TW591333B - Positive photoresist composition and forming method for resist pattern for manufacturing liquid crystal display - Google Patents

Abstract

A resist material being inexpensive, and having excellent macro property (applicability, uneven heating property, uneven developing property) even in a process using a large glass plate is provided. Also a resist material suitable for manufacture of system LCD, excellent linearity, and suitable for I-line exposure is provided. The resist material is a photoresist which comprises (A) 100 parts by mass of alkali soluble resin, (B) 5 to 25 parts by mass of phenol compound having a specific chemical constitution as a sensitizer, and (C) 15 to 40 parts by mass of two kind quinonediazide compounds each having a 2-naphtoquinondiazide-5-sulphonyl group having a specific chemical constitution.

Description

591333 A7 ________B7 V. Explanation of the invention (4) Sensitivity enhancer) and two types of positive photoresist compositions with benzoquinonediazide ester compounds (photosensitive components) containing specific chemical structures, which can solve the above problems The material that reached the cost of invention. That is, the present invention contains 5 to 25 parts by mass of the phenol compound (B) represented by the following general formula (1) based on 1,000 parts by weight of the alkali-soluble resin (A). R10 R9

[In the formula, 'R1 to R8 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkane having 3 to 6 carbon atoms. R9 ~ R11 show each independently hydrogen atom or alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom or alkyl group having 1 to 6 carbon atoms, which is combined with R9 to form a carbon atom chain of 3 to 6 Cycloalkyl radicals, or bases shown by the following formula (II) are printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where R12 to R13 show the number of hydrogen, halogen, and carbon atoms independently) Alkyl groups of 1 to 6, alkoxy groups of 1 to 6 carbon atoms, or cycloalkyl groups of 3 to 6 carbon atoms; c is an integer of 0 to 3); a and b are 1 to 3 D is an integer of 0 to 3; η is an integer of 0 to 3]; Contains 15 to 40 parts by mass relative to 100 parts by mass of the total mass of the component (A) and the component (B) The benzoquinone diester-8- shown in the following general formula (III) (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) Α4 specification (2 丨 〇 > < 297 Mm) 59133 3 A7 B7 / 5 V. Description of the invention A photosensitive component formed by Γ nitrogen-based esterified product (photosensitive component 1) and benzoquinonediazide-based esterified product (photosensitive component 2) represented by the following general formula (IV) Mixture (C)

(m) (wherein R14 is an independent alkyl group having 1 to 5 carbon atoms; D is an independent hydrogen atom or 1,2-naphthoquinonediazide-5-sulfonyl group, At least one of D is 1,2 · naphthoquinonediazide-5-sulfofluorenyl; each of 1, m

Self-contained 1 or 2) DO

(IV) (In the formula, D is an independent hydrogen atom or 1,2-naphthoquinonediazide-5-sulfonyl, and at least one of D is 1,2-naphthalene Nitro-5-sulfonyl (Please read the notes on the back before filling this page) The Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs has printed a positive photoresist composition with organic solvent (D) as the feature. The present invention can provide a photoresist material that is inexpensive and excellent in overall characteristics (coatability, uneven heating characteristics, and uneven development characteristics) when used in a large glass substrate process. Furthermore, it is suitable for The LCD produced by the system has excellent linearity and is suitable for photoresistive materials for i-line exposure. The above (B) component is preferably a phenol compound represented by the following formula (V) or (VI). This paper size applies the Chinese National Standard (CNS) A4 Specifications (210X 297 mm) 591333 Α7 Β7 V. Description of the invention (6

0H

(V)

(VI) These compounds are highly sensitive photoresist films, high residual film rate, and excellent linear improvement. In the component (A), the total phenol-based repeating unit contains 60-mol% or more of P-cresol-based repeating units and 30-mole or more of m-formamidine-based repeating units. Phenolic lacquer type resin having a molecular weight (Mw) of 2000 to 8000. This resin has particularly good sensitivity, and it is unlikely to cause a change in sensitivity to temperature differences during heat treatment. The above-mentioned photosensitive component 1 is represented by the following formula (VII) (Please read the precautions on the back before filling this page)

