TW200300866A - 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

200300866 A7 B7 V. Description of the invention (1) 1. The technical field to which the invention belongs (please read the precautions on the back before filling out this page) The present invention is related to photoresist compositions, especially liquid crystal display elements, and is particularly applicable Positive photoresist composition for manufacturing liquid crystal display devices using large glass substrates of more than 500 mm X 600 m m2, and positive photoresist composition suitable for system LCD manufacturing. 2. The prior art has been relatively inexpensive in the field of manufacturing liquid crystal display elements using glass substrates. Most of them use photoresist patterns that can form sensitivity, resolution, and shape. 'Phenolic resin containing benzoquinone diazide Positive photoresist material for the manufacture of semiconductor elements based on base compounds. However, for the manufacture of semiconductor elements, only round silicon wafers with a maximum diameter of 8 inches (about 200 mm) to 12 inches (300 mm) can be used, and the manufacture of liquid crystal display elements uses square glass of 500 mm X 600 mm2 or more. Substrate. In the field of manufacturing of liquid crystal display elements, of course, the material and shape of the substrate coated with the photoresist composition are different. The biggest difference from silicon wafers is the size. 0 It is better to focus on the improvement of the overall characteristics of the photoresistive materials used in the manufacture of liquid crystal display elements and the fine characteristics required in the field of semiconductor element manufacturing. The overall characteristics include, for example, the formation of a coating film with no difference in coating on a large substrate surface, the heat treatment of large substrates due to the unstable heating, and the formation of a photoresist pattern with excellent shape and dimensional stability. During the development process, 'the large substrate is caused by less development differences, and the shape and size stability are excellent. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -5- Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative 200300866 A7 _________ B7 V. Description of the invention (2) Photoresistance pattern, etc. In addition, since the manufacture of liquid crystal display elements requires a large amount of photoresist materials to be consumed, materials other than characteristics are also expected to be inexpensive materials. Conventional photoresist materials for semiconductor device manufacturing cannot sufficiently obtain this characteristic. For example, the materials specifically described in Japanese Patent Application Laid-Open No. 丨 0_ 丨 42783 cannot fully discover the above-mentioned overall characteristics. On the one hand, there have been many reports of photoresist materials for the manufacture of liquid crystal elements so far. Examples include Japanese Patent Laid-Open No. 9-160231, Japanese Patent Laid-Open No. 9_ 2 1 1 855, and Japanese Patent Laid-Open No. 2000- 1 1 2 1 20 Japanese Patent Laid-Open No. 2000- 1 3 1 835, Japanese Patent Laid-Open No. 2000- 1 8 1 055, and Japanese Patent Laid-Open No. 2001-7 5 272. These materials are cheaper and have a smaller size of 360 X 460 mm2, which can form a photoresist pattern with excellent coating, sensitivity, resolvability, shape and size stability. However, for large substrates with a substrate size of 500 X 600 mm2 or more, the coatability is a problem. The peripheral and central portions of the substrate are subject to changes in the size of the pattern due to heating instability, and the end and end portions of the substrate are not visible. The development of image instability caused by time difference is a major problem. Therefore, in the field of manufacturing large-scale liquid crystal display devices in Japan and North Korea, the use of large substrates with a size of 500 X 600 mm2 or more is expected, and a photoresist material with excellent overall characteristics is expected. On the one hand, the next-generation LCD (liquid crystal display element), the collective circuit of the driver, DAC (digital-to-analog conversion), day image processing program, image controller, RAM and other display parts are simultaneously formed on a single glass substrate. Formation and development of high-performance LCD technology called "system LCD" now (please read the precautions on the back before filling in this page)

This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -6-200300866 A7 _B7 V. Description of the invention (3) Very popular (Semiconductor FPD World 200 1.9, pp. 50 — 67) ο (Please Please read the notes on the back before filling in this page) However, the size of the pattern of the relative display part is about 3 ~ 10 / zm, the size of the pattern of the collective part must be formed as a small size of about 0.5 ~ 2.5 / zm, the same For the exposure conditions, to form this collective circuit and display part, expect to have excellent linearity . In addition, when forming a photoresist pattern with a small size of about 0 · 5 to 2 · 5 // m, it is necessary to change the exposure from the conventional g-line (436 nm) exposure to the short-wavelength i-line (365 nm) exposure. Lithography. However, conventional photoresist materials for the manufacture of liquid crystal display elements are not suitable for i-line exposure materials with excellent linearity, and development of materials to solve this problem is expected. 3. Summary of the Invention [Problems to be Solved by the Invention] An objective of the present invention to print by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is to provide a low-cost, overall characteristic (coatability) for a large glass substrate manufacturing process. , Heating instability, and development instability) are also excellent photoresistive materials. Another object of the present invention is to provide a photoresist material with excellent linearity suitable for system LCD manufacturing and suitable for i-line exposure. [Problem solving means] In order to solve the above-mentioned problems, the present inventors have thoroughly researched the results, and found a specific mixing ratio of alkali-soluble resins and specific chemical structure phenol compounds (This paper is applicable to the standard. National Standard (CNS) A4 Specifications (210 X 297 mm) ~ " 200300866 Α7 Β7 V. Description of the invention (4) Sensitization enhancer), and 2 kinds of benzoquinonediazide ester compounds (photosensitive components) with specific chemical structure The photoresist composition can be used as a material for solving the above-mentioned g-problem, and has reached the present invention. That is, the present invention refers to 100 parts by weight of the alkali-soluble resin (A), -25 parts by mass of the phenol compound (B) represented by the following general formula (I), and contains R 10 Rb

-(〇H) b (1) a radical having 1 to 6 atoms, a radical having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; R9 to R11 are shown as each independently A hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which is combined with R9 to form a cycloalkyl group having a carbon atom chain of 3 to 6, or the following chemical formula The base shown in (II)

JL _Lp13 (〇H) c -------- install-(Please read the precautions on the back before filling this page) Order

