TW200428142A - Positive photoresist composition for manufacturing system LCD, manufacturing method for the positive photoresist and formation method of resist pattern - Google Patents

Abstract

A positive photoresist composition is provided which is excellent in storage stability and is favorable for manufacturing system LCD having integrated circuits and liquid crystal display portions on a substrate. The positive photoresist composition for manufacturing system LCD is obtained by dissolving into an organic solvent, (A) an alkali soluble resin, (B) a naphthoquinonediazido ester compound containing esterification reaction product of a compound represented by the following general formula (I) with 1,2-naphthoquinonediazide sulfonyl compound, (C) a phenolic hydroxyl group-containing compound with a molecular weight no more than 1000, and (D) a reduction inhibiting agent.

Description

200428142 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a positive-type photoresist composition for LCD manufacturing in which an integrated circuit and a liquid crystal display portion are formed on a substrate. The positive-type photoresist composition Material modulation method and method for forming photoresist pattern using the positive photoresist composition. [Previous technology] Conventionally, most of the photoresist materials used in the manufacture of semiconductor elements, liquid crystal display elements (LCD), and especially TFTs are exposed by light suitable for the ghi line (g-line, h-line, and i-line). Inexpensive, high sensitivity, phenolic lacquer resin for alkali-soluble resins, photosensitive component (hereinafter abbreviated as PAC) phenolic lacquer-naphthoquinonediazide positive photoresist for compounds containing naphthoquinonediazide groups Composition (refer to, for example, Patent Documents 1 to 4). When manufacturing an LCD, since only the pixel portion of the display is formed on the substrate, the positive photoresist composition has a sensitivity capable of forming a very coarse pattern (for example, about 3 to 5 μm). Therefore, PAC is mainly used for the esterification reaction product of low-priced diphenyl ketone phenol compound and 1,2-naphthoquinonediazide-5-succinyl compound (diphenyl ketone PAC ). In addition, the diphenyl ketone PAC has excellent storage stability, especially small changes in sensitivity over time. The photoresist pattern formed in the LCD manufacturing is also the same as above, and the target is an extremely coarse size. So far, the storage stability of the photoresist composition is stable. No problem. In recent years, for the new generation of LCD, drivers, DACs (digital-to-analog converters), image processors, and video controllers are simultaneously formed on a glass substrate with the display part of -5- (2) (2) 200428142. High-function LCDs called "system LCDs" with integrated circuit parts such as RAM, RAM, etc., have prevailed in technology development (see, for example, Non-Patent Document 1). Hereinafter, in this specification, an LCD in which an integrated circuit and a liquid crystal display portion are formed on a substrate in this manner is conveniently referred to as a system LCD. In such a system LCD, for example, the pattern size of the display portion is about 2 to 10 μm, and in contrast, the integrated circuit portion is formed with a fine size of about 0.5 to 2.0 μm. Therefore, the positive photoresist composition used in the manufacture of system LCDs has the basic requirement of the ability to form fine patterns and coarse patterns with good shapes (high resolution and linearity) simultaneously. Also, as the substrate of the system LCD, low-temperature polycrystalline silicon, especially low-temperature polycrystalline silicon formed by a low-temperature process below 600 ° C, is suitable because of its low resistance and high mobility. Therefore, the development of a system LCD using low-temperature polycrystalline silicon as a substrate is being actively carried out. The composition suitable for the manufacture of a system LCD using low-temperature polycrystalline silicon is expected to be developed. In the manufacture of the system LCD described above, fine light is formed. It is difficult to apply the conventional diphenyl ketone pAc suitable for ghi line exposure, and it is predicted that the use of non-diphenyl ketone PAC suitable for i line exposure is suitable. In addition, since it is necessary to form a fine photoresist pattern, as in the manufacture of the above-mentioned semiconductor device, the change in the photoresist characteristics over time is strictly controlled, and a photoresist composition with excellent stability is expected to be required. However, as far as the present inventors know, the light-containing (3) (3) 200428142 non-diphenyl ketone PAC-containing resist composition has a good resolution and is difficult to maintain stability. Changes over time may cause changes in photoresistance characteristics such as sensitivity and resolution. Therefore, when the photoresist composition is stored, it is necessary to strictly control the storage temperature in a temperature range of about 0 to 20 ° C. Moreover, even with such temperature control, there is still a problem of preservation stability of not more than six months. Because of the change of the photoresistance characteristics over time, the shape of the photoresist pattern formed is affected, and the cost of tight temperature control is high, which is still not suitable for the manufacture of system LCDs. Patent Literature 1 Japanese Patent Laid-Open No. 2000-1 3 1 83 5 Patent Literature 2 Japanese Patent Laid-Open No. 2001-75272 Patent Literature 3 Japanese Patent Laid-Open No. 2000-1 8 1 055 Patent Literature 4 Japanese Patent Laid-Open No. 2000-112120 Patent Document 1 Semiconductor FPD World 2001.9, pp.50-67. [Summary of the Invention] The problem to be solved by the invention Therefore, the problem of the present invention is to provide a system LCD suitable for forming an integrated circuit and a liquid crystal display part on a substrate, and containing non-diphenyl ketone PAC photosensitivity. Ingredients, and store a positive photoresist composition with excellent stability, a modulation method of the positive photoresist composition, and a method of forming a photoresist pattern. Means to solve the problem

In order to solve the above problems, the inventors have carefully studied and found that PAC (4) 200428142 is a positive reaction product of an esterification reaction using a non-diphenyl ketone-based polyphenol compound and a 1,2-naphthoquinonediazidesulfonium compound. In the photoresist composition, a positive photoresist composition obtained by blending with an anti-reducing agent such as benzoquinone. The phenomenon that the photoresistance characteristics change with time during the storage in the bottle is suppressed, and the stability of storage is improved. Materials suitable for the manufacture of system LCDs complete the present invention. That is, the present invention is characterized in that (A) an alkali-soluble resin and (B) contain the following general formula (I)

R > • if (• / R8 R ”

(〇H) b… ① [wherein R1 to R8 each independently represent 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 3 to 6 carbon atoms Cycloalkyl; R11 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R9 may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; at this time, Q1 represents a hydrogen atom and a carbon atom of 1 Alkyl formula to 6 of the following chemical formula (II)