(ΥΠ) The average esterification of the phenol compounds and 1,2-naphthoquinonediazide esters shown. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -10- 591333 Intellectual Property of the Ministry of Economic Affairs A7 __ B7 printed by the Bureau ’s Consumer Cooperatives V. Description of the invention (8) The glass substrate is ideal. The positive-type photoresist composition of the present invention is particularly preferably used for manufacturing a system LCD. The positive-type photoresist composition of the present invention is excellent in linearity and can be simultaneously exposed by i-line exposure to a small pattern and a large pattern to form a photoresist pattern. The above-mentioned system L C D is preferably made by a large glass substrate of 5 0 × 60 m 2. The above-mentioned system LCD is ideally made by an i-line (3 65 nm) exposure process. Because it can form a fine pattern of 0.5 to 2.5 // m degrees. The present invention includes (1) the step of forming the positive photoresist composition described above on a large glass substrate having a size of 500 X 600 mm2 or more to form a coating film, and (2) the glass substrate forming the coating film is subjected to a heat treatment ( A step of forming a photoresist film on a glass substrate after pre-baking), (3) a step of selectively exposing the photoresist film, and (4) applying an alkaline aqueous solution to the photoresist film after the selective exposure Development process, a step of forming a photoresist pattern on the glass substrate, and (5) a rinsing step of washing the developing solution remaining on the photoresist pattern surface, the liquid crystal display photoresist pattern of its characteristic Formation method. Although the photoresist pattern for manufacturing the liquid crystal display element formed in this manner is produced using a large glass substrate having a size of 500 X 600 mm2 or more, it is still a high-precision size. The above (3) selective exposure step is performed by using a photoresist with a different pattern size on the cover film with the pattern already drawn, and simultaneously forming a photoresist pattern with a different pattern size on the glass substrate. (Please read the precautions on the back before filling out this page)-Binding. The size of the paper used in the book is applicable to the Chinese National Standard (CNS) M specification (210 > < 297 mm) Print A7 _ B7 V. Description of the invention (9) The above-mentioned photoresist patterns for photoresist patterns with different pattern sizes must be printed with at least a photoresist pattern with a size of 0.5 to 2.5 / zm The mask film and the photoresist pattern with a pattern size of 3 to 1 0 // m are ideal for the mask film (parent cross line) mixed with the pattern mask film. In this case, a photoresist pattern having a pattern having a size of 0.5 to 2.5 // m and a pattern having a size of 3 to 10 / zm at the same time on the glass substrate is desirable. The positive photoresist composition of the present invention can simultaneously form patterns with different sizes. The above (3) selective exposure step is ideal for an exposure process using an i-ray (3 65 mm) light source. Since the pattern of local dimensional accuracy can be formed using the i-line, the positive-type photoresist composition of the present invention can be exposed using the i-line and subsequent development. [Implementation Mode of the Invention] Regarding the component (A): The alkali-soluble resin as the component (A) is not particularly limited, and the relevant positive-type photoresist composition can be arbitrarily selected as a film-forming substance from among those generally available. . For example, examples of the resin for forming a thin film of the positive-type photoresist composition include phenol resin, acrylic resin, copolymer of styrene and acrylic acid, polymer of hydroxystyrene, polyvinyl phenol, and polyα-methylethylene. Phenol and so on. Among them, a phenolic lacquer resin which is not swellable and easily dissolved and developed by an alkaline aqueous solution is preferable. Examples of phenol resins include condensation reaction products of phenols and aldehydes, condensation reaction products of phenols and ketones, vinyl phenolic polymers, and this paper applies Chinese National Standard (CNS) A4 specifications ( 210X297 mm) -13- i binding (please read the precautions on the back before filling this page) 591333 A7 ____B7_ V. Description of the invention (10) Hydrogenation reaction products of isopropenol-based polymers and phenol resins Wait. Examples of the phenols forming the phenol resin include phenol, m-cresol, P-cresol, 0-cresol, 2,3 · xylenol, 2,5-xylenol, and 3,5-xylenol. Dimethylphenols such as phenol and 3,4-xylenol; ethylphenol, p-ethylphenol, 0-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylfluorene No. of acid bases; P-methoxy acid, m-methoxy acid, p-ethoxyfluorene, m-ethoxyphenol, p-propoxyphenol, m-propoxyphenol, etc. Alkoxyphenols; 0-isopropenol, P-isopropenol, 2-methyl-4-isopropenol, 2-ethyl-4-isopropenol and other isopropenols; phenylphenol and others Arylphenols; 4,4'-dihydroxydiphenols, bisphenol A, resorcinol, hydroquinone, pyrophenol, etc. These may be used