R 12. (Π) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where R12 to R13 show independent hydrogen, halogen, alkyl with 1 to 6 carbon atoms, and 1 to 6 carbon atoms) Alkoxy group 6 or 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 Η is an integer of 0 to 3]; It contains 15 to 40 parts by mass of benzoquinone di 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). The scale of the folded paper is applicable to the Chinese National Standard (CNS) A4 specification (210 > < 297 mm) -8- 200300866

A7 B7 V. Description of the invention (5) Photosensitive component formed of nitrogen-based esterified product (photosensitive component 1) and benzoquinonediazide-based esterified product (photosensitive component 2) represented by the following general formula (IV) Mixture (C) (In the formula, R14 is an independent alkyl group having 1 to 5 carbon atoms; D is an independent hydrogen atom, or 1,2-naphthyldiazide-5-fluorenyl group 'At least one shown in D is 1,2-naphthoquinonediazide-5 -sulfofluorenyl; 丨 and m are each independently 1 or 2) (Please read the precautions on the back before filling in this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where D is an independent hydrogen atom, or 1,2-naphthoquinonediazide-5-sulfonyl, and at least one of D is 1 , 2-naphthoquinonediazide-5-sulfonyl); and a positive photoresist composition characterized by an organic solvent (D). According to the present invention, it is possible to provide a photoresist material that is inexpensive and excellent in overall characteristics (coatability, heating instability, and development instability) when used in a large glass substrate process. Furthermore, it provides photoresistive materials with excellent linearity suitable for system LCD manufacturing and i-line exposure. The component (B) is preferably a phenol compound represented by the following formula (V) or (VI). This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -9- 200300866 A7 B7 V. Description of the invention (6

C——C——C

OH

CH3 (V)

(VI) (Please read the notes on the back before filling this page) Intellectual Property Bureau of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperative)

These compounds are highly sensitive photoresist films, high residual film rate, and excellent linear improvement. The above-mentioned (A) component contains 60 mol% or more of P-cresol-based repeating units and 30 mol% or more of cresol-based repeating units in its all repeating units, and its polystyrene equivalent weight average molecular weight (Mw) Phenolic lacquer type resin of 2000 ~ 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 an average esterification of a phenol compound and 1,2-naphthoquinonediazide esterified product represented by the following formula (VII) (ΥΠ): The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297) (Mm) -10- 200300866 A7 B7 V. Description of the invention (7) A benzoquinonediazide esterified product having a ratio of 40 to 60%, and the photosensitive component 2 is represented by the following formula (VIII)

(Please read the precautions on the back before filling this page) The average esterification rate of the phenol compound and 1,2-naphthoquinonediazide esterified product is 50 ~ 70%. ideal. By using these two kinds of photosensitive components, the positive-type photoresist of the present invention can provide excellent overall characteristics (coatability, heating instability, and development instability), high residual film rate, good sensitivity, and preservation. Photoresist material with good stability The photoresist composition of the present invention preferably contains propylene glycol monomethyl ether acetate (PGMEA) as the component. Since the PGMEA is contained, the photoresist composition of the present invention can be excellent in coating properties and excellent in film thickness uniformity of the photoresist film on a large glass substrate. The Intellectual Property Bureau of the Ministry of Economic Affairs (the total amount of the components (A), (B), and (C) printed by the industrial and consumer cooperatives is preferably less than 30% by mass relative to the total mass of the composition. This makes the above The content of the organic solvent in the photoresist composition is large, and the total amount of the components (A), (B), and (C) is reduced, so that the positive photoresist composition described above can be an excellent coater. The positive photoresist composition is particularly suitable for the manufacture of liquid crystal display elements. The positive photoresist composition of the present invention has excellent overall characteristics (coatability, heating instability, and development instability), and residual film Those with a high rate and good sensitivity. In addition, the above-mentioned liquid crystal display device uses a large size of 500 X 600 mm2 -11-the standard of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Printed 200300866 A7 __B7_ 5. Description of the invention (8) The glass substrate is ideally made. The positive photoresist composition of the present invention is particularly ideal for system LCD manufacturing. The positive photoresist composition of the present invention has excellent linearity and can be i-line exposure will be small Simultaneous exposure with a large pattern to form a photoresist pattern. The above system LCD is ideally made using a large glass substrate of 500 x 600 m2. The above system LCD uses i-line (365 nm) exposure It is ideal for the producer of the process. It can form a good fine pattern of 0.5 ~ 2.5 // m degree. And the present invention is (1) the positive photoresist composition containing the above is coated on 500 X 600 a step of forming a coating film on a large glass substrate of at least mm2, (2) a step of forming a photoresist film on the glass substrate after the above-mentioned coating film-forming glass substrate is subjected to heat treatment (pre-baking), and (3) the above-mentioned light The selective exposure step of the resist film, (4) the step of forming a photoresist pattern on the above-mentioned glass substrate by using an alkaline aqueous solution for the photoresist film after the selective exposure, and (5) washing The rinsing step of the developing solution remaining on the surface of the photoresist pattern described above is a method for forming a liquid crystal display pattern having a characteristic of the liquid crystal display pattern. Although the photoresist pattern used in the manufacture of the liquid crystal display element is 500, X 600 mm2 large glass substrates The above (3) selective exposure step is performed using a photoresist pattern with a different pattern size and a patterned cover film, and a pattern size is formed on the glass substrate at the same time. Those with different photoresist patterns. This paper size applies to China National Standard (CNS) A4 specifications (210X 297 public holidays) ~ (Please read the precautions on the back before filling in this page j