(Wherein R12 and R13 each independently represent a hydrogen atom, a halogen atom, a carbon atom-8- (5) (5) 200428142 alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, or carbon atoms A cycloalkyl group of 3 to 6; c represents an integer of 1 to 3), or Q1 may be bonded to the terminal of R9, at this time, Q1 together with R9 and the carbon atom between Q1 and R9, indicating the carbon chain A cycloalkyl group of 3 to 6; a and b are integers of 1 to 3; d is an integer of 0 to 3; a, b or d is 3 each without R3, R6 or R8; η is an integer of 0 to 3. ] The naphthoquinonediazide ester product of the esterification reaction of the compound with 1,2-naphthoquinonediazidesulfonium sulfonium compound, (C) a compound containing a phenolic hydroxyl group with a molecular weight of 1,000 or less, and (D) an anti-reducing agent It is obtained by dissolving in an organic solvent, and can form a positive type photoresist composition (hereinafter referred to as the positive type photoresist composition of the present invention) for LCD manufacturing of integrated circuits and liquid crystal display parts on a substrate. The present invention also provides a method for preparing the positive photoresist composition in which the resin solution containing the component (D), the component (B), and the component (C) are mixed in an organic solvent solution in which the component (A) is mixed. In addition, the present invention provides: (1) a step of applying the positive photoresist composition on a substrate to form a coating film; and (2) performing a heat treatment (preliminary process) on the substrate on which the coating film has been formed. Baking), the step of forming a photoresist film on the substrate, (3) For the above photoresist film, use a photomask pattern for forming a photoresist pattern below 2.0 μm, and a photoresist for forming a photoresist pattern exceeding 2.0 μm The photomasks of the two mask patterns are subjected to the steps of selective exposure, (4) the step of applying heat treatment (post-exposure baking: PEB) to the photoresist film after the selective exposure, and (5) the above heat treatment. The photoresist film is subjected to a development treatment using an alkaline aqueous solution to simultaneously form a photoresist pattern for an integrated circuit having a pattern size of less than 2.0 μm on the above substrate, and a photoresist pattern for a liquid crystal display portion exceeding 2.0 μm Step of the light-9- (6) (6) 200428142 Method for forming a resist pattern. [Embodiment] The present invention will be described in detail below. "Positive Photoresist Composition for LCD Manufacturing" < (A) component > (A) Component is alkali-soluble resin (A) component is not particularly limited 'can be formed from a coating film which can generally be used as a positive photoresist composition Among the material ones, one kind or two or more kinds are arbitrarily selected. For example, 'phenols (phenol, m-cresol, p-cresol, xylenol, tricresol, etc.), and aldehydes (formaldehyde, formaldehyde precursors, propionaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, etc.) and / or ketones (butanone, acetone, etc.), phenolic lacquer resins obtained by condensation in the presence of acid catalysts; hydroxystyrene monopolymers, hydroxystyrene and other styrenes Copolymers of monomers, copolymers of hydroxystyrene with acrylic acid or methacrylic acid or its derivatives; hydroxystyrene resins such as copolymers of acrylic acid or methacrylic acid and its derivatives; acrylic or methacrylic resins. Phenolic lacquer containing at least two phenols selected from the group consisting of m-cresol, p-cresol, 3,4-xylenol and 2,3,5-tricresol and formaldehyde-containing aldehydes Resin, suitable for the modulation of photoresist with high sensitivity and excellent resolution. (A) The component can be produced by a general method. (A) The average polystyrene-equivalent mass of the component subjected to gel permeation chromatography is -10- (7) (7) 200428142 The molecular weight varies depending on the type, but it is based on sensitivity and pattern formation. It is 2,000 to 1,000,000, more preferably 3,000 to 300,000. The component (A) can be produced by a general method. < (B) component > (B) The component is a naphthoquinonediazide quinone compound, an esterification reaction product containing the phenol compound of the general formula (VII) and a 1,2-naphthoquinonediazidesulfonium compound ( It is hereinafter referred to as non-diphenyl ketone PAC). The positive photoresist composition containing the non-diphenylketone-based PAC has high sensitivity and high resolution. In addition, it is suitable for photolithography using i-rays, and is also good in linearity and depth of focus (DOF). In the general formula (I), R1 to R8 each independently represent a hydrogen atom, a halogen atom, and a carbon. A straight or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group having a straight chain or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; R1 (), R11 each independently represents a hydrogen atom, or a straight or branched alkyl group having 1 to 6 carbon atoms; R9 may be a hydrogen atom or a straight or branched alkyl group having 1 to 6 carbon atoms, and at this time Q1 represents a hydrogen atom , A linear or branched alkyl group having 1 to 6 carbon atoms, or a residue of the above formula (II), or Q may be bonded to the terminal of R9, at this time Q1 together with R9 and the carbon between Q1 and R9 Atoms, cycloalkyl groups of carbon chains 3 to 6; a, b are integers of 1 to 3; (1 are integers of 0 to 3; n are integers of 0 to 3; and Q1 and R9 together with Q1 and R9 Carbon atom, when forming a cycloalkyl group of carbon chain 3 to 6, 'Q1 and R9 are combined to form an alkylene group having 2 to 5 carbon atoms. The phenol compound of general formula (I) is, see (4-hydroxyphenyl group) ) Methane, bis (4-hydroxy-1, 3-tolyl), 2 Hydroxyphenyl methane, bis (4-hydroxyphenyl a -11--200428142