alone or in combination of two or more. Among these phenols, m-cresol, p-cresol, 2,5-xylol, 3,5-xylenol, and 2,3,5-trimethylphenol are particularly preferable. Examples of the aldehydes include formaldehyde, p-formaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, butyraldehyde, cyclohexanal, furanal, furan acrolein, benzaldehyde, Terephthalaldehyde, phenylacetaldehyde, α-phenylpropanal, / 3-phenylpropanal, 0-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, 0-methylbenzoic acid, m-methylbenzyl, ρ-methylbenzyl, 〇-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, etc. These can be used alone or two or more It can also be used in combination. Among these aldehydes, formaldehyde, which is easy to obtain, is preferred, and in particular, a combination of hydroxybenzaldehyde and formaldehyde is preferred to improve heat resistance. The above-mentioned ketones can be exemplified by acetone, methyl ethyl ketone, diphenyl ketone, etc. The size of this paper is applicable to the Chinese National Standard (CNS) 84 (210X297 mm) ~~ (Please read the precautions on the back before filling in this Page). Binding and ordering of the Ministry of Economic Affairs, Intellectual Property Bureau, 8 Industrial and Consumer Capital Cooperatives, 591333 A7 B7 V. Description of Invention (11) These can be used alone or in combination of two or more. The combination of phenols and ketones is particularly preferably a combination of pyrogenol and acetone. The condensation reaction product of phenols and aldehydes can be produced by a known method under an acidic catalyst. Examples of the acidic catalyst used in this case include hydrochloric acid, sulfuric acid, formic acid, citric acid, and p-tolylsulfonic acid. The condensed product thus obtained is preferably subjected to a treatment such as classification to remove the low-molecular domain, and it is desirable that the heat resistance is excellent. Treatments such as classification are performed by dissolving the resin obtained by the condensation reaction with a good solvent such as alcohols such as methanol and ethanol, ketones such as acetone and ethyl ethyl ketone, or ethylene glycol monoethyl ether acetate and tetrahydrofuran. , Followed by water and other methods. In the above-mentioned substance of the present invention, the total phenol-based repeating unit contains 60 mol% or more of P-cresol-based repeating unit and 30 mol% or more of m-cresol-based repeating unit. A phenolic lacquer type resin having a molecular weight (Mw) of 2,000 to 8,000 is desirable. P-cresol-based repeating units of less than 60 mol% tend to cause changes in sensitivity to temperature differences during heat treatment, and m-cresol-based repeating units of less than 30 mol% tend to deteriorate sensitivity. In addition, the alkali-soluble resin of the present invention may contain other phenol-based repeating units such as xylene-based repeating units or trimethylphenol-based repeating units, and most preferably 60-70 mol% of P-cresol-based repeating units, and The content of the two-component phenolic lacquer resin made of m-cresol-based repeating units of 40 to 30 mol%, the content of phenolic dinuclear bodies (condensation molecules with two phenolic cores) depends on GPC ) Method is preferably a low-molecular-weight phenolic lacquer resin with a low content of phenols of 10% or less. The above-mentioned dinuclear substances are used at high temperature (such as 1 3 (TC) pre-baked paper size applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) (please read the precautions on the back before filling out this page)-binding Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, 8th Industrial Cooperative Cooperative, and printed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumers' Cooperative, 591333 A7 B7 V. Description of the Invention (B) component (sensitivity enhancer): The (B) component of the present invention uses the phenol compound represented by the general formula (I) described above. Examples of the (B) component include tris (4-hydroxyphenylmethane). , Bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, bis ( 4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-methylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy -3,5-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2, 5-methylphenyl) -3-hydroxy Phenylmethane, bis (4-hydroxy-2,5-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-methylphenyl) -3,4-dihydroxybenzene Methane, bis (4-hydroxy-2,5-methylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-methylphenyl) -2,4-di Hydroxyphenylmethane, (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenyl Methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxy Phenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl]- 4- [1, Bubis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis ( 3-methyl-4-hydroxyphenyl) ethyl] benzene, 2- (2,3,4-trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4, dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4'-dihydroxybenzene paper size In use National Standard (CNS) A4 Specification (210X 297 mm): ---------- 1T ------ (Please read the precautions on the back before filling this page) 591333 A7 _B7_ printed by S.T.C. Consumer Cooperatives of the Citizenship