C • Order 200300866 Α7 Β7 V. Description of the invention (9) (Please read the precautions on the back before filling out this page) The photoresist patterns with different pattern sizes mentioned above should be at least the used size. 5 ~ 2 · 5 // m pattern mask film for photoresist pattern formation and pattern size 3 ~ 1 0 // m pattern mask film mixed with pattern mask film (cross line ) The performer is ideal. At this time, a photoresistive pattern having a pattern of 0 · 5 to 2 · 5 // m size and a pattern of 3 to 1 0 // m size 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 (365 mm) light source. Since a pattern with high dimensional accuracy can be formed by using the i-line, the positive-type photoresist composition of the present invention can be exposed using i-line and subsequent development. [Implementation form of the invention] Relevant (A) component: Alkali-soluble resin printed as (A) component by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and there is no particular limitation. Among the winners, the film-forming substance was arbitrarily selected. For example, examples of the resin for forming a thin film of a positive photoresist composition include phenol resin, acrylic resin, copolymer of styrene and acrylic acid, polymer based on styrene, polyethylene fluorene, and poly α-methyl. Ethylphenol, etc. Among them, phenolic lacquer resins which are not swellable and easily dissolved and developed by an alkaline aqueous solution are preferable. Examples of phenol resins include condensation reaction products of phenols and aldehydes, condensation reaction products of phenols and ketones, vinyl phenol-based polymers, and the Chinese paper standard (CNS) A4 specification (applicable to this paper standard) ( 210X297 mm) -13- 200300866 A7 ___ B7 _ 5. Explanation of the invention (10) Isopropene phenol-based polymers, hydrogenation reaction products of these phenol resins, etc. (Please read the notes on the back before filling this page) The phenols forming the above phenol resins include phenol, m-cresol, P-cresol, 0-cresol, 2,3-xylenol, 2 Xylphenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol; ethylphenol, p-ethylphenol, 0-ethylphenol, 2,3,5-trimethylphenol Phenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol , 2-tert-butyl-5-methylphenol and other alkyl phenols; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p- Propoxyphenol, m-propoxyphenol, etc. alkoxyphenols; o-isopropenol, P-isopropenol, 2-methyl-4-isopropenol, 2-ethyl-4-iso Isopropenols such as propene phenol; aryl phenols such as phenylphenol; 4,4'_ diacryl diphenol, bisfluorene A, m-xylylenedifluorene, p-xylylenedifluorene, pyrofluorene, etc. Hydroxyphenols and so on. These may be used alone or in combination of two or more. Among these phenols, m-acetol, p-cresol, 2,5-xylol, 3,5-xylenol, and 2,3,5-trimethylphenol are particularly preferred. The above-mentioned aldehydes printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs can be listed as formaldehyde, paraformaldehyde, trioxin, acetic acid, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, butyraldehyde, cyclohexanaldehyde, furan Aldehyde, furan acrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, ^ -phenylpropanal, Θ-phenylpropanal, 0-mercaptobenzoic acid, m-mercaptobenzoic acid, p- Benzaldehyde, 0-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzoic acid, 0-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamic acid, etc. It can be used alone or in combination of two or more. Among these wake-ups, 'the formic acid starting from Gu Yi is preferable', and in particular, a combination of a benzaldehyde and formaldehyde is preferably used to improve heat resistance. The above ketones can be exemplified by acetone, methyl ethyl ketone, diphenyl ketone, etc. The size of this paper is applicable to Chinese National Standard (CNS) A4 (210X 297 mm), 14 < 200300866 A7 B7 V. Description of the invention (11) These may 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. (Please read the precautions on the back before filling out this page.) The condensation reaction products of phenols and aldehydes can be produced by known methods under an acid 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 excise the low-molecular domain, which is excellent in heat resistance. Treatments such as classification are dissolved in a good solvent such as alcohols such as methanol, ethanol, ketones such as acetone, methyl ethyl ketone, or ethylene glycol monoethyl ether acetate, tetrahydrofuran, etc. according to the condensation reaction. Next, it is carried out in water by a method such as coagulation and precipitation. In the above-mentioned substance of the present invention, the total phenolic repeating unit contains 60 mol% or more of P-cresol-based repeating units and 30 mol% or more of m-cresol-based repeating units, and its polystyrene equivalent weight average A phenolic lacquer type resin having a molecular weight (Mw) of 2,000 to 8000 is desirable. P-cresol-based repeating units of less than 60 mol% tend to cause sensitivity changes due to temperature differences during heat treatment, and m-cresol-based repeating units of less than 30 mol% tend to deteriorate sensitivity. The Bureau of Intellectual Property of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperatives and said that the alkali-soluble resin of the present invention may contain xylene-based repeating units "or other phenol-based repeating units such as trimethylphenol-based repeating units, most preferably P-formaldehyde 60 to 70 mol% of phenolic repeating unit, 40 to 30 mol% of m-cresol based repeating unit, two-component phenolic lacquer resin, phenolic dinuclear (condensation product with two phenolic cores) (Molecule) content is preferably a low-molecular-weight phenolic lacquer resin containing less than 10% phenols by GPC (colloidal permeation chromatography) method. The above-mentioned dinuclear material is pre-baked at a high temperature (eg, 130 ° C). The Chinese paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -15-200300866 A7 B7 V. Description of the invention (12) Sublimation and contamination of the ceiling of the furnace, and pollution of the photoresist coated glass plate becomes the yield The reason for the decline. (Please read the precautions on the back before filling out this page.) About the component (B) (sensitivity enhancer The component (B) of the present invention uses the phenol compound represented by the general formula (I) above) Intellectual Property Bureau, Ministry of Economic Affairs Cargo Workers' Cooperatives Seal Examples of the component (B) include tris (4-hydroxyphenylmethane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, and bis (4-hydroxy-2,3,5-tris Methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-methylbenzene Group) -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-hydroxyphenylmethane, bis (4-hydroxy-2,5-methylphenyl) -2-hydroxybenzene Alkyloxane, bis (4-hydroxy-3,5-methylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-methylphenyl) -3,4- Dihydroxyphenylmethane, bis (4-hydroxy-2,5-methylphenyl) -2,4-dihydroxyphenylmethane, (4-hydroxyphenyl) -3-methoxy-4-hydroxybenzene Methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3- Hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl -4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane, 1- [丨-(4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4 -Hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxybenzene Group) ethyl] benzene, 2- (2,3, cardiotrihydroxyphenyl) -2- (2 \ 3 \ 4, trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl)- 2- (2 ', 4, dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4, dihydroxybenzene) Paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297) PCT) 