2,3,5_trimethylphenyl) _2_hydroxybenzyl'bis (4-hydroxy-3,5-xylyl) -4-hydroxybenzyl, bis (4-hydroxy-3,5-xylyl) ) A 3_ via Benzene Institute, bis (4_ via _3,5-xylyl) _2-hydroxybenzyl, bis (4-hydroxy_2,5-xylyl) -4-hydroxybenzyl, Bis (4-hydroxy_2,5_xylyl) _3_hydroxybenzyl, bis (4_hydroxy-2,5_xylyl) -2_hydroxybenzyl, bis (4-hydroxyl-3, 5_xylyl) _3,4-dihydroxybenzyl, bis (4-hydroxyl-2,5-xylyl) -3,4_dihydroxybenzyl, bis (4-hydroxyl_2,5-di Tolyl) _2,4-one via Benzene Institute, bis (4-via phenyl) _3-methoxy-4-hydroxybenzyl, bis (5_cyclohexyl-4-hydroxy_2_tolyl)-4 —Hydroxybenzyl, bis (5-cyclohexyl-4_hydroxy-2—tolyl) —3_hydroxybenzyl, bis (5—cyclohexyl-4—hydroxy_2—tolyl) -2—hydroxybenzyl , Bis (5_cyclohexyl-4-hydroxyl_tolyl) -3,4_dihydroxybenzyl and other phenolic compounds; 2,4_bis (3,5_dimethyl_4 monohydroxybenzyl) ) _5_hydroxyphenol, 2,6 _Bis (2,5_dimethyl-4-hydroxybenzyl) -4-cresol and other linear trisphenol compounds; 1,1 bis [3_ (2_hydroxy_5_toluylmethyl) -4 —Hydroxy-5_cyclohexylphenyl] isopropane, bis [2,5-dimethyl_3_ (4_hydroxy_5 —toluylmethyl) -4 —hydroxyphenyl] methane, bis [2,5 —di Methyl-3- (4-hydroxybenzyl-4-hydroxyphenyl) methane, bis [3- (3 ;;

, 5-Dimethyl_4_hydroxybenzyl] -4_hydroxy-5-tolyl] methane, bis 3- [3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5_ Ethylphenyl] methylamine, bis [3- — (3'5_diethyl-4_ via benzyl) —4- _5_tolyl] methane, bis [3_ (3,5_diethyl_4_hydroxy Benzyl) _4 -12- (9) (9) 200428142 —Hydroxy-5_ethylphenyl] methane, bis [2_hydroxy_3- (3,5-dimethyl-4-4-hydroxyphenylmethyl) — 5_tolyl] methane, bis [2-hydroxy_3— (2_hydroxy-5—tolylmethyl) -5-tolyl] methane, bis [4-hydroxyl_3_ (2 —hydroxyl-5 —toluidine) A) 5-tolyl] methane, bis [2,5 —dimethyl—3 — (2 — via —5 —toluylmethyl) — 4 — via phenyl] methylbenzene, etc., tetralins; 4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-tolylmethyl] -6_cyclohexylphenol, 2,4-bis [4-hydroxy-3_ (4-hydroxybenzyl) ) _5 —Toluylmethyl] _6_cyclohexylphenol, 2,6-bis [2,5 —dimethyl_3_ (2 —hydroxy-5 —toluylmethyl) — 4-hydroxybenzyl]-4 -methyl Phenol and other linear polyphenol compounds, such as pentachlorophenol; bis (2,3,4_trihydroxybenzene Group) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4_trihydroxybenzene-4'_hydroxyphenylmethane, 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'-hydroxyphenyl) propane-2-(3_fluoro_4_hydroxyphenyl) -2- (3'_fluoro_4'_hydroxyphenyl) propane, 2_ (2, 4_ —Phenyl) —2— (4′_Phenyl) propionate, 2- (2,3,4-trihydroxyphenyl) _2— (4′—hydroxyphenyl) propane, 2_ (2, 3,4_trihydroxyphenyl) -2- (41-hydroxy-3,5'-xylyl) bisphenol compounds such as propane; 1- [1 ((4-hydroxyphenyl) isopropyl] 1 4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4_hydroxyphenyl) isopropyl] -4- [1,1_bis ( Polymethylbenzene branched compounds such as 3-methyl-4-hydroxyphenyl) ethyl] benzene; and condensation phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane. -13- (10) (10) 200428142 These can be used singly or in combination of two or more kinds. Among them, ginsenolate-based compounds are used as the main component, which has high sensitivity and better resolution, especially bis (5-cyclohexyl-4-hydroxy-2-2-tolyl) -3,4-dihydroxybenzyl [ Abbreviation (B Γ). : I. Bis (4-hydroxyl-2,3,5_trimethylphenyl) _2_hydroxyphenylmethane [hereinafter referred to as (B3 '). ] Is better. It is also a photoresist composition that has excellent overall balance of photoresistance characteristics such as modulation resolution, sensitivity, heat resistance, DOF characteristics, and linearity, in order to combine linear polyphenol compounds, bisphenol compounds, polybenzene branched compounds, and condensation types. Phenol compounds and the like are preferably used with the above-mentioned phenol-type compounds, especially bisphenol-type compounds, among which bis (2'4-dihydroxyphenyl) methane [hereinafter referred to as (B2 '). ] Can be used to produce a photoresist composition with excellent overall balance. Hereinafter, each of the naphthoquinonediazide esters of (BΓ), (B2 ·), and (B3 ·) is abbreviated as (B1), (B2), and (B3). When (B1) and (B3) are used, the amount of each of the components (B) is preferably 10% by mass or more, and more preferably 15% by mass or more. It may be 90% by mass or less, and more preferably 85% by mass or less. Because (Bl), (B2), and (B3) are all effective when used, each blending amount is (B1) 50 to 90% by mass '60 to 80% by mass, and the (B2) blending amount is 5 to 2 5 The mass% '10 to 5 mass% is more preferable, the (B 3) compounding amount 5 to 25 mass%, and more preferably 10 to 15 mass%. The phenolic hydroxyl group of the compound of general formula (I) mentioned above, all or a part of the naphthoquinonediazide sulfonate