and Welfare Bureau Among them, the esterification rate of 50% is the most ideal. On the one hand, the photosensitive component is formed by 1,2-naphthoquinonediazide-5-sulfonyl group of the compound 2,3,4,4'-tetrahydrobenzophenone represented by the formula (VIII). The compound benzoquinonediazide ester is desirable. Among them, those with an average esterification rate of 50 to 70% are ideal, and more preferably 55 to 65%. When it is less than 50%, film reduction is likely to occur after development, and the residual film rate is liable to decrease. On the other hand, when it exceeds 70%, storage stability tends to decrease. The photosensitive component 2 is preferably a very inexpensive sensitive and excellent photoresist composition from the viewpoint of being adjustable. Among them, the esterification rate of 59% is the most ideal. (C) Photosensitive components In addition to the above-mentioned photosensitive components 1 and 2, other benzoquinonediazide esters may be used, such as the phenol compound represented by the general formula (I) and 1,2-naphthoquinonediazide. A method for esterifying a -5- (4) -sulfonyl compound. All or a part of the phenolic hydroxyl group of the compound represented by the general formula (I) is esterified with naphthoquinonediazidesulfonic acid. According to a conventional method, for example, it can be obtained by condensing a naphthoquinonediazidesulfofluorenyl group with a compound represented by the general formula (I). Specifically, the compound represented by the general formula (I) and naphthoquinone chloride-1,2-diazidyl-4 (or 5) -sulfonyl group, in a specified amount of dioxane, η-methylpyrrolidone After dissolving organic solvents such as dimethylacetamide and tetrahydrofuran, basic catalysts such as triethylamine, triethanolamine, pyridine, alkali carbonate, and bicarbonate are added for reaction, and the resulting product is washed with water and dried to prepare a solution. The amount of the other quinonediazide esters mentioned above, in the (C) photosensitive component, is 30% by mass or less, and especially 25% by mass does not harm this (please read the precautions on the back before filling in this Page) • Binding 'Order it This paper size is applicable. National Standard (CNS) A4 (210 X 297 mm) -19- 591333 A7 B7 V. Description of the invention (16) The effect of the invention is ideal. (Please read the precautions on the back before filling out this page} The mixing ratio of the photosensitive components 1 and 2 is 40 to 60 parts by mass relative to 50 parts by mass of the photosensitive ingredient 1, especially 45 to 60 parts by mass. The range of 55 parts by mass is ideal. When the blending amount of the photosensitive component 2 is less than this range, the sensitivity tends to deteriorate, and in many cases, the resolution and linearity of the photoresist composition tend to deteriorate. Composition related to the present invention The compounding amount of the component (C) is 15 to 40 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B) of the alkali-soluble resin, and is preferably selected from a range of 20 to 30 parts by mass. C) When the compounding amount of the component is lower than the above range, a pattern of a faithful image cannot be obtained, and the transferability is reduced. On the one hand, when the compounding amount of the component is higher than the above range, the sensitivity and resolution are bad, and Residues tend to occur after image processing. When adjusting the photoresist composition for system LCDs, it is 20 to 40 parts by mass based on 100 parts by mass of the alkali-soluble resin (A) component and (B) component. It is ideal to choose from a range of 25 to 35 parts by mass The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the composition of the present invention. The components (A) to (C) and various additives are preferably used in the form of a solution in which the following (D) component of the organic solvent is dissolved. Related (D) Ingredient (organic solvent): Examples of the solvent used in the present invention include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isopentanone, and 2-heptanone; ethylene glycol, propylene glycol, and Ethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monobenzene Polyethers and their derivatives such as diethyl ether; such as dioxane. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 〇n '" 591333 Printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs A7 B7 V. Cyclic ethers of the invention description (17); and ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, Esters of ethyl ethoxypropionate, etc. These can be used alone or in combination The above combinations can also be used. Among them, propylene glycol monomethyl ether acetate (PGMEA) is also used to impart excellent coating properties to the photoresist composition of the present invention, and to impart excellent film thickness uniformity to the photoresist film on a large glass substrate. PGMEA is best used as a separate solvent, and solvents other than PGMEA can be used in combination with this solvent. Examples of this solvent include ethyl lactate, r-butyrolactone, and propylene glycol monobutyl ether. The mass ratio of PGMEA is 0.1 to 10 