200300866 Α7 Β7 V. Description of the invention (13) (Please read the notes on the back before filling this page) Basic) Bingyuan, 2-(3-fluoro-4 -hydroxyphenyl) -2-(3 '- Fluoro-4'-hydroxyphenyl), 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- ( 4. Hydroxy U-dimethylphenyl) propane, 2- (2,3,4-trihydroxyphenyl) methane, 2- (2,4-dihydroxyphenyl) methane, 2,3,4-tris Hydroxyphenyl-4, hydroxyphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,4- [b (4-hydroxyphenyl) Propyl] -5-hydroxy-phenol. Among them, those with excellent sensitivity improvement effects include bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane and bis (4-hydroxy-2,3,5-trimethylphenyl) -2 -Hydroxyphenylmethane, 2,4- [1- (4-hydroxyphenyl) isopropyl] -5-hydroxyphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1- [1 -(4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene is desirable. In the field of liquid crystal display devices, increasing the production capacity is a very big problem. It is ideal to achieve high sensitivity and help increase the production capacity based on the compounding of the phenol compound. In addition, according to the compound of the phenol compound, the photoresist film can strongly form a surface hardly soluble layer, and the film loss of the photoresist film that is not exposed during the development is reduced, and the occurrence of the development instability caused by the time difference of the development can be suppressed. As ideal. Among the phenol compounds printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the compound shown in (V) above (1- [Ια-hydroxyphenyl) propyl] -4- [1,1- (4-hydroxyl Phenyl) ethyl] -benzene) and the compound shown in (VI) above (bis (2,3,5-trimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane), with high sensitivity, It is desirable to have a high residual film rate and excellent linear improvement. When the (B) component is used as the composition of the present invention, the content is 5 to 25 parts by weight relative to 100 parts by mass of the alkaline soluble resin of the component (A). The paper standard is applicable to Chinese National Standard (CNS) A4 specifications ( 210 × 297 mm) -17- 200300866 A7 B7 5. Description of the invention (14), ideally selected from the range of 0 to 20 parts by weight. (Please read the precautions on the back before filling in this page.) Below the lower limit of this range, the enhancement effect of high sensitivity and high residual film rate cannot be fully obtained. When the upper limit of this range is exceeded, the surface of the substrate after development is easy. Residues occur, and the cost of raw materials becomes high. When adjusting the photoresist composition for the system LCD, the proportion of the component (B) is 5 to 20 parts by weight relative to 00 parts by weight of the alkali-soluble resin (A). Ideally, it is 7 to 15 parts by weight. The range of servings is preferably selected. Forms with different sizes also fall within this range, and can achieve sufficient high sensitivity and high residual film rate improvement effects. Component (C): A benzoquinonediazide esterified product (photosensitive component 1) represented by the general formula (III) and a benzoquinonediazide esterified product (photosensitive component) represented by the general formula (IV) are used. 2) Mixed materials, when making large glass substrates with a size of 500x 600 mm2 or more, a photoresist material that can provide excellent overall characteristics (coatability, heating instability, and development instability). Photoresistive materials with excellent linearity and i-line exposure are available for system LCD manufacturing. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Industrial Cooperative Cooperative. The average esterification rate of the photosensitive component 1 is preferably 40 to 60%, and more preferably 45 to 55%. When it is less than 40%, film reduction is easy to occur after imaging, and the residual film rate is easy to decrease. When it exceeds 60%, the sensitivity tends to deteriorate significantly. The photosensitive component 1 is 1,2- of a compound represented by the formula (VII) (bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-dihydroxyphenylmethane). Naphthoquinonediazide-5-sulfonyl benzoquinonediazide esterate is a relatively inexpensive photoresist composition with excellent sensitivity, resolution, and linearity. It can be adjusted to the size of this paper for China Standard (CNS) A4 specification (210X297 mm) 200300866 Α7 B7 V. Description of the invention (15) The whole point is ideal. Among them, the esterification rate of 50% is the most ideal. (Please read the precautions on the back before filling out this page) — In terms of the photosensitive component, the 1,2-naphthalene of the compound 2,3,4,4'-tetrahydrobenzophenone represented by the above formula (VIII) A compound formed from a quinonediazide-5-sulfonyl group is a benzoquinonediazide esterified product. 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 low-sensitivity 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. --5- (4) -Ester of sulfofluorenyl compound. All or part of the phenolic hydroxyl group of the compound represented by the general formula (I) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is naphthoquinone diester The process of esterifying nitrogen sulfonic acid can be carried out according to a conventional method. For example, it can be obtained by condensing a naphthoquinonediazidesulfonamido chloride with a compound represented by the general formula (I). Specifically, the compound represented by the above general formula (I) and naphthoquinone chloride-1,2-diazidyl-4 (or 5) -sulfonyl If group, in a specified amount of After the organic solvents such as alpha ketone, dimethylacetamide, and tetrahydrofuran are dissolved, triethylamine, triethanolamine, pyridine, alkali carbonate, and bicarbonate are added to the basic catalyst to react. The material was washed with water and dried. The use amount of the other quinonediazide esters mentioned above in the photosensitive component (C) is 30% by mass or less, and especially 25% by mass does not damage the paper. The Chinese National Standard (CNS) applies A4 specification (210 × 297 mm) -19- 200300866 A7 B7 5. 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. A range of 55 parts by mass is desirable. When the blending amount of the photosensitive component 2 is less than this range, the sensitivity tends to deteriorate, and when it is in this range, the resolution and linearity of the photoresist composition tend to deteriorate. Regarding the composition of the present invention, the blending 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 component (A) and (B) of the alkali-soluble resin, and the range is from 20 to 30 parts by mass. The choice is ideal. (When the blending amount of the component is lower than the above range, a pattern of a faithful image cannot be obtained, and the transferability is lowered. On the one hand, when the blending amount of the component (C) 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 the 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, and the following (D) of an organic solvent The component is preferably used in the form of a solution. (D) Component (organic solvent): Examples of the solvent used in the present invention include acetone, methyl ethyl ketone, cyclohexanone, methyl isopentanone, and 2-heptane. Ketones such as ketones; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or these monomethyl ethers, monoethyl ethers , Monopropyl ether, monobutyl ether, or monophenyl ether And its