esterification method may be a general method. For example, it can be prepared by condensing naphthoquinonediazidesulfonium chloride with the compound of the general formula (I). -14- (11) (11) 200428142 Specifically, for example, the compound of the above general formula (I), and naphthoquinone-1,2-diazide-4 (or 5) -pentyl chloride can be specified to The amount is dissolved in organic solvents such as dioxane, N-methylpyrrolidone, dimethylacetamide, and tetrahydrofuran, and one or more basic catalysts such as triethylamine, triethanolamine, pyridine, sodium carbonate, and sodium bicarbonate are added thereto. The reaction was performed, and the obtained product was washed with water and dried to prepare it. (B) The components are as described above. In addition to the preferred naphthoquinonediazide esters exemplified above, other naphthoquinonediazide esters which are generally used as the photosensitive component of a positive photoresist composition can be used. Esterification reaction products of phenolic compounds such as hydroxydiphenyl ketone and alkyl gallic acid with naphthoquinonediazidesulfonic acid compounds. These other naphthoquinone diazide esters can be used arbitrarily, or two or more kinds can be selected. The use amount of these other naphthoquinonediazide esters is 80% by mass or less, especially 50% by mass or less of the component (B), and the effect of the present invention is improved. The blending amount of the (B) component in the photoresist composition is 20 to 70% by mass, and more preferably 25 to 60% by mass relative to the total amount of the (A) and (C) components. The blending amount of the (B) component is as described above. Above the lower limit, a faithful image can be obtained on the pattern, improving the transferability. When it is below the upper limit 値, the deterioration of sensitivity can be prevented, the uniformity of the formed photoresist film can be improved, and the effect of improving the resolution can be obtained. The photoresist characteristics required for the photoresist composition in system LCD manufacturing are as follows. For example, with system LCD, in the field of LCD manufacturing, there is a need for high sensitivity based on improving the controllability of (12) (12) 200428142 output and processing. In the manufacturing of LCDs, glass substrates larger than those in the semiconductor field are used. Therefore, in order to increase the exposure area, an exposure procedure using a low NA (numerical aperture of lens: numerical aperture) condition is preferred. Among them, those who use LCDs, in addition to the display part, also form integrated circuit parts on the substrate. The substrate tends to be larger, so it is lower than when manufacturing LCDs, such as 0.3 or less, especially 0.2 or less. Low NA exposure procedures are preferred. For the above exposure procedures under low NA conditions, the resolution tends to deteriorate. In the system LCD, for example, the pattern size of the display part is about 2 to 10 μm. In contrast, the integrated circuit part is formed to 0.5 to 2 · Fine size of about 0μm, so high resolution can form fine photoresist patterns. It is also required that the photoresist pattern of the display part with greatly different dimensions and the linear pattern of the photoresist pattern of the integrated circuit part can be formed correctly at the same time. In the present invention, as the component (B), an esterification reaction product of a specific phenol compound of the general formula (I) and a 1,2-naphthoquinonediazidesulfonium sulfonium compound can be used to obtain high-sensitivity conditions such as low NA conditions. Positive photoresist composition with high resolution and good linearity. < (C) component > (C) The component is a compound containing a phenolic hydroxyl group. The use of this component (C) can obtain excellent sensitivity improvement effect, i-line exposure under low NA conditions (13) 200428142 High sensitivity, high resolution and excellent linearity in the program are suitable for the positive photoresistance composition of the system LCD Thing. The molecular weight of the component (C) is 1,000 or less, more preferably 700 or less, and essentially 200 or more, and particularly 300 or more, is more effective than the above effects. (C) If the component is a phenolic hydroxyl group-containing compound that is generally used as a sensitivity enhancer or sensitizer in a photoresist composition, it is preferred that there is no special restriction for satisfying the above molecular weight conditions, and one or two can be selected arbitrarily the above. Among them, the following general formula (III)

