modifications and changes made without departing from the spirit of the invention are within the scope of the present invention. (Please read the precautions on the back and then fill out this page) The standard paper for thread binding is suitable for China National Prototype (CNS) A4 wash grid (210X297mm 2 83.3 · 10,000) 5. Description of invention (2) Table 1 Photoresist Composition: A7 B7 Novolac Resin (MW = 40,000) Formaldehyde / Formaldehyde = 1: 0.82 100 g Photoactive Compound 2,3,4-Trihydroxybenzophenone / diazide-5 -Sulfonyl chloride (1 / 2.0) 25 g Cellulose acetate 360 g Composition of photoresist B: Novolac Resin (MW = 40,000) Formaldehyde / formaldehyde = 1: 0.82 1〇〇g Photosensitive matter (Photoactive Compound) 2,3,4-trihydroxybenzophenone / diazide-5-sulfonyl chloride (1 / 2.5) 30 g cellulose acetate 390 g

Composition of photoresist C I (please read the notes on the back before filling this page), \ se

Novolac Resin (MW = 40,000) Cresol / Formaldehyde = 1: 0.82 100 8 Photoactive Compound 2,3,4-Trihydroxybenzophenone / Di Azide-5-sulfonyl chloride (1 / 2.5) 30 g carbon black 33 R cellulose acetate 490 g The standard of this paper method is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -23- 83 . 3. 10,000 A7 B7 5. Description of the invention (22) Table 2

Light-curing anionic electro-lipid composition Red, green, blue and black anionic resin + 100 g 100 g 100 r 100 g Triethylamine (100% neutralization amount) Trimethoxypropane triacrylate 2〇β 20 g 20 β 20 g phenyl dimethyl acetal 5 R 5 R butanol- (η) 10R 10g 10R 10R isopropanol 20g 20g 20g 20g deionized water 1635g 1655g 1545 g 1545 g CI red pigment 177 60 g CI green pigment 7 70 g CI blue pigment 15: 3 50 g carbon black 50 R + anionic resin composition is as follows:

Methyl methacrylate 104 8 acrylic acid 72 β hydroxyethyl acrylate 177 g ethyl acrylate-15〇r cellulose acetate 503 S (please read the precautions on the back before filling this page) -Subscribe

Printed by Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs This paper scale is applicable to China National Standards (CNS) Μ specifications (210X297 mm) 83.3. 10,000 24-

Claims (1)

