TW200428152A - Positive photoresist composition for spinless (slit) coating - Google Patents

Abstract

A positive photoresist composition for spinless(slit) coating is disclosed. The positive photoresist composition includes 5~50 parts by weight of an acrylic or novolac binder resin, 0.1~50 parts by weight of a photoactive compound, 0.001~5 parts by weight of a silicon compound containing epoxy or amine group, and 0.001~5 parts by weight of a fluorine-based or silicon-based surfactant. A solvent is added to the composition so that viscosity becomes 2~20 cps. The positive photoresist composition may form a uniform coating layer without any coating defects when a layer such as an organic insulating layer is formed on a substrate with a spinless coaler, and is easy to control edge profile of the coating layer.

Description

200428152 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a photoresist composition for slit coating, and more particularly to a positive photoresist composition for slit coating. When a coater forms a layer on a substrate, it can form a uniform coating without coating defects, and it is easy to control the edge contour of the coating. [Previous Technology] Flat displays, such as liquid crystal displays (LCDs), are currently undergoing large-scale development. Therefore, substrates for LCDs are also being developed. Currently, a production line for fifth-generation substrates has been established, and larger substrates (such as the sixth or seventh generation) are being developed. With the trend of increasing substrates, the ageing method of shirts has changed due to *. In other words, for the fourth-generation glass substrate, the cracking and spin coating method is used, in which the button composition penetrates the cracked alkali board and contacts the car. Thin, for the fifth generation or later glass substrates with dimensions exceeding € m> d_mm, the crack coating method has been used because it cannot be rotated, where light is applied as the composition passes through the crack On the substrate, and then complete the coating process without rotation. As mentioned above, since the coating method has been changed, the button change is currently using light. Especially in the case where the slit k cloth method is applied to a large-sized substrate, a coating formed of a photoresist composition should be uniformized and applied without any defects. Furthermore, applying the program to the slit should allow easy control of the edge profile of the coating. 6 200428152 [Summary of the Invention] The Ben Fanna test_ solves the problems of the prior art, therefore, the object of the present invention is to provide a positive photoresist composition, which forms a layer (such as an organic insulating layer) on a substrate. 'It can form a coating without uniformity and coating defects, and easily control the edge contour of the coating. In order to achieve the above object, the present invention provides a positive photoresist composition, which comprises: 5 to 50 parts by weight of an acrylic or Novolak adhesive resin; 0 to 50 parts by weight of a photoactive compound; 0.001 to 5 parts by weight Parts of a silicone compound containing an epoxy or amine group, and 0.001 to 5 parts by weight of a fluorine-based or silicone-based surfactant, wherein an ice agent is added so that the viscosity is 2 to 20 centipoise (cps). [Embodiment] The present invention will be explained in detail as follows. The positive photoresist composition for slit coating of the present invention contains 5 to 50 parts by weight of an acrylic or Novolak adhesive resin. As the acrylic adhesive resin, any of conventional acrylic adhesive resins used in a positive photoresist composition can be used. It is more preferable to use a resin having the following general formula 1 or 2 alone or in a mixture. Formula 1

XXX 200428152

COOY1 COOH COOY2 In Formula 1, X is a fluorene atom or a methyl group, Y1 is an alkyl group or a hydroxyalkyl group having 1 to 16 carbon atoms, and Y2 is selected from the group having the following chemical formulae (I) to (XX) Group of compounds.