[Wherein R21 to R28 each independently represent 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 cycloalkyl group having 3 to 6 carbon atoms; R3l), R31 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R29 may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in this case, Q2 is a hydrogen atom and an alkyl group having 1 to 6 carbon atoms Or the residue shown in the following chemical formula (IV)

". (IV) -17- (14) (14) 200428142 (where R32 and R33 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms Group, or a cycloalkyl group with 3 to 6 carbon atoms; g represents an integer from 0 to 3), or Q2 can be bonded to the terminal of R29 'At this time, Q2 together with R29 and the carbon atom between Q2 and R29, table A cycloalkyl group having 3 to 6 carbon atoms; e, f are integers of 1 to 3; h is an integer of 0 to 3; e, "or 11 is 3, each does not have R23, R26 or R28; m represents 0 to An integer of 3] is preferably a phenol compound because the above characteristics are good. More specifically, for example, bis (3-methyl-4-hydroxyphenyl) -4 other than the phenol compound of general formula (I) used in the naphthol diazide ester as exemplified in the above-mentioned (B) component _Cumene methane, bis (3-methyl-4-hydroxyphenyl) benzene methane, bis (2-methyl-4-hydroxyphenyl) benzene methane, bis (3-methyl-2-hydroxyphenyl) benzene methane , Bis (3,5_dimethyl_4_hydroxyphenyl) benzenemethane, bis (3-ethylene-4-hydroxyphenyl) benzenemethane, bis (2-methyl-4-hydroxyphenyl) benzenemethane, bis ( Phenyl-type compounds such as 2-tertiary butane-4,5-dihydroxyphenyl) benzenemethane are applicable. Among them, bis (2-methyl-4 monohydroxyphenyl) benzene methane and I-. — (4-hydroxyphenyl) isopropyl] —4-mono [1 ’1-bis (4-hydroxyphenyl) ethyl] benzene is preferred. The blending amount of the component (C) is 10 to 70% by mass, and more preferably 20 to 60% by mass relative to the component (a). < (D) component > (D) The component is an anti-reducing agent. The use of an anti-reducing agent can obtain a positive photoresist composition which is excellent in stability and suitable for a system LCD. The present inventors have discovered that one of the reasons for the poor storage stability of the composition using the conventional non-diphenylketone PAC (15) (15) 200428142 is that the non-diphenylketone PAC has a higher acidity than the diphenylketone. The PAC is low, so the acidity of the photoresist composition using the PAC is relatively low, so the reduction effect in the photoresist composition is easy to carry out, and the photoresist characteristics in the bottle are degraded over time, especially the sensitivity over time. From this insight, the problem of preservation stability was solved by the cooperation of materials that prevent this reduction. Anti-reducing agents can be used, for example, those generally used as inhibitors of radical chain reaction. Examples of such an anti-reducing agent include compounds described in Japanese Patent Application Laid-Open No. 10-2 3 2 4 8 9 and quinone compounds such as benzoquinone and naphthoquinone. Among them, benzoquinone is more suitable. Benzoquinone includes o-benzoquinone, p-benzoquinone and the like, and p-benzoquinone is preferred. The naphthoquinones include 1,2-naphthoquinone, 1,4-naphthoquinone, 2,6-naphthoquinone, and the like, and 1,4-naphthoquinone is more preferred. The compounding amount of the (D) component in the positive-type photoresist composition is about 0.1 to 1.0% by mass based on all solid components except the (D) component contained in the photoresist composition. The anti-reducing agent used in the present invention is itself reduced in the positive-type photoresist composition during storage. Therefore, in the photoresist composition, instead of the anti-reducing agent, a reducing substance corresponding to the anti-reducing agent is present, and the amount thereof is increased with the storage time. This reduced product is, for example, a hydroquinone in the case of an anti-reducing agent benzoquinone. Therefore, because reducing substances such as hydroquinone are positively added to the positive type photoresist composition containing the reduced product, that is, when no antioxidant is contained, -19- (16) (16) 200428142, also It can be the positive photoresist composition of the present invention, and it can be said that it can be produced by the method for preparing the positive photoresist composition of the present invention. < Organic solvents > Organic solvents are not particularly limited if they are generally used in photoresist compositions, and one or two or more can be selected; those containing propylene glycol-alkyl ether acetate, and / or 2-heptanone, It has excellent coating properties, and the uniformity of the thickness of the photoresist film on the large glass substrate is better. Although both propylene glycol-alkyl ether acetate and 2-heptanone can be used, each of them is used alone or mixed with other solvents, and the film thickness uniformity is good when applied by a spin coating method, etc. . Preferably, the content of the 'propylene glycol-alkyl ether acetate is 50 to 100% by mass in all organic solvents. Propylene glycol monoalkyl ether acetate, for example, a linear or branched alkyl group having 1 to 3 carbon atoms, in which propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) is glazed by a large glass substrate The uniformity of the film thickness of the barrier film is excellent and particularly good. On the other hand, 2-heptanone is not particularly limited, and it is a suitable solvent when the (b) naphthoquinone diazide ester is combined with a non-diphenyl ketone-based photosensitive component. 2-Heptanone has better heat resistance than PGME A, has a photoresist composition with reduced scum production, and is an excellent solvent. When 2-heptanone is used alone or mixed with other organic solvents, the content of all organic solvents is preferably 50 to 100% by mass. -20- (17) (17) 200428142 These preferred solvents can be mixed with other solvents. For example, methyl lactate, ethyl lactate, etc. (preferably ethyl lactate) are blended, and the uniformity of the thickness of the photoresist film is excellent, and a photoresist pattern having a good shape can be formed. When propylene glycol-alkyl ether acetate is mixed with alkyl lactate, the blending amount of alkyl lactate should preferably be 0.1 to 10 times and 1 to 5 times the mass ratio of propylene glycol-alkyl ether acetate. Better. Organic solvents such as r-butyrolactone and propylene glycol-butyl ether can also be used. When r monobutyrolactone is used, the compounding amount is preferably 0.10 to 1 time, and more preferably 0.05 to 0.5 time relative to the mass ratio of propylene glycol-alkyl ether acetate. Other organic solvents that can be blended include the following specific examples. That is, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isoamyl ketone; ethylene glycol, propylene glycol, diethylene glycol 'ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol Diols such as glycol monoacetate, methyl ether, monoethyl ether, -propyl ether, -butyl ether, or monophenyl ether and their derivatives; cyclic ethers of dioxane; and methyl acetate Ester, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate and other esters. When these solvents are used, it is preferable that they are 50% by mass or less of the total organic solvents. When the amount of the organic solvent used is preferably a solid component (A) to (D) and other components used when necessary, as described later, it is appropriately adjusted to obtain a uniform positive photoresist composition. The preferred amount is 10 to 50% by mass, more preferably 20 to 35% by mass. Positive light (18) (18) 200428142 The solid content of the resist composition is equal to the total of (A) to (D) components and other components used when necessary. The positive-type photoresist composition of the present invention may contain compatible additives, such as additional resins, plasticizers, etc., for improving the performance of the photoresist film, as long as the purpose of the present invention is not impaired. Preserving stabilizers and surfactants are commonly used additives such as colorants that make the developed image more visible, sensitizers that enhance the sensitization effect, anti-halo dyes, and adhesion improvers. Anti-halation dyes can use UV absorbers (such as 2,2 ', 4,4'-tetrahydroxydiphenyl ketone, 4-dimethylamine-2', 41-dihydroxydiphenylketone, 5-amine-3 —String-1_benzene-4— (4-hydroxybenzazo) pyrazole, 4-dimethylamine—4′-hydroxyazobenzene, 4-diethylamine—ethoxyazobenzene, 4-diethyl Amine azobenzene, curcumin, etc.). Surfactants can be added for anti-glow, for example, FLUORAD FC-430, FC431 (trade name, made by Sumitomo 3M (stock)), EFTOP EF122A, EF122B, EF122C, EF126 (brand name, TOCHEM PRODUCTS (stock)) Manufactured) and other fluorine-based surfactants, XR—104, MEGAFAC R — 08 (trade name, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) and the like. The positive type photoresist composition of the present invention is preferably prepared so that the solid content Mw (hereinafter referred to as the photoresist molecular weight) of the photoresist composition may be in the range of 5,000 to 30,000, and more preferably Mw is 6000. Up to 1 0000. When the amount of the photoresist molecule is in the above range, no decrease in sensitivity can be achieved, and high resolution can be achieved. At the same time, a positive photoresist composition having excellent linearity and DOF characteristics and excellent heat resistance can be obtained. -22- (19) (19) 200428142 When the molecular weight of the photoresist is less than the above range, the resolution 'linearity, 00? Characteristics and insufficient heat resistance' will exceed the above range, the sensitivity will decrease significantly, and the coating of the photoresist composition will be impaired. Sexual concerns. In the present specification, the photoresist molecular weight is used, and 値 measured by the following GPC system. Device name: SYSTEM 11 (product name, manufactured by Showa Denko Corporation) Item 丨 J column: KF—G (product name, manufactured by Shodex) column: KF — 805, KF-803, KF-802 (product name,