derivatives; such as dioxane-20- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 200300866 A7 _____ B7 V. Description of the invention (17) (Please read the precautions on the back before (Fill in this page) of cyclic ethers; and ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxypropionic acid Ester such as ethyl ester. These can be used alone or in combination of two or more kinds. Among them, propylene glycol monomethyl ether acetate (PGMEA) is also used to impart excellent coating properties to the photoresist composition of the present invention. It is ideal to impart excellent film thickness uniformity to a 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. Examples of such solvents include ethyl lactate, r »butyl Lactone, propylene glycol monobutyl ether, etc. The mass ratio of ethyl lactate to PGMEA is 0 to 1 to 10 times, and it is ideal to mix in the range of 1 to 5 times. About the manufacture of liquid crystal display elements 5 〜 The photoresist film is usually 0.5 ~ 2.5 " m, especially the thin film on the glass substrate must be 1.0 ~ 2.0 // m. Therefore, using these organic solvents, the above (A) in the composition ~ Intellectual Property Bureau of the Ministry of Economic Affairs 8 Industrial Cooperative Cooperative The total amount of printed components is 30% by mass or less with respect to the total mass of the composition, and is preferably adjusted to the range of 20 to 28% by mass. It is a photoresist material for manufacturing a liquid crystal display element having excellent coating properties. The following (E) and cakes can be arbitrarily used at the time, and the amount of the solvent (D) used is 65 to 85% by mass, and preferably 70 to 75% by mass for the total mass of the composition. (E) Ingredients (other additives) are within the scope of not impairing the object of the present invention, and are ultraviolet absorbers for preventing halo, for example, 2,2,4,4-tetramenthyl-monomethanone, 4-monomethyl Amine-2 ', 4'-dihydroxy dibenzoyl This paper is sized to the Chinese National Standard (CNS) A4 (210X 297 mm) '-------21-200300866 Λ7 B7 V. Description of the invention ( 18) ketone, 5-amino-3-methylbuphenyl-4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'- Di-, 4-ethylamino-4'ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin, etc., or surfactants to prevent streaks, such as FLORATO FC-430, FC431 (trade names , Fluorine-based surfactants such as Sumitomo 3M Co., Ltd., F-TOP EF-122A, EF-122B, EF-122C, EF126 (trade name, manufactured by TOKAM PRODUCT Co., Ltd.), etc. Stabilizers such as ketones, peronaphthone, and P-toluenesulfonic acid can be added as necessary. To the extent that they do not interfere with the purpose of the present invention, additives containing additional resins, plasticizers, stabilizers, contrast enhancers, etc. can be added. Custom additives. For an example of a method for forming a photoresist pattern suitable for manufacturing a liquid crystal display element using the composition of the present invention, first, on a square glass substrate, (A) to (C) components, and additional components used as necessary (E) The solution dissolved in the appropriate solvent (D) is applied using a spin coater to form a coating film. The glass substrate used at this time is 500 X 600 mm2 or more, and it can also be a large board of 550 x 650 mm2 or more. By using the composition of the present invention to manufacture a liquid crystal display element (including a system LCD) using a large glass substrate, excellent overall characteristics (coatability, heating instability characteristics, and aberration characteristics) and excellent linearity can be obtained. Resistive pattern. Next, the glass substrate on which the coating film is formed is heated and dried (pre-fired) at about 100 to 140 ° C to form a photosensitive layer. Next, ultraviolet rays are used as light sources, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and xenon lamps are used to intervene in a desired pattern cover film for selective exposure. In addition, for the manufacture of system LCDs, this selective exposure is performed by using a patterned masking film for the formation of photoresist patterns with different pattern sizes. The paper size is subject to Chinese National Standard (CNS) A4 specifications ( 210X 297 mm) (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-22- 200300866 A7 _B7 _ V. Description of the invention (19) (Please read the back first Note on this page, please fill in this page again), the above-mentioned glass substrate can be formed at the same time with different patterns. For example, for this selection light, a patterned mask film for forming a photoresist pattern having a pattern size of 0.5 to 2.0 // m and a pattern for forming a photoresist pattern having a size of 3 to 1 0 // m can be used. Masking film (cross line). In this way, patterns with different sizes can be formed at the same time, and the excellent linear effect of the photoresist composition of the present invention can also be exerted. In this case, it is desirable to use an i-line to form a fine pattern. Continuing, the exposed photoresist-coated glass substrate is coated with a developing solution, such as an alkaline aqueous solution of 1 to 10% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution, from one end of the plate to the other end, and The liquid is sprayed from a developing liquid dropper provided near and above the center, and the entire substrate is supplied with liquid. The liquid holding method from one end of the substrate to the other end is to use a large glass substrate to form a photoresist pattern. The device can be simplified and extremely useful. When the liquid is held from one end to the other end of the board, the respective ends The liquid holding period is different. The photoresist composition at this end is different from the alkaline developing solution in time, which is the cause of unstable imaging. With the photoresist composition of the present invention, the development instability is extremely small and there is no problem in implementation. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The photoresist pattern is formed on the above glass substrate for about 50 to 60 seconds. Thereafter, the developing solution remaining on the photoresist pattern surface is subjected to a rinsing step of washing off with a rinsing solution such as pure water. 4. Embodiment The physical properties of the positive-type photoresist composition are obtained in the following manner. -23- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 200300866 A7 B7 V. Description of invention (20) (1) Evaluation of heating instability (please read the precautions on the back before filling this page) ) Using a spinner to coat the sample on a glass substrate (550 X 650 mm2) where a chromium film has been formed, adjust the hot plate to not :, and dry the first proximity baking for 60 seconds at an interval of about 1 mm. Secondly, the temperature of the hot plate was adjusted to 120 ° C, and the second proximity baking was performed for 60 seconds at 0.5 mm mm intervals to form a photoresist film with a thickness of 1.5 // m. In the second drying step, the substrate temperature of the substrate edge portion A is about 105 ° C, the substrate temperature of the substrate center portion B is 110 ° C, and the substrate temperature of the core portion of the substrate is 115 ° C (refer to FIG. 1). ). Secondly, a pattern mask film including a test pattern film (cross line) for interventional drawing was used to reproduce a photoresist pattern of 3.0 // m L & S (Line and Space). Mirror Projection · Aligner MPA-600FA (brand name, Japanese version) (Manufactured by CANON Co., Ltd.). 