CH2 = C-CO—O-Ra CH2 == C—CO—〇—R2h

ch2 ~ c-co-o ~ r2

(I) (Π) an) (IV) (V) (VI) (VB) 01) (IX) 200428152

chU ~, OH

chU

CH2 = C-CO-I ^ RiT, 〇H CH2 = C-C0-0-R2-O- (C〇-R2-OJk-CO-N ^

Re

R2—〇- (C〇-Ra-〇) k-CO—N CH2 = C—C0—0—R2—0— {CO—R2—C〇-N \

-¾ one 0— (CO—R3—0} k—CO-N R4

ohJW

CH2 == C—CO-Ο-R2 HI

co-o—ch2

CH2 = C—CO—O— R-Hi CH2 = C—CO—O-R2-CH ·

CH2—O—CO

o-ch2〉 ch o-ch / ch2— CH2—

(X) (XI) (ΧΠ) (xm) (XIV) (XV) (XVI) (XVH) (XVffl) (XIX) (XX) In the formulae (I) to (xx), Ri is a 氲 atom or 曱The group 'R2 is an alkylene group having 1 to 10 carbon atoms, R3 is a hydrocarbon having 1 to 10 carbon atoms, R4 is a hydrogen atom or a fluorenyl group, and Rs is 10 having. A hydrocarbon of 1 to 10 carbon atoms, and k is an integer of 0 to 2 in Formula 2 /, the repeating unit A is selected from the group consisting of methacrylic acid vinegar, styrene, di + isopropyl isobornyl vinegar And isobornyl methacrylic acid purpose, acrylic acid dicyclopentane purpose, methacrylic acid dicyclohexyl acetate, acrylic acid dicyclopentene vinegar, methacrylic acid U-pentene I, acrylic acid dicyclopentyl ethoxy acid purpose, A group consisting of propyl dicyclopentyl ethoxy vinegar, acrylic dicyclopentyl ethoxy g, f-based dicyclopentyl fluorenyl ethoxy vinegar, etc. B is selected from the group consisting of f-based glycidyl acetic acid vinegar , Methacrylic acid, gs, -methylaminomethacrylic acid, acrylic acid, methacrylamine, etc., and C is acrylic acid or methacrylic acid, in which the adhesive cellulosic structure with the general formula 2 structure Contains random copolymers regardless of A, B and c order. The purpose of the adhesive having the structure of the general formula 1 is a silk material consisting of a monomer containing fine t and a monomer city containing double bonds. When the positive photoresist composition of the present invention containing this object is applied to a substrate and then patterned, the uniformity is excellent without any defects (such as a residue after development). In other words, an alkyl group or a hydroxyalkyl group having a carbon atom in the formula 丨 is used to improve the adhesion. In addition, γ2 contains a huge cycloaliphatic 200428152 group structure (unlike the conventional acrylic copolymer adhesive resins containing aromatic groups) to improve film retention and heat resistance (based on high glass transition temperature). Furthermore, the adhesive resin having the structure of the general formula 2 shows almost the same effect as the adhesive resin having the structure of the general formula 1. As for the adhesive resin of the general formula 2, 'other kinds of repeating units, such as alkyl acrylate or fluorenyl acrylate having 2 to 16 alkyl groups as shown in general formula 3 (D), may be included in Within the scope of the present invention. More specifically, the repeating unit may be methacrylate, butyl methacrylate, methacrylate lauryl, methacrylate, butyl acrylate, lauryl acrylate, styrene, and the like. Formula 3