Shodex company) Detector: UV 41 (product name, manufactured by Shodex company), measured at 280 m. Solvents: flow through tetrahydrofuran at a flow rate of 1.0 / min. (: Measurement. Preparation method of measurement sample: The photoresist composition to be measured is prepared to have a solid content concentration of 30% by mass, and it is diluted with tetrahydrofuran to prepare a measurement sample with a solid content concentration of 0.1% by mass. Samples of 20 microliters were injected into the above device for measurement. In addition, in the manufacture of system LCDs, photolithography was used instead of the conventional g-line (436nm) exposure for LCD manufacturing, and the i-line (365nm) exposure with a shorter wavelength was used. In other words, the (B) component and the arbitrary (C) component are non-diphenyl ketone-based positive photoresist compositions of the present invention, and (B) component And (C) the absorption of i-rays is suppressed, so it is suitable for i-ray exposure procedures and can achieve higher resolution. -23- (20) (20) 200428142 The positive photoresist composition of the present invention In the preparation, the method of adjusting the molecular weight of the photoresist to the above-mentioned suitable range includes, for example, (1) In order to make the Mw of all components into the above range, perform a classification operation on the (A) component before mixing, etc. The method of adjusting Mw to an appropriate range, And (2) a method of preparing most (A) components with different Mw, and appropriately mixing them to adjust the Mw of the solid component to the above range. Among these modulation methods, the above (2) modulation method is due to the adjustment of the molecular weight of the photoresist The method of preparing the positive photoresist composition for system LCD manufacturing is particularly preferable. The positive photoresist composition of the present invention is preferably the component (A), (B), and (C). ) Component, (D) component, and other components, if necessary, are prepared by dissolving in an organic solvent. The preparation may be performed by mixing (D) component with other components at the same time as the preparation of the positive photoresist composition. That is, a method for preparing a positive type photoresist composition by using an organic solvent solution compounded with the component (A) of the (D) component, and a method for preparing the positive type photoresist composition for LCD manufacturing of the system of the present invention. A method for preparing a positive-type photoresist composition for LCD manufacturing is to mix a resin solution prepared by mixing the component (D) with the organic solvent solution of the component (A), and mixing the component (B) and the component (C) Method. According to the present inventors It was learned that in the preparation of the positive photoresist composition for the manufacture of the system LCD of the present invention, the (D) component alone was mixed with an organic solvent containing the (A) component and the like, and sometimes the quality of the photoresist composition could not be prevented- 24- (21) (21) 200428142 changes over time, even if they are the same product, there will be variations in characteristics between batches. The present inventors and others have further explored the results and found that the deterioration of the photoresist composition has always been thought only by PAC The deterioration of the organic solvent solution of component (A), which is stored for the purpose of photoresist modulation, causes the variation of the photoresistance characteristics between the above batches. That is, the component (A) is in the organic solvent solution. Storage in this state will deteriorate over time, resulting in variations in photoresistance characteristics between batches. Therefore, in the method for preparing the positive-type photoresist composition of the present invention, first, an organic solvent solution (solution (I)) of the component (A) is obtained. The concentration of the component (A) in the solution (I) is not particularly limited, but is usually 20 to 60% by mass, and generally 35 to 55% by mass is particularly preferred. Next, the solution (I) prepared as above is compounded with the component (D) to obtain an organic solvent solution (solution (II)) containing the component (A) and the component (D). (D) The combination of components is to avoid the problem of particle generation after photoresist modulation, and it should be done according to the following methods. 1. At room temperature (20 to 25 ° C), in an organic solvent like the organic solvent used in solution (I), mix the component (D) so that the concentration can be 10 to 20% by mass. Stir for more than 10 minutes, completely. Dissolving into a solution "2. Add the above-mentioned (D) component solution to the solution (I) in small amounts one by one to obtain a solution (II). Secondly, add (B) component and (C) component to the solution (II), if necessary, add ultraviolet absorber, surfactant, etc., and if necessary, add a solvent to adjust the concentration to a uniform solution (III) to obtain the positive photoresist of the present invention.组合 物。 Composition. So -25- (22) (22) 200428142 plus the kind of solvent may be the same or different from the organic solvent used in the solution (I), (11), etc. The obtained solution (II) may be filtered with a filter or the like. Surprisingly, in the present invention, only the (D) component required for the stability of the (A) component in the solution (I) is added to the preparation solution (11), and the solution (Π) is used to modulate the positive photoresist composition. A stable positive photoresist composition. In other words, the addition of the (B) component, the (D) component, and the like, and the addition of an additional stabilizer are not necessary. Thus, in the preparation method of the present invention, the preservation stability of the component (A) is maintained, and the preservation stability of the positive-type photoresist composition using the component (A) is also ensured. << Method for Forming Photoresist Pattern >> An example of a suitable method for forming a photoresist pattern in the case of manufacturing a system LCD using the positive photoresist composition of the present invention is exemplified below. First, the positive-type photoresist composition of the present invention is applied to a substrate by a spin coater or the like to form a coating film. The substrate is preferably a glass substrate. In the field of system LCD where amorphous silicon oxide is usually used, a glass substrate is preferably a glass substrate formed by forming a low-temperature polycrystalline silicon layer. The glass substrate has a high resolution under low NA conditions due to the positive photoresist composition of the present invention, and a large substrate of 500 mm x 600 mm or more, especially 550 mm x 650 mm or more can be used. Next, the glass substrate on which the coating film has been formed is subjected to a heat treatment (pre-baking) at 100 to 140 ° C to remove the residual solvent 'to form a photoresist film. The pre-baking method is preferably a neighboring baking that maintains a gap between the hot plate and the