times the amount, and it is ideal to mix in the range of 1 to 5 times. In the field of manufacturing liquid crystal display elements, the photoresist film is usually 0.5 to 2.5 μm, especially on glass substrates. The thickness of the thin film must be 1.0 to 2.0 // m. Therefore, using these organic solvents, the total amount of the above (A) to (C) components in the composition is 30% by mass or less relative to the total mass of the composition. Ideally, it is adjusted to the range of 20 to 28% by mass. It is an ideal photoresist material for manufacturing liquid crystal display elements with excellent coating properties. In this case, the following (E) and the amount thereof can be used arbitrarily, and the amount of the solvent (D) to be used is 65 to 85% by mass with respect to the total mass of the composition, and preferably 70 to 75% by mass. The component (E) (other additives) related to the present invention is an ultraviolet absorber for preventing halo, such as 2,2 \ 4,4, tetrahydroxybenzophenone, 4 -Dimethylamine-2 \ 4'-dihydroxydibenzoyl (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -21-591333 A7 ___ B7 V. Description of the invention (21) After applying the sample to a glass substrate (550 × 650 mm2) with a chromium film, use a spinner to adjust the hot plate to 13 (TC, at intervals of about 1 mm) Dry for 60 seconds for the first approximation firing, adjust the hot plate temperature to i20 ° C, and dry for 60 seconds for the second approximation firing at 0.5 mm mm intervals to form a photoresist with a film thickness of 1.5 // m Secondly, to reproduce the photoresist pattern of 3.0 // m L & S (Line and Space), a pattern mask film using a test pattern film (cross line) drawn by intervention was used. Mirror Projection Aligner MPA-600FA (trade name, (Manufactured by CANON, Japan), 3.0 / zm L & S at the center of the substrate However, the exposure should be performed under the condition of 30 or less. Secondly, a developing device (device name · TD-39000 display machine with a slit coating nozzle) was used at 23 ° C with a 2.38% by mass TMAH aqueous solution. Manufactured by Tokyo Chemical Industry Co., Ltd., from the substrate ends X to Z (refer to FIG. 2), the solution was held for 10 seconds, held for 55 seconds, washed for 30 seconds in water, and spin-dried. Thereafter, the obtained The cross-sectional shape of the photoresist pattern is related to the end X, center Y, and end Z of the substrate. The SEM (scanning electron microscope) image is used to observe the pattern. The size of the pattern is 2.80 ~ 3.20 // m is 〇, X is lower than 2.80 // m, XX is higher than 3.20 // m, and the results are shown in Table 2. (3) Linear evaluation: The sample was coated with a chromium film using a spinner. Glass substrate (550 (please read the precautions on the back before filling out this page)-installed · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) -25 -591333 A7 __B7 5. After the description of the invention (22) X 650 mm2), adjust the hot plate to At 130 ° C, the first approximation firing is performed for 60 seconds at an interval of about 1 mm. Then, the hot plate temperature is adjusted to 120 ° C, and the second approximation firing is performed at an interval of 0.5 mm for 60 seconds. Photoresist film with a film thickness of 1.5 / zm. Next, a pattern mask film using a test pattern film (cross line) drawn by intervention was used to reproduce the photoresist patterns of 3.0 // mL & S '2.0 β m L & S and 1.5 / zm L & S with an i-ray exposure device. (Device name, FX-702 J, manufactured by NIKON, Japan), the central part of the substrate 3.0 // m L & S is selectively exposed with an exposure amount capable of reproducing such a size. Next, a developing device with a slit coating nozzle (apparatus name: TD-39000 display machine, manufactured by Tokyo Japan Chemical Industry Co., Ltd.) with a 2.38% by mass TMAH aqueous solution at 23 ° C was used as the substrate end X To Z (refer to FIG. 2) 'Contain liquid for 10 seconds, hold for 55 seconds, wash with water for 30 seconds, and spin dry. Thereafter, the obtained cross-sectional shape of the photoresist pattern is related to the end portion X, the central portion Y, and the end portion Z of the substrate and observed with a SEM (scanning electron microscope) image. 3.0 / zm L & S, The reproducibility of the photoresist pattern of 2.0 / zm L & S and 1.5 / zm L & S was evaluated from the actual photoresist pattern size, and the results are shown in Table 3. (Example 1) (A) Component: 100 parts by mass of alkali-soluble resin [weight average molecular weight (Mw obtained by adding oxalic acid and formaldehyde condensation reaction using a mixture of m-cresol 35 mole% and p-cresol 65 mole%) ) This paper size of 4,000 applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling out this page). 11 System-26- 591333 A7 V. Description of the invention (25 (however, the esterification rates of C2 ', C3, and C4 are 75%, 66%, and 66%, respectively) (Please read the precautions on the back before filling this page) Economy The paper size printed by the Ministry of Intellectual Property Bureau's Consumer Cooperatives applies the Chinese National Standard (CNS) A4 specification (210 > < 297 mm) -29- 591333