In particular, when the adhesive resin of the general formula 1 and the adhesive resin of the general formula 2 are used, the hardness of the pattern can be improved and the whitening phenomenon can be eliminated because of the compatibility between the adhesive resin and other photoresist components in the composition Sexual increase: now. As far as Volak resin is concerned, any well-known Novolak resin can be used, which can be disclosed through "Chemistry and Application of Phenolic Resins, Knop A and Scheib, W .; Springer Verlag, New York, 1979 Chapter 4" Method synthesis. Furthermore, the positive photoresist composition of the present invention contains 0.1 to 50 parts by weight of a photoactive compound. As far as photoactive compounds are concerned, any conventional photoactive compounds can be used, such as 2,2004,152,152,2,2,3,4,4'-pentahydroxybenzophenone, 2,2,3,4,4 ,, 5-Hexahydroxybenzophenone, 2,2,3,4,4,5 pentagreen diphenyl sincere, 2,21,3,4,4 ,, 5-reading diphenyl propane, 2,3 '4-—Mesityl benzophenone, 2,3,4-trihydroxyacetophenone, 2, from trihydroxyphenylhexylpyridine with 2,4,4-dichazylbenzophenone with 2, 4,6_trisyl benzophenone, 2,3, trisyl 2-methyl-benzone, 2,2i, 4,4L tetrahydroxybenzophenone, tetrabenzyl benzophenone Wait for 1,2-diazo f carbon bucket or 5-sulfonate. The paste compound containing an epoxy or amine group in the positive photoresist composition of the present invention improves the adhesion between the ITO electrode and the composition and the financial and thermal properties after hardening. This gelatinized material is selected from the group consisting of (3 'glycidyloxypropyl) trimethoxysilane, (3-glycidyloxypropyl) triethoxy, and (3'glycidyloxypropyl). ) Methyldimethoxy oxamine O'glycidyloxypropyl) Methyldiethoxy stone yaki, (S 'Glycidyloxypropyl) monomethyloxy oxy stone yaki, (3' Shrink Glyceryloxypropyl) dimethylethoxylate, 3,4-epoxybutyltrimethoxylate, 3,4-epoxybutyltriethoxylate, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyldiethoxysilane, aminopropyltrimethoxysilane, etc. At least one. The content of the silicone compound is from 0.001 to 5 parts by weight, and preferably from 0.05 to 500,000 parts by weight. Furthermore, the positive photoresist composition of the present invention contains 0.001 to 5 parts by weight of a fluorine-based or silicone-based surfactant. Fluorine- or silicone-based surfactants are trade names Megaface F142D, F172, F-172D, F177P, R-08, F-470, P_471 'F475 (manufactured by Dainippon Ink & Chemicals), FC-170C, 12 200428152 FC-430, FC-431 (manufactured by Sumotomo 3M Co., Ltd.), BYK 306, 307, 310, 331, 333 (manufactured by BYK-Chemie), etc. are sold. In addition, if necessary, additives such as a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent, and a leveling agent may be used in the positive photoresist composition. A solvent is preferably added so that the positive photoresist composition of the present invention has a viscosity of 2 to 20 centipoise. It is better to adjust the viscosity to 3-10 centipoise (this is more conducive to controlling the thickness of the thin layer without pinholes). The solvent contains a solvent selected from the group consisting of ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl, ethyl methoxy propyl propionate, and ethyl ethyl propionate Ethyl vinegar (EEP), ethyl lactate, propylene glycol methyl ether acetate (pGMEA), glycerol methyl ether, propylene glycol propyl_, methyl cellosolve acetate, ethyl cellosolve acetate, a Diethylene glycol acetoacetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexyl, dimethylformamide (DMF), n, n_di Fluorenylacetamide (DMAc), N-fluorenyl-2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether, ethylene glycol-fluorenyl ether, monoethylene glycol difluoride | (digiyme) , Tetrahydrofuran (thf), methanol, ethanol, isopropanol, methyl cellosolve, ethyl cellosolve, diethylene glycol ethyl ether, diethylene glycol ethyl ether, At least one of the group consisting of dipropylene glycol methyl ether, toluene, dioxan, hexane, heptane, octane and the like. The present invention will be explained in detail as follows. However, it should be understood that the detailed description and representative of this U car are also good: ^ The special embodiment of the system is for illustration purposes only. For those skilled in this art, from this detailed description, # can understand that it is within the spirit and scope of the present invention Many changes and retouching. 13 200428152 Specific Examples 1 to 20 According to the components and contents of Table 1 below, a positive photoresist composition was prepared. Cresol-formaldehyde novolak resin: 10% by weight of 1,2_diazo of 2,2,5,5'-tetrahydroxybenzophenone | Each sulfonate: 2 plus% (3-glycidyl (Propyl) trimethoxysilane: 5% by weight, surfactant based on fluorine: 0.03% by weight, solvent: residual amount