substrate. -26- (23) (23) 200428142 For the above photoresist film, a mask with a mask pattern is used for selective exposure. In order to form a fine pattern, an i-line (365iim) is preferably used as the light source. The preferred exposure program used for this exposure is N A 0 · 3 or less, more preferably 0 · 2 or less, and 0.1 5 or less and a better low NA condition exposure program. Second, the photoresist film after selective exposure is subjected to heat treatment (post-exposure baking: PEB). The PEB method includes adjacent baking that maintains a gap between the hot plate and the substrate, and direct baking without leaving a gap; in order to prevent the substrate from warping, the diffusion effect of PEB is obtained, and direct baking is performed after the adjacent baking. The method is better. The heating temperature is 90 to 15 (TC, 100 to 14 (TC) is preferred. For the above-mentioned photoresist film after PEB, use a developing solution, such as an alkali aqueous solution of 1 to 10% by mass of tetramethylammonium hydroxide aqueous solution. The development process dissolves and removes the exposed part, and simultaneously forms a photoresist pattern for integrated circuits and a photoresist pattern for the liquid crystal display part on the substrate. The developing solution remaining on the surface of the photoresist pattern is pure water, etc. The photoresist pattern can be formed by washing away the eluent. In the photoresist pattern formation method, in the above-mentioned step of performing selective exposure when manufacturing a system LCD, the photomask is formed by using a photoresist pattern with a length of less than 2.0 μm. It is preferable to use both a mask pattern and a mask pattern for forming a photoresist pattern exceeding 2.0 μm. Therefore, the positive photoresist composition for LCD of the present invention can obtain a mask pattern because of its high resolution. The fine pattern is faithfully reproduced by the photoresist pattern. Therefore, in the step of forming the above photoresist pattern at the same time, on the above substrate, the shape can be simultaneously shaped -27- (24) (24) 200428142 into a pattern size of 2.0 μm or less Photoresist pattern for integrated circuit And a photoresist pattern for a liquid crystal display portion exceeding 2. 0 μιυ. As explained above, the positive photoresist composition of the present invention contains a non-diphenyl ketone-based PAC, has high sensitivity, and is suitable for i-line exposure. It also has high resolution under low NA conditions. Due to the combination of anti-reducing agents, the diachronic changes in the bottle during long-term storage, the diachronic changes in photoresistance characteristics (sensitivity, size, film thickness, etc.) are suppressed, and the storage stability is excellent. In addition, in order to prevent this diachronic change, it is necessary to strictly control the storage temperature within a range of, for example, 0 to 20 ° C. The positive photoresist composition of the present invention has a large allowable storage temperature range, and can be controlled, for example, from −1 to 0. + 25 ° C. And also has good linearity, DOF and other characteristics, suitable for the manufacture of system LCDs. Examples The following examples illustrate the present invention in detail. Use the modulation in the following Examples 1 to 3 and Comparative Examples] The positive photoresist composition is evaluated in the following (1) to (3). Evaluation method (1) Storage stability evaluation: Dimensional evaluation is performed on the positive photoresist composition prepared in the following examples or comparative examples. Prepare each, 25 1Sample (丨) 'stored for six months' and sample (Π) stored for 6 months under refrigerated storage (5 ° C). EOP exposure when using the above sample (ii) (1.5 ^ m L &amp; S photoresist pattern can be faithfully reproduced under the exposure amount (mJ)) to determine the above-mentioned test-28- (25) (25) 200428142 sample (i) when the same photoresist pattern is formed l.hmL &amp; The dimensional change rate of the S pattern. The formation of the photoresist pattern was performed as follows: The sample was coated on a silicon wafer with a spin coater, and dried on a hot plate at 90 ° C for 30 seconds to obtain a film thickness of 1.05. μηι photoresist film. An i-ray exposure device (product name &quot; FX 702 · r, manufactured by NIKON Corporation, NA = 0,14) was used for selective exposure on this film, and PEB was performed at 110 ° C for 90 seconds. (Post-exposure baking) treatment. Next, a 2.38% by mass TMAH aqueous solution (product name &quot; NMD-3 &quot;, manufactured by Tokyo Chemical Industry Co., Ltd.) was used for development at 23 ° C for 90 seconds, and pure water was rinsed for 30 seconds. The treatment was followed by a drying step to form a 1.5 μm L &amp; S pattern. (2) Evaluation of resolution: Under the exposure of Eορ when using the above-mentioned sample (ii), determine the limit resolution using the above-mentioned sample (i). (3) Linearity evaluation: Each of the above samples (i) was coated on a glass substrate on which a Ti film was formed using a photoresist coating device for large substrates (device name: TR36000, manufactured by Tokyo Chemical Industry Co., Ltd.) ( 550nm X 650mm), the hot plate temperature was set to 100t, the first drying was carried out for 90 seconds after the adjacent baking with an interval of about 1mm, and then the hot plate temperature was set to 90 ° C, which was maintained at 0.1. The adjacent baking at a 5mm interval was subjected to a second drying for 90 seconds to form a photoresist film with a film thickness of 1.5 μm. Secondly, a test pattern of a photomask (26) (26) 200428142 (reticle) is drawn by simultaneously depicting a photomask pattern that is a reproduction of a photoresist pattern of 3.0 μm lines and spaces (L &amp; S) and 1.5 μm L &amp; S. A selective exposure was performed using an i-ray exposure device (device name: FX-702J 'manufactured by NIKON Corporation; NA = 0.14) with an exposure amount (Eoρ exposure amount) that faithfully reproduces 1.5 μm L &amp; S. Secondly, the temperature of the hot plate was set to 120 ° C, and the interval was 0.5mm, and the baking process was applied for 30 seconds, followed by the same temperature for 60 seconds. Secondly, a developing device using a slit coating nozzle at a temperature of 2 3 ° C and a 2.38% by mass TM AH aqueous solution (device name: TD-39000 demonstration machine, manufactured by Tokyo Chemical Industry Co., Ltd.), as shown in Figure 1, since After the substrate end X passes through Y to Z, it is held on the substrate for 55 seconds for 10 seconds, and then washed with water for 30 seconds and spin-dried. Then, the cross-sectional shape of the obtained photoresist pattern was observed with a SEM (scanning electron microscope) photograph, and the reproducibility of the photoresist pattern at 3.C ^ mL &amp; S was evaluated. The dimensional change rate is less than ± 10% as A, and more than 10% to 15% is B 'and more than 15% is C. (Example 1) The following were prepared as components (A) to (D) as component (A): (A1) mixed phenols 1 using m-cresol / 3'4-xylenol = 8/2 (molar ratio) Mol, synthesized with formaldehyde 0.82 Mol according to a general method,