.. * The Ministry of Economy * Xin Er "Work Consumers ^ Cooperation Du Yin *-| 4 Ling f) f, supplement I —_ 六. Patent application 1. The method of making color filters by energy accumulation method, including The steps are as follows: (a) A layer of positive photoresist is coated on a transparent conductive substrate, and the photoresist is formed into areas with at least three different exposure levels, and their exposure amounts are: Dl, D2, ..., and Dn , Where D1 represents the exposure amount that allows the photoresist to be completely developed, and Dl > D2 > .. > Dn, η ^ 3; (b) development removes the area that can be completely dissolved by the developer and the exposure amount is D1 And expose the conductive substrate, and then in this area, the electrosetting configuration of the photo-curable electro-resin, that is, the pixel; (C) the exposure amount of the full irradiation energy IE m, which is the energy difference between D m and D m + 1 (Ie, IE m = (D m-D m + 1)), where m = l, 2, ..., nl (n23), harden the pixels that have been written, and increase the exposure of all areas, The cumulative exposure of the D m + 1 area (D m + 1 + IE m = D 1) has been reached. The amount developed completely by the same developer in step (b); (cl) using step (b) The Dm + 1 area described in step (c) is removed by the same developer, and the conductive plate is removed naked, and then the 汜 荇 resin is smeared in this area, which is the step of removing the oxychloride; and (C ) ® Steps (C), (d), Ιι'ι: to complete the Πϋ 尜 match ίί_'ί of the color of the fu, and harden the end "2. Such as the price of the vortex Gongli 丨 1 item can be cut The method of making color light jV by the method of accumulating, the choice of the station board system is to select the compound of the tin, marry, antimony intermediary companies into their mixture or ... the general commercial guide ηι slope glass. This paper The ft scale is applicable to the Chinese standard (CNS) A4 specification (210X 297mm) -25- ----------- installed --- called !.-:-order --- --- Line "-(Please read the notes on the back and fill in ft? This page) Α8 Β8 C8 D8 Central Standard of the Ministry of Economic Affairs ^ Only ^ Cooperative cooperative printing 6.Applicable patent scope 3. If applying A method of making a color filter by the energy accumulation method in item 1 of the patent scope, wherein the positive photoresist is selected from the group consisting of phenolic resin and naphthoquinone diazo compounds or their derivatives. 4. If applied One of the first items in the patent scope A method of making a color filter by energy accumulation method, in which the photoresist is formed into areas with three different exposure levels, a mask with three areas with different transmittances can be used, and the range of different transmittances is 100 ~ 40%, 85 ~ 20%, 70 ~ 0%. 5. For example, a method of making a color filter by energy accumulation method in item 1 of the patent application scope, in which the photoresist is formed into areas with three different exposure levels, and a photomask with three areas with different transmittances can be used, The range of different light transmittances is 100 ~ 70% '70 ~ 40%, 40 ~ 0% ° 6. Such as the method of applying the first item in the scope of the application of the method of making color light film by the method of M, which is The photoresist is formed into areas with four different exposure levels, which can make the light with four different transmittance areas: it + Η light transmittance range is 100 ~ 40%, 85 ~ 20% , 70 ~ 5%, 50 ~ 0%. 7. If you please ask Li Fan_ Item 1 __ · Μ method to make color filters by the tipping method, in which the photoresist is formed into four different degrees of exposure. This paper scale is applicable to the national standard of China Hua (CNS> Λ4 specifications (210X297mm) ^^ 1 I---! I 1 Ϊ—, ...... mu I (please read the precautions on the back before filling this page), -u '线 26- ABCD Ministry of Economics, Yanyang, Pingping, Azhigong & Co., Ltd. Print 31. 6. For areas where patents are applied, photomasks with four areas with different transmittances can be used. The range of different transmittances and degrees is 100 ~ 80%, 80 ~ 50%, 50 ~ 3 0%, 3 0 ~ 0%. 8. A method of making a color data light sheet by the energy accumulation method as described in item 1 of the patent scope, in which the photoresist is formed Areas with three or four different exposure levels can use a photomask with partial light transmission through fine displacement, and then expose the photoresist with different exposures to make the photoresist with different exposure areas. 9 . Such as a method of making a color filter by energy accumulation method as in item 1 of the patent scope, in which the light To form three or four areas with different exposure levels in the whole area, multiple (three or four) photomasks can be used to expose the photoresist to areas with different exposure levels. 10. If applying for patent scope item 1 A method of making color furnace light sheet by energy accumulation method, in which the developer used is selected from sodium carbonate, sodium bicarbonate, sodium silicate, sodium hydroxide, tritium oxide, and quaternary amine compounds or Aqueous solution of the mixture. 11. As one of the first item of 劮 Μ 簀 利范 Μ 語, we can use the power to make the color of the daughter-in-law's light film, jM1 is the material of light hardening and feeding resin is 彳! R light hardening. VII Copy the resin and the nails of the tea. I2 If one of the items 1 and 1 of the patent fan park is claimed, the color paper made by the energy method is applicable to the Zhongguanjia 'standard (CNS) 84 specifications ( 21Gx297 degrees) ~~ ~ ----H — ^ ϋ--ii—. I— I (please read the precautions on the back side before filling in this page) Μ • -5 27- ABCD Advise: ^ Printed by the Industrial Consumer Capital Cooperative? 六. Method of applying for patent Fanyuan furnace light film, in which light hardening The electro-resin is selected from a composition containing anionic resin, photoreactive monomer, photoinitiator, solvent and water. The method of optical sheet ', wherein the anionic resin is selected from acrylic resins containing acid groups (residual acid groups, sulfonic acid groups) and ammonia, trimethylamine, diethylamine, monomethyl alcohol atmosphere, or A resin composed of a diethylethanolamine neutralizer. M. A method for making a color filter by the energy accumulation method as described in the first item of the patent scope, where the photo-curable electro-resin is selected from cation-containing resins , Photoreactive monomers' composition of photoinitiator, solvent and water. 15. For example, a method of making a color filter by energy accumulation method as described in item 14 of the patent application letter wherein the cationic resin is selected from acrylic resins containing amine (tertiary amine or quaternary amine) and Resin containing neutralizing agent of formic acid, acetic acid, propionic acid or lactic acid. 16. Such as Φ to run a profit 丨 such as 1 item. Ke Yi can use the frame method to make color Muguang film force method, w 屮: coloring matter π η 丨 α dyes, pigments into Μ objects. 17. If you want to make a color filter with the energy accumulative method in one of the first items of the patent range 丨 ft 丨 -------- install. (Please read the precautions on the back before filling this page_ Mi 、 -u line ί This paper's thick scale is applicable to the Chinese standard (CNS) Μ specification (210 > (297 male cage) 28- B8 C8 D8! S it, 1 central rate; goods i work j consumer I fee *; Zuosha: The method of printing 'patent-applied light sheet, in which step (a) can perform a photoresist process on a conductive substrate with a black shading matrix pre-completed. The material of the black shading matrix mentioned here can be Alloys of chromium, nickel and other metals or their oxides or their mixtures or organic polymer coatings doped with black colorants. 18. If one of the patent application items 6 or 7 is used to make color filters The film method may further include coating a layer of black resin resin on the naked cod in the fourth area, irradiating ultraviolet light from below the conductive substrate, and using the red, green and blue pixels as a light-shielding barrier. The black resin in the hole hardens to become a black shading matrix. Patent Fanyuan Item No. 18 is a method for making color filters by the accumulative accumulation method, in which the material type and manufacturing method of the black shading matrix can be selected from the following three types: (a) The heat can be mixed with black coloring material The hardened positive photoresist, the least exposed part can be left as the black shading matrix at the end; (b) Use the black electroresin with the same resin formula as the best, the black shading matrix is made in the same way as the best way On the conductive substrate; and (c) use photosensitive black resin containing light-curing type. (Please read the note on the back side and then fill out this page) —Install ^ ------ Order the paper size Applicable to Chinese National Standard (CNS > A4 Washing (21〇X297mm) -29-