Megaface F142D (manufactured by Dainippon Ink & Chemicals co.) Is a surfactant used as a messy substrate. The viscosity of the formed positive photoresist composition was about 4 centipoise (cps). ^ MMJ2U39 According to the composition and content of Table 2 below, a positive photoresist composition was prepared. Acrylic resin · 10% by weight of 2,2,5,5'-tetrakisylbenzophenone 1,2_diazo | carbon_5_ lutein: plus% (3-glycidylpropyl ) Trimethoxylithium: 0.05% by weight. Surfactant based on fluorine: 0.03% by weight. Solvent: Residual amount. Use acrylic adhesives of general formula 1 (where χ is methyl and γ1 is Methyl 'and hydrazone 2 is a chemical formula (II) having a methyl group. 14 200428152

Megaface F142D (manufactured by Dainippon & Chemicals Co) is a surfactant used as a fluorine substrate. The viscosity of the formed positive photoresist composition was about 4 centipoise (cps). Specific examples 40 to 71 Except for the production of DMC as a solvent, the type and content of the secret agent were changed according to Table 3, and the method was used to produce a red miscellaneous composition. The viscosity of the formed positive photoresist composition was about 4 centipoise (CP). The evaluation of the positive photoresist composition according to these specific examples was performed on a core glass. The test coating's coatability #, uniformity and edge contour are as follows. The results are shown in Tables 1 to 3. (1) Coating properties The positive photoresist composition was coated on a glass with a non-rotary coater, and then pre-baked at 9 ° C for about 2 minutes. Then, Zuo Zuo Yong Tsao Choi was under the forest Observe the coating with the naked eye. If there is no coating defect, the job list is "good", and the marriage is "no (2) uniformity. The positive photoresist composition is coated at 90 ° C with a non-coagulation coating machine. Pre-bake about 2 minutes shovel pull # 乂, 、, 钟. Then, use a film thickness gauge (nanospec) to measure the thickness of the coating at 1 position. Very much. If the right; maximum and minimum passes, then It stands for "good", and butterfly is "poor." Produced by 3 15 200428152 (3) The edge profile was coated on a Cr glass with a non-rotary coater, and then pre-cured at 90 ° C. Bake for about 2 minutes. Next, scan the edge area with a profilometer. If the angle between the inner wall of the