A phenolic lacquer tree with a Mw = 20000 and Mw / Mn = 5.2. (B) Ingredients: (B1): bis (5-cyclohexyl-1, 4-mer-2, tolyl) -3,4-dihydroxyphenylmethane (ΒΓ) 1 mole and 1,2-naphthoquinone Nitrogen 5 — -30- (27) 200428142 Sulfuryl chloride [abbreviated below (5-NQD). ] 2 Molar esterification reaction product (B2): bis (2,4-dihydroxyphenyl) methane (B2,) 丨 Molar and 5 — NQD 2 Molar esterification reaction product (B3): Bi ( Esterification reaction product (C) component of 4-hydroxy_2,3,5-trimethylphenyl)-2-hydroxybenzidine (B3 ') 1 mole and 5-NQD 2 mole:

(C1): bis (5-cyclohex-4--4-hydroxy-2-tolyl) -3,4-dihydroxybenzenemethane (D) component: (D1): p-benzoquinone organic solvent: (El): PGMEA ( Examples 1 to 3 and Comparative Example 1) The above-mentioned (A) component in a compounding amount (parts by mass) described in Table 1 below was dissolved in an organic solvent (E 1), and the compounding amount (mass in Table 1 below) was blended therewith. (D) of the component) to dissolve it into a solution. To this solution, the components (B) and (C) in the blending amounts (parts by mass) shown in Table 1 below were added and dissolved, and then filtered through a filter having a pore size of 0.2 μηα to prepare a positive photoresist composition. The photoresist molecular weight of the obtained positive type photoresist composition is shown in Table 1. Each of the obtained positive-type photoresist compositions' was evaluated in each of the above (1) to (3). The results are shown in Table 2 below. -31-(28) 200428142 Table 1 (A) Ingredients (combined amount) (B) Ingredients (mixing ratio) (combined amount) (C) (combined amount) (D) (combined amount) (E) composition ( Compounding amount) Photoresist molecular weight Example 1 Al (15) B1 / B2 / B3 (mixing ratio 6/1/1) (1 hemp amount 5.5) Cl (4.5) Dl (0.3) El (75) 10000 Example 2 Ibid. Ibid. Dl (Ol) Ibid. Ibid. Example 3 Ibid. Ibid. Dl (0.5) Ibid. Ibid. Comparative Example 1 Ibid. Ibid. M Ibid. Table 2

Size duration evaluation (%) Resolution evaluation (μηι) Linear evaluation Example 1 -1.1 1.2 A Example 2 + 2.0 1.2 A Example 3-3.3 1.2 A Comparative Example 1 + 3.6S1) 1.4 A Note 1) Results at 25 ° C for one month

The positive-type photoresist composition of Examples 1 to 3 has a better dimensional evaluation and a better storage stability than the photoresist composition of Comparative Example 1 without the addition of an anti-reducing agent. In addition, the resolution is still high under low NA conditions (NA = 0.14), and the linearity is also good. -32- (29) (29) 200428142 Effects of the Invention As explained above, the positive photoresist composition of the present invention has excellent storage stability and is suitable for the manufacture of system LCDs. [Schematic description] Figure 1. For linearity evaluation under low NA conditions, a positive photoresist composition is coated on a glass substrate and baked and dried 'after pattern exposure' to develop a gap applicator. The device is used to make the developing liquid from the end of the substrate to two gushing liquid.

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Claims (1)

(1) 200428142 Patent application scope 1. A positive type photoresist composition, which is a positive type photoresist composition for LCD manufacturing, which can form integrated circuits and liquid crystal display parts on a substrate, which is characterized by: The (A) alkali-soluble resin, (B) contains the following general formula (I) [Wherein R1 to R8 each independently represent 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 cycloalkyl group having 3 to 6 carbon atoms; R1C) And R11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R9 may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. At this time, Q1 represents a hydrogen atom and an alkyl group having 1 to 6 carbon atoms Or the following chemical formula (II) R12 (Wherein R12 and R13 each independently represent 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 cycloalkyl group having 3 to 6 carbon atoms; c shows Residues shown in the integers from 1 to 3 'or' Q1 can be combined with the terminal of R9, at this time, (^ together with R9 and, the carbon atom between Q1 and r9 -34- (2) (2) 200428142, table Cycloalkyl groups of carbon chain 3 to 6; a, b are integers of Tables 1 to 3; d are integers of Tables 0 to 3; a, b or d are 3 each without r3, R6 or R8; η of Tables 0 to 3 Integer] The naphthoquinonediazide esters of the esterification reaction products of the compounds shown in the table with the 1,2-naphthoquinonediazidesulfonium sulfonium compound, (c) phenolic hydroxyl-containing compounds having a molecular weight of less than 1,000, and D) The anti-reducing agent is dissolved in an organic solvent to obtain 02. For example, the positive photoresist composition in the scope of patent application No. 1 contains a reduced substance corresponding to the component (D). 3. If the scope of patent application is No. 1 Or the positive photoresist composition of item 2, wherein the component (D) is benzoquinone. 4- The positive photoresist composition of item 2 or 3. of the patent application scope, wherein the above-mentioned reduction is hydroquinone. 5 . — Positive A method for preparing a photoresist composition is a method for preparing a positive type photoresist composition as described in any one of claims 1 to 4, and is characterized in that: the above-mentioned (A) component is mixed in an organic solvent solution; The resin solution composed of the component (D) and the components (B) and (C). 6. A method for forming a photoresist pattern, which is characterized by: The step of applying the positive photoresist composition of any one of 4 items to a substrate to form a coating film, and (2) heating (pre-baking) the substrate on which the above coating film has been formed to form light on the substrate (3) For the above photoresist film, use a photomask that depicts both a photoresist pattern forming photomask pattern below 2.0 μm and a photoresist pattern forming photomask pattern exceeding 2.0 μm The steps of performing selective exposure, (4) the step of applying -35- (3) (3) 200428142 to the photoresist film after the selective exposure described above, and applying heat treatment (post-exposure baking · PEB), and ( 5) Apply alkali water to the photoresist film after the heat treatment Solution development process, the step of simultaneously forming a photoresist pattern for integrated circuits with a pattern size of 2.0 μm or less and a photoresist pattern for a liquid crystal display part exceeding 2_0 μm on the above substrate. 7. If the scope of patent application is 6 The method of forming a photoresist pattern according to the item, wherein the step of (3) performing selective exposure is performed according to an exposure procedure in which the light source uses i-rays, and NA is at a low na of 0.3. -36-