3.0 / mL & S of the central portion of the substrate is selectively exposed at an exposure amount capable of reproducing such a size. However, the exposure should be performed under 30 conditions. Next, it was contacted with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ° C for 60 seconds, washed with water for 30 seconds, and spin-dried. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ The cross-sectional shape of the obtained photoresist pattern is related to the outer edge portion A, the central portion B, and the core portion C of the above substrate by SEM (scanning electron microscope) ) According to the photographic observation, the size of the pattern is 2.90 ~ 3.10 // m is 0, those below 2.90 μm are X, and those above 3.10 / m are XX. The results are shown in Table 2. (2) Evaluation of development instability This paper is in accordance with Chinese National Standard (CNS) A4 size (210X297 mm) 200300866 A7 _B7 V. Description of the invention (21) (Please read the precautions on the back before filling this page) Use rotation After the sample was coated on a glass substrate (550 X 650 mm2) where a chromium film had been formed, the hot plate was adjusted to 13 (TC, and the first approximation firing was performed at an interval of about 1 mm for 60 seconds, followed by drying. The temperature of the hot plate was adjusted to 120 ° C, and the second proximity baking was dried for 60 seconds at 0.5 mm mm intervals to form a photoresist film with a thickness of 1.5 // m. Second, to reproduce 3.0 // m L & S ( Line and Space) photoresist pattern uses the mask pattern of the test pattern film (cross line) drawn by intervention ^^!:!:.!; Projection · Aligner MPA-600FA (trade name, manufactured by CANON, Japan), The central part of the substrate 3.0 // m L & S is selectively exposed at an exposure amount that can reproduce the size. However, the exposure amount is performed under the condition of 30 m or less. Second, at 2.38 mass% TMAH aqueous solution at 23 ° C. , Using a development device with a slit coating nozzle (device name: TD-3 9000 display machine, manufactured by Tokyo Chemical Industry Co., Ltd., from the substrate end X to Z (refer to Figure 2), holding the liquid for 10 seconds, holding it for 55 seconds, and then washing it for 30 seconds with water and spin drying it. The cross-sectional shape of the photoresist pattern obtained by the employee's consumer cooperative of the Ministry of Intellectual Property Bureau was printed. The end X, center Y, and end Z of the substrate were observed with a SEM (scanning electron microscope). The size of the pattern is 2.80 to 3.20 // 111 is 0, and the number is less than 2.80 // 111 is \ '. The number is greater than 3.20 // 111 is > < \, the results are shown in Table 2. 3) Linear evaluation: The sample was coated on a glass substrate on which a chromium film has been formed using a spinner (55 paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 〇 > < 297 mm) -25 = · 200300866 A7 B7 V. Description of the invention (22) (Please read the precautions on the back before filling in this page) X 650 mm2), then adjust the hot plate to not :, perform the first time at an interval of about i mm Drying by proximity baking for 60 seconds, followed by adjusting the hot plate temperature to 120 ° C, and performing a second proximity baking for 60 seconds at 0.5 mm mm intervals It is dried to form a photoresist film with a thickness of 1 · 5 / zm. Second, the photoresist pattern of 3.0 " m L & S '2.0 μm L & S and i.5 / zm L & S is reproduced using interventional drawing The test pattern film (cross line) of the pattern cover film is an i-ray exposure device (device name, FX_702), made by NIKON Corporation of Japan, 3.0 / m L & S to reproduce as large as The amount of exposure for selective exposure. Next, a developing device with a slit coating nozzle (apparatus name: TD-39000 display machine, manufactured by Tokyo Japan Chemical Industry Co., Ltd.) was used with a 2.38% by mass TMAH aqueous solution at 23t, and the substrate ends X to Z were used. (Refer to Figure 2) 'Contain liquid for 10 seconds, hold for 55 seconds, wash with water for 30 seconds, and spin dry. Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the cross-sectional shape of the photoresist pattern obtained later by the cooperative, and related the end X, center γ, and end Z of the substrate with a SEM (scanning electron microscope) photo As observed, the reproducibility of the photoresist pattern of 3.0 / zm L & S, 2.0 / zm L & S, 1.5 / zm L & S was evaluated from the actual photoresist pattern size, and the results are shown in Table 3. Show. (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% The paper size of 4000 is suitable for financial standards (CNS) A4 size (210x7 ^ Gongchu) -26- 200300866 A7 ________ 87____ V. Description of the invention (23) (Please read the precautions on the back before filling this page) Cresol novolac Type lacquer resin obtained through classification treatment, Mw = 4500, cresol novolac type lacquer resin (product name, GTR-M2 'Made by Japan Group Chemical Co., Ltd.') having a dinuclear content of phenols of about 6%. The dinuclear content of phenols was measured by GPC using the following apparatus and conditions. Device ·· SYSTEM 11 (Japan P Matsukoku Electric Co., Ltd.) PRECOLOUM: KF-G (made by SH0DEX); C0L0UM: KF-802 (made by SH0DEX); Detector: UV41 (at 280 nm (Measurement); Conditions of solvent, etc .: Tetrahydrofuran flow rate of 1.0 m / min, measured at 35.0. (B) Component: Sensitizer (B1: Phenol compound represented by the above formula (V)): 15 parts by weight (C) Component · Photosensitive component i / Photosensitive component 2 [50/50 (mass ratio) ] ·· 26 parts by mass (Photosensitive component 1: ci: 1 mole of the compound represented by the formula (VII) and 1, 2 naphthoquinonediazide-5-sulfonic acid chloride (hereinafter referred to as 5- "NQD" Description) 2 Molar esters (esterification rate 50%); photosensitive components 2 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs: C2: Compound 1 Molar and 5-NQD 2.34 Mo Ear esters (esterification rate 59%) (D) Ingredients · Solvent (PGMEA) · 423 parts by mass of the above (A) ~ (D) components are uniformly dissolved, and the membrane filter with a pore size of 0.2 # m It is filtered and prepared into a positive photoresist composition. The composition is measured for the above-mentioned heating instability and development instability, and the results are shown in Table 2. The paper size is applicable to towel steel household fresh (CNS) M specifications. (21 () X 297) -27- 200300866 A7 _______B7 V. Description of the Invention (24) (Examples 2 to 6, Comparative Examples 丨 to ί) The components of (A) to (D) are shown in Table 1. Show In addition, various positive photoresist compositions were prepared in the same manner as in Example i. The above-mentioned heating instability, development instability, and linearity related to this composition were measured, and the results are shown in Tables 2 and 3 as described above. The abbreviations and contents of the compounds used in the examples and comparative examples are as follows: 'Bi'Cl, C2 is as described above, 2, C, 2, C3, C4 and EL are as described below. 5B. (Double (2, 3, 5 -Trimethyl · 4-hydroxyphenyl) -2-hydroxyphenylmethane) Hexagonal pain: C2 '(Compound of formula (III) 1 mole and 5_Nqd3 tritium | Compound) Hexylamine: C3 (Bis (3,5-dimethyl-4-hydroxy) -2-hydroxyphenylmethane (described below) 1 mole and 5_NqD2 mole of benzoquinonediazide esters) (Please read first Note on the back then fill out this page} Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Industry and Consumer Cooperatives