pattern and the substrate is greater than 55 °, it means "good", otherwise it is "poor". Table 1 Specific examples Solvent uniformity edge contour Coating defect I II Ill Proportion% (1: 11: 111) 1 PGMEA--100: 0: 0 Jiajiajia 2 PGMEA MCA 95: 5: 0 Jiajiajia 3 PGMEA MCA- 90: 10: 0 Allison 4 PGMEA MCA-85: 15: 0 Allison 5 PGMEA MCA-80: 20: 0 Allison 6 PGMEA MCA-70: 30: 0 Allison 7 PGMEA MCA NBA 95: 5: 5 Allison 8 PGMEA MCA NBA 80:10:10 Allison 9 PGMEA MCA NBA 70:15:15 Allison 10 DMC--100: 0: 0 Allison 16 200428152 11 DMC NBA-90: 10: 0 Allison 12 DMC NBA-80: 20: 0 Allison 13 ECaA--100: 0: 0 Allison 14 ECaA NBA _ 95: 5: 0 Allison 15 ECaA NBA-90:10: 0 Allison 16 ECaA NBA-80: 20: 0 Allison 17 PGMEA EEP-90: 10: 0 Allison 18 PGMEA EEP-80: 20: 0 Allison 19 PGMEA EEP NBA 90: 5: 5 All Jiajia 20 PGMEA EEP NBA 80:10:10 Jiajiajia Table 2 Specific examples Solvent uniformity Edge contour coating defect I II Proportion% (I: II) 21 DMC-100: 0 Jiajiajia 22 DMC NBA 90:10 Allison Jia 23 DMC NBA 80:20 Allison Jia 24 DMC NBA 70:30 Allison Jia 25 DMC MCA 90:10 Allison Jia 26 DMC MCA 80:20 Allison Jia 17 200428152 27 DMC MCA 70:30 Allison Jia 28 DMC CHX 90:10 Allison Jia 29 DMC CHX 80:20 Allison 30 DMC CHX 70: 30 Allison 31 DMC PGMEA 90: 10 Allison 32 DMC PGMEA 80: 20 Allison 33 DMC PGMEA 70: 30 Allison 34 DMC EEP 90: 10 Allison 35 DMG EEP 80: 20 Jiajiajia 36 DMC EEP 70:30 Jiajiajia 37 DMC PGPE 90:10 Jiajia 'Jia38 DMC PGPE 80:20 Jiajiajia 39 DMC PGPE 70:30 Jiajiajia Table 3 Surfactant uniformity of specific examples Edge contour coating defect type content 40 Megaface F142D 0.01 Allison 41 F142D 2 Allison 42 F172 0.01 Allison 18 200428152 43 F172 2 Allison 44 F-172D 0.01 Allison 45 F-172D 2 Allison 46 F177-P 0.01 Allison Plus 47 F177-P 2 Allison Plus 48 R-08 0.01 Allison Plus 49 R-08 2 Allison Plus 50 F-470 0.01 Allison Plus 51 F-470 2 Allison Plus 52 F -471 0.01 隹 Allison 53 F-471 2 Allison. Allison 54 F-475 0.01 Allison Allen 55 F-475 2 Allison Allen 56 FC-170C 0.01 Allison Allen 57 FC-170C 2 Allison Allen 58 FC- 430 0.01 隹 佳佳 59 FC-430 2 隹 佳佳 60 FC-431 0.01 佳佳 佳 61 FC-431 2 佳佳 佳 62 BY K306 0.01 Allison Plus 63 BYK306 2 Allison Plus 64 BYK307 0.01 Allison Plus 19 200428152 65 ΒΥΚ307 2 Allison Plus 66 ΒΥΚ310 0.01 ----— Allison Plus ― 67 ΒΥΚ310 2 Allison Plus 68 — ΒΥΚ331 0.01 Good — Good Jiayi 69 —ΒΥΚ331 2 Jiajia 70 ΒΥΚ333 0.01 Jiajiajia ~~ 71 ΒΥΚ333 One · 1 2 Jiajiajia