7 B V. Description of the invention (26) Printed by the consumer cooperation of the Intellectual Property Bureau of the Ministry of Economy [Table 1] (A) (B) [Mixed amount] (C) (Mixed ratio) [Mixed amount] (D) [Matched Amount] Solid content concentration (%) [(A + B + C) / (A + B + C + D) x 100] Example 1 GTR-M2 B1 [15 parts by mass] C1 / C2 (50/50) [ 26 parts by mass] PGMEA [423 parts by mass] 25 2 same as B2 [15 parts by mass] same as 25 3 same as B1 [15 parts by mass] same as PGMEA / EL (30/70) [423 parts by mass] 25 4 same as B1 [10 parts Parts] Same as above PGMEA [408 parts by mass] 25 5 Same as above C1 / C2 (50/50) [33 parts by mass] PGMEA [429 parts by mass] 25 6 Same as above C1 / C2 (50/50) [33 parts by mass] Same as above 25 Comparative Example 1 Same as Μ j \ w C2 [26 parts by mass] PGMEA [378 parts by mass] 25 2 Same as above 2,3,4,4'-tetrabenzophenol C1 / C2 (50/50) [26 mass Parts] PGMEA [423 parts by mass] 25 3 Ibid B1 [15 parts by mass] C2 [26 parts by mass] Ibid 25 4 Same as above I C1 P6 parts by mass] Ibid 25 5 Same as above C1 / C2 (50/50) [26 parts by mass ] PGMEA [260 parts by mass] 35.2 6 Same as above C3 / C2 (50/50) [26 parts by mass] PGMEA [423 parts by mass] 25 7 Same as above Above C4 / C2 (50/50) [26 parts by mass] Same as above 25 8 Same as B1 [10 parts by mass] C2 [33 parts by mass] PGMEA [429 parts by mass] 25 9 Same as above C4 / C2 (50/50) [33 Parts by mass] Ibid. 25 10 Ibid. B1 [50 parts by mass] C1 / C2 (50/50) [26 parts by mass] PGMEA [423 parts by mass] 29 (Please read the notes on the back before filling this page) This paper size applies China National Standard (CNS) A4 specification (210X297 mm) -30-