1 Wu Er and 5-NQD4 Mole Benzoquinone Diazide Esterate

OH mesh number: EL (ethyl lactate)

200300866 A7 B7 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) Bureau of Intellectual Property, Ministry of Economic Affairs The paper size printed by employee consumer cooperatives is in accordance with the Chinese National Standard (CNS) A4 specification (210X 297 mm) -29- 200300866 V. Description of the invention (26) [Table 1] Printed by S Industrial Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs 经济⑻ [Mixing amount] (C) (Mixing ratio) [Mixing amount] (D) [Mixing 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 Ibid. B2 [15 parts by mass] Ibid. 25 3 Ibid. B1 [15 parts by mass ] Ibid. PGMEA / EL (30/70) [423 parts by mass] 25 4 Ibid. B1 [10 parts by mass] Ibid. PGMEA [408 parts by mass] 25 5 Ibid. Ibid. 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 25 Comparative Example 1 Same as above JSW C2 [26 parts by mass] PGMEA [378 parts by mass] 25 2 Same as above 2,3,4,4 , Tetrabenzol C1 / C2 (50/50) [26 Quantities] PGMEA [423 parts by mass] 25 3 Ibid. B1 [15 parts by mass] C2 [26 parts by mass] Ibid. 25 4 Ibid. Ibid. C1 [26 parts by mass] Ibid. 25 5 Ibid. Ibid. 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 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] same as above 25 10 Same as B1 [50 parts by mass Γ C1 / C2 (50/50) [26 parts by mass] PGMEA [423 parts by mass] 29 (Please read the notes on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)- 30- 200300866

7 7 A B

V. Description of the invention (27) [Table 2] Heating 3 (1) ^ Stability evaluation (#m) (1) Heating development evaluation (" m) Substrate outer edge portion Substrate center portion Substrate core portion Substrate end portion Substrate center Substrate end ABCXYZ Actual I 200000 Application 2 200000 Example 3 30000 40000 1 0 XX X XX 2 X 〇XX 〇〇〇〇 3 X 〇XX X 〇XX is less than 4 _ 1) _ 1) _ 1) _ 1) 1) _ 1) Example 5 • 2) • 2) _ 2) 2) 2) _ 2) 6 X 〇 XX 〇〇 〇 7 X Ο XX X Ο XX (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1) The conditions of exposure below 30 cannot form a separation pattern. 2) A photoresist film with a thickness of 1.5 / zm cannot be formed. As is clear from Table 2, when the specific component of the present invention is not used, the development of the photoresist composition may be unstable, and the heating instability may be significantly deteriorated. -31-This paper size applies Chinese National Standard (CNS) A4 specification (210X 297mm) 200300866 A7 ______B7 V. Description of the invention (28) __ [Table 3 1.50 Example 5 1.50 6 1.5 2 Comparative Example 8 1.95 9 1.89 10 _ 3) ^ _____ ^ — one (3) linear evaluation (um) ----- 2.00 3.00 2.00 called 3.00 2.00 3.00 2.01-3.00 ^^ ~ * 2.01-3.00 3) (Please read the precautions on the back first Fill in this page again)-Binding and binding 3) There are too many residues, and the resulting shape cannot be an excellent photoresist pattern for evaluation. As is clear from Table 3, when the specific component of the present invention is not used, the linearity of the photoresist composition film is poor. Efficacy of the invention Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, according to the present invention, provides a low-cost, large-scale glass substrate process that can be used for 5000x600mm2 or more. Photoresistive material with excellent stability and development instability). According to the present invention, a photoresistive material pattern suitable for system LCD manufacturing and suitable for i-line exposure can be provided. The paper wave size is applicable to China National Standard (CNS) A4 (210X297 mm) -32- 200300866 A7 _______ B7 V. Description of the invention (29) [Figure 1] (Please read the precautions on the back before filling in this f) The heating is unstable, the positive photoresist composition is coated on the sloped glass substrate, and the substrate is pre-baked and dried The areas of the outer edge portion A, the substrate center portion β, and the substrate core portion C are illustrated. [Figure 2] For g parity development is unstable and linear, a positive photoresist composition is coated on a glass substrate 'After pre-baking and drying, after the pattern is exposed, the developing liquid is passed from the substrate end with a slit coater The illustrations of the meanings of the sections X to Z containing the liquid. Component comparison table A: Substrate outer edge part B: Substrate center part C: Substrate core part X: Substrate part Y: Substrate center part Z: Substrate part Part of the Ministry of Economic Affairs, Intellectual Property Bureau, Employee Consumption Cooperative Print f -33- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm)