The industrial applicability is as described above. When the non-rotary coater is used to form a layer (such as an organic insulating layer) on a substrate, the positive photoresist composition of the present invention can form a uniform coating without coating defects, and is easy Controls the edge profile of the coating. The invention has been described in detail above. However, it should be understood that the detailed description and the specific embodiments simultaneously representing specific examples of the present invention are for illustration purposes only, as they are familiar with this technology

Artists, from the detailed outline of this book, we should be able to understand the many changes and retouching in this book. [Brief description of the diagram] [Description of the main component symbols] There is no diagram description in this case, so no component symbol 20

Claims (1)

200428152 10. Scope of patent application: 1. A positive photoresist composition for slit coating, which comprises: 5 to 50 parts by weight of acrylic or Novolak adhesive resin; 0 to 50 parts by weight Photoactive compound; 0 ~ 5 parts by weight of an oxalate compound containing an epoxy or amine group; and 0.001 ~ 5 parts by weight of a fluorine-based or silicon-based surfactant, wherein a solvent is added so that the viscosity is 2 ~ 20 centipoise (Cp❸. 2. The positive photoresist composition for slit coating as described in item 1 of the scope of patent application, wherein the acrylic adhesive resin is selected from resins having the following general formula ^ Groups of resins and mixtures thereof having the following general formula 2: <General formula 1> XXX COOY1 COOH C〇〇Y2 Wherein X is a hydrogen atom, γ1 is an alkyl group or an alkyl group having an ionic group, and Y is selected from the group consisting of compounds having the following chemical formulas ① to (bright structure; ch2: CH2 = 0— C〇 ~ C—CO 〜 (I) (Π) 21 200428152 CH2 === C—C〇—〇—R2 一 CH on― CHg = C—CO—O— R2 ~ R4 CH2 = C—CO—N-R2—〇 ~ Rf, 〇H ChH 0142 = 0-CO-O-R2--0_ (CO-R2-0) k-CO ~ Re R2—O— (CO—R3—0) k—CO—N R4 chJ-co-o-r.-o-^-o.-oo-S; Re (m) (IV) (V) (VI) (w) (VUI) (K) (X) (XI) (ΧΠ) (xm) (XIV) CH2 = &lt;! i-CO-0-¾ -Rg —0— (CO-Ra—0) k-C0 ~ N R4 22 (XV) (XVI) 200428152 ? Η c (χνπ) (xvm) (XIX) (XX) /, Bu,, 11 atoms or fluorenyl groups, R2 is a fluorinated group having Ui0 carbon atoms, r3 is a hydrocarbon having a UK) atom, an atom or a methyl group, &amp; is an atom having 1 to 10 carbon atoms Hydrocarbon, and k is an integer G to &lt; &lt; Formula 2 &gt; Is the repeating unit A selected from methylphosphonic acid? Ester, styrene, styrene-based, isobornyl acrylate and isobornyl methacrylate, dicyclopentyl acrylate, dicyclopentyl methacrylate, di_enyl acrylate, methacrylic acid Bicyclopentyl, bicyclosilethoxy, acrylic acid, dicyclopentylethoxy methacrylate, propylene dicyclopentane; ^ Congyiyu g, and dicyclopentyl f serene Group 23 200428152 group consisting of ethoxy esters, B is selected from the group consisting of glycidyl methacrylate, hydroxyethyl methacrylate, dimethylamino methacrylate and acrylamide, and C is acrylic acid Or methacrylic acid, wherein the adhesive resin having the structure of the general formula 2 contains a random copolymer regardless of the order of A, B, and C. 3. The positive photoresist composition for slit coating according to item i of the scope of the patent application, wherein the silicone compound containing an epoxy or amine group comprises a compound selected from (3-glycidoxypropyl) trimethyl Oxyhydroxyl, (3'glycidyloxypropyl) triethoxyxanthane, (3-glycidyloxypropyl) methyldimethoxysilane, (Iglycidyloxypropyl) methyl Diethoxybenzyl, (3-glycidyloxypropyl) dimethylmethoxy dream, 0glycidoxypropyl) dimethylethoxymonu, 4-epoxybutyltris Phenoxybenzyl, 3,4-epoxybutyltriethoxy sulphate, 2- (3,4-epoxycyclohexyl) ethyltrimethoxydream, 2- (3,4 · epoxy At least one of the group consisting of cyclohexyl) ethyltriethoxylate and aminopropyltrimethoxylate. 4. The positive photoresist composition for slit coating as described in item i of the scope of the patent application, wherein the solvent contains a material selected from the group consisting of ethyl acetate, butyl acetate, diethylene glycol, methyl, Monoethylene glycol dimethyl ethyl, methyl methoxy vinegar propionate, ethyl ethoxy propyl propionate (EEP), ethyl lactate, glycolide methyl acetic acid vinegar (PGMEA), propylene glycol a Ether, propylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, pyrene Methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), dimethyl methyl alkane, etc. 24 200428152 (NMP), γ-butane Lactone, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol diglyme, tetrahydropyran (THF), methanol, ethanol, isopropanol, methyl cellosolve, ethyl solvent Fiber agent, diethylene glycol methyl group, diethylene glycol ethyl group, -dipropylene glycol fluorenyl ether, toluene, dimethylbenzyl, hexane, heptane and octane At least one of them. 5. As described in item 1 of the patent application, the positive photoresist composition for slit coating, the fluorine-based or lithoxone-based surfactant is selected from Megaface F142D, F172, F-172D, F177P, R 〇8, i? _470, F-471, F-475 (manufactured by Dainippon Ink &amp; Chemicals), FC-170C, FC-430, FC-431 (manufactured by Sumotomo 3M co., Ltd.), BYK 306 , 307, 310, 331, 333 (manufactured by BYK-Chemie) and mixtures thereof. 25 200428152 VII. Designated Representative Chart (1) The designated representative map in this case is: (). (2) Brief description of the component symbols of the representative diagram: There is no designated representative diagram in the present invention, so there is no component symbol 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (XX) 5