Claims (1)

591333 A8 B8 C8 D8 々 、 Scope of patent application 1 1. A positive type photoresist composition is characterized in that it contains 5 to 25 parts by mass of the alkali-soluble resin (A), and contains 5 to 25 parts by mass of the following general formula (1). Phenol compound (B) R10 R9 [wherein R1 to R8 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or carbon A cycloalkyl group having 3 to 6 atoms; V to R11 are shown as independent hydrogen atoms or a carbon group having 1 to 6 carbon atoms; Q is a hydrogen atom or a fluorenyl group having 1 to 6 carbon atoms, which is combined with R9 A cycloalkyl group forming a carbon atom chain of 3 to 6, or a group represented by the following chemical formula (II) (please read the precautions on the back before filling this page). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Silk Economy (where R12 and R13 show independent hydrogen, halogen, alkyl with 1 to 6 carbon atoms, and alkoxy with 1 to 6 carbon atoms Or a cycloalkyl group having 3 to 6 carbon atoms; c is an integer of 0 to 3); a and b are integers of 1 to 3; d is an integer of 0 to 3; n is an integer of 0 to 3 Integer of 0 to 3]; Contains 15 to 40 parts by mass of the benzoquinonediazide group represented by the following general formula (III) with respect to 100 parts by mass of the total mass of the component (A) and the component (B). Ester compound (photosensitive component 1) and benzoquinone shown by the following general formula (IV) The paper size applies to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ^ 34- 一 " 591333 A8 B8 C8 D8 • 、 Patent application scope 2 A mixture of photosensitive components (C) made of a diazide ester (photosensitive component 2) (Melon) (In the formula, R14 is an independent alkyl group having 1 to 5 carbon atoms; D is an independent hydrogen atom or 1,2-naphthoquinonediazide-5-sulfonyl group, At least one of D is 1,2-naphthoquinonediazide-5-sulfonyl; 1 and m are each independent 1 or 2) DO OD (IV) (wherein, [) shows an independent hydrogen atom, or a 1,2-naphthyldiazide- · 5-sulfonic acid group, and at least one of D is a zaquinonediazide -5-Sulfonyl (read first. Please note on the back before filling out this page.) The Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives printed more organic solvents (D). 2. The positive photoresist composition (B) according to item 1 of the patent application scope is a phenol compound represented by the following formula (V), where 0H (V) This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -35-591333 ABCD VI. Application for patent scope 3 3. For the positive photoresist composition in the first scope of patent application, where ( B) The component is a phenol compound represented by the following formula (VI). 4. For example, the positive photoresist composition in the scope of the patent application, wherein (A) component is a phenolic lacquer type resin with a weight average molecular weight (Mw) of 2000 to 8000 in terms of polystyrene, and its phenolic repeating unit It contains 60 mol% or more of P-cresol-based repeating units and 30 mol% or more of m-cresol-based repeating units. 5. The positive photoresist composition according to item 1 of the patent application, wherein the photosensitive component 1 is an average esterification of a phenol compound represented by the following formula (VII) and a 1,2-naphthoquinonediazide ester. Benzoquinonediazide esters with a rate of 40 to 60% · (Please read the precautions on the back before filling this page) • Equipment · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Photosensitive component 2 is a benzoquinonediazide esterified silk paper having an average esterification rate of 50-70% of a hydrazone compound represented by the following formula (VII) and 1,2-naphthoquinonediazide esterified product. Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) _ 36. 591333 A8 B8 C8 D8 6. Application scope 4 HO 0H Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. For example, the positive photoresist composition in the scope of patent application No. 1 in which (D) contains propylene glycol monomethyl ether acetate. 7. For example, the positive photoresist composition of the scope of patent application, wherein the total amount of (A), (B) and (C) components is 30% by mass or less relative to the total mass of the composition. 8. The positive photoresist composition according to any of claims 1 to 7 of the scope of patent application, which is used for manufacturing liquid crystal display elements. 9. For example, a positive photoresist composition in the scope of patent application No. 8 in which the above-mentioned liquid crystal display element is made by a glass substrate with a size of 500 X 600 mm2 or more. 10. The positive photoresist composition according to any one of claims 1 to 7, which is used for manufacturing a system LCD. 11 · The positive photoresist composition of item 10 in the patent application scope, in which the above system LCD is made by using a glass substrate with a size of 500 X 600 mm2 or more. 12. The positive photoresist composition according to item 10 of the patent application, wherein the system LCD is made by using an i-line (365 nm) exposure process. 1 3. A method for forming a photoresist pattern for the manufacture of a liquid crystal display element, comprising: (1) coating the photoresist composition with a positive photoresist composition according to any one of claims 1 to 7 The step of forming a coating film on a large glass substrate with a size of 500 X 600 mm2 or more, (2) the step of forming a photoresist film by heating the glass substrate forming the coating film, and (3) the paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) _ 37--------- install ------ order ----- reference silk • _ (Please read the precautions on the back first (Fill in this page again) 591333 A8 B8 C8 D8 6. Scope of patent application 5 (Please read the precautions on the back before filling out this page) Steps for selective exposure of the film, (4) Photoresist film after selective exposure A step of applying a development treatment using an alkaline aqueous solution to form a photoresist pattern on the glass substrate, and (5) a rinsing step of washing the developing solution remaining on the photoresist pattern surface. 14. For example, the method for forming a photoresist pattern in item 13 of the scope of patent application, wherein the above (3) selective exposure step is performed using a photoresist pattern with a different pattern size and a cover film with a drawn pattern. At the same time, photoresist patterns with different pattern sizes are formed on the glass substrate. 15. For example, a method for forming a photoresist pattern in the scope of application for patent No. 14, wherein the photoresist pattern with a different pattern size is a photoresist pattern with a size of 0.5 to 2.5 / zm. Patterned masking film for forming and a masking film (cross line) mixed with patterned masking film for patterning of photoresist patterns with a pattern size of 3 to 10/2 m. 16. The method for forming a photoresist pattern according to item 13 of the patent application, wherein (3) the selective exposure step is an exposure process using an i-line (365 mm) as a light source. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -38- This paper size is applicable to National Standards (CNS) A4 (210X: 297 mm)