Claims (1)

200300866 8 8 8 8 ABCD Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Scope of patent application 1 1 · A positive photoresist composition characterized by containing 5 to 25 parts by mass of the following with respect to 100 parts by weight of an alkali-soluble resin (A) Phenol compound (B) represented by general formula (I) R10 R9 [wherein R1 to R8 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms Alkoxy, or a cycloalkyl group having 3 to 6 carbon atoms; R9 to RU show each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom or 1 to 6 carbon atoms Alkyl, a cycloalkyl group bonded to R9 to form a carbon atom chain of 3 to 6, or a group represented by the following chemical formula (II) (In the formula, R12 and R13 are not 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. Base; 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]; relative to 100 mass Parts (A) and (B) of the total mass of the component, containing 15 to 40 parts by mass of the benzoquinonediazide esterified product (photosensitive component 1) represented by the following general formula (III) and the following general formula (IV) Benzoquinone (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 34 _ 200300866 8 8 8 8 ABCD VI. Patent application scope 2 Diazide ester (photosensitive component 2) Photosensitive component Mixture (C) (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, and D is shown At least one of them is 1,2 · naphthoquinonediazide-5-sulfonyl; 1 and m are each independent 1 or 2) (Please read the precautions on the back before filling this page) Do D Do CHO D 〇 (IV (wherein D is an independent hydrogen atom or 1,2-naphthoquinonediazide- · 5-sulfofluorenyl group, and at least one of D is 1,2-naphthoquinone Diazyl-5-sulfonyl group also contains organic solvents (D). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 2. For example, the positive photoresist composition in the first scope of the patent application, where (B) component Is a phenol compound OH represented by the following formula (V). OH (V) -35- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297mm) 200300866 A8 B8 C8 D8 VI. Patent application scope 3 3 · If the photoresistance composition of the first patent scope is applied (B) is a phenol compound represented by the following formula (VI). 4. The positive photoresist composition according to item 1 of the patent application range, wherein (A) component is a polyphenol-equivalent lacquer-type resin having a weight average molecular weight (Mw) of 2,000 to 8000 in terms of polystyrene, and the entire phenolic repeating unit thereof 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-type photoresist composition according to item 1 of the 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 ratio of 40 ~ 60% · II— III-—.---—- I -i i. SI--I n (Please read the precautions on the back before filling this page) Printed by aT Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs The photosensitive component 2 is a benzoquinonediazide esterified product having an average esterification rate of 50 to 70% of a phenol compound and 1,2-naphthoquinonediazide esterified product represented by the following formula (VII). Applicable to China National Standard (CNS) A4 specification (2 〖0X297mm） -36-Silk · 200300866 Application for patent scope 4 HO HO OH c- O ABCD OH (VIII) (Please read the precautions on the back before filling out this page) 6. If the positive photoresist composition in item 1 of the patent application scope, the (D) component further contains propylene glycol monomethyl ether acetate. 7. For example, the positive photoresist composition in 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 one of claims 1 to 7, which is used for manufacturing a liquid crystal display element. 9. For example, the positive photoresist composition in the scope of patent application No. 8 in which the above-mentioned liquid crystal display element is made by using 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 · If the positive photoresist composition of item 10 of the patent application scope, wherein the above system LCD is made by using a glass substrate of 500 X 600 mm2 or more. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 12 · For example, the positive photoresist composition in the scope of patent application No. 10, where the above system LCD is made using i-line (3 65 nm) exposure process. 1 3 · A method for forming a photoresist pattern for manufacturing 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 heat-treating the glass substrate forming the coating film. Standards are applicable to Chinese National Standards (CNS) M specifications (21〇 < 297 public directors) 200300866 ABCD VI. Application for patent scope 5 The steps of selective exposure of the film, (4) the photoresist film after the above 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 · if applying for a patent The method for forming a photoresist pattern in the item 13 of the range, wherein the above (3) selective exposure step is performed using a photoresist pattern with a different pattern size using a cover film with a pattern drawn, and simultaneously on the glass Pattern size phase 1 5 · The method for forming a photoresist pattern according to item 14 of the scope of application for a patent, wherein the photoresist pattern with a different size of the above pattern has a size of 0.5, and the size of the cover film is 0.5. ~ 2.5 // m photoresist pattern forming pattern cover film and pattern size 3 to 1 0 // m photoresist pattern forming pattern cover film mixed drawing pattern film (cross line). 16 · For example, for the method of forming a photoresist pattern in the scope of patent application No. 13, where (3) the selective exposure step is performed by using an i-line (365 mm) as the light source. (Please read the precautions on the back first (Fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-38- This paper size applies to China National Standard (CNS) A4 (210X297 mm)