TWI285789B - 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

1285789 (1) Field of the Invention 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, and the positive-type photoresist composition is used. A method of modulating a substance, and a method of forming a photoresist pattern using the positive-type photoresist composition. [Prior Art] Conventionally, semiconductor elements, liquid crystal display elements (LCDs), and especially TFTs used in the manufacture of TFTs have been exposed to light suitable for ghi lines (lights including g lines, h lines, and i lines). Low-cost, high-sensitivity, phenolic phthalocyanine resin for alkali-soluble resin, photosensitive component (hereinafter abbreviated as PAC), phenolic enamel-naphthoquinonediazide-type positive light with naphthoquinonediazide-containing compound The resist composition (refer to, for example, Patent Documents 1 to 4). When the LCD is manufactured, since the pixel portion of the display is formed only on the substrate, the positive resist composition has a sensitivity capable of forming a very thick pattern (for example, about 3 to 5 μm). Therefore, PAC mainly uses an esterification reaction product of a low-sensitivity but inexpensive phenyl ketone-based phenol compound with 1,2-naphthoquinonediazide-5-a-based compound (diphenylketone-based PAC). ). Further, the diphenyl ketone-based PAC has excellent storage stability, and particularly has a small change in sensitivity over time, and the photoresist pattern formed in the LCD manufacturing is also as described above, and the target is extremely thick, and the storage stability of the photoresist composition has been hitherto. Not a problem. In recent years, for the new generation of LCD, a driver, DAC (digital-to-analog converter), image processor, video controller, RAM, etc. are simultaneously formed on a glass substrate and display (2) (2) 1285789. The high-performance LCD of the so-called "system LCD" in the integrated circuit portion has a prevailing technology development (refer to, for example, Non-Patent Document 1). Hereinafter, in the present specification, an LCD in which an integrated circuit and a liquid crystal display portion are formed on a substrate 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 ΙΟμιη, and the integrated circuit portion is formed with a fine size of about 55 to 2.0·μμι. Therefore, the positive-type photoresist composition for system LCD manufacturing has a basic requirement of the ability to simultaneously form a fine pattern of a good shape and a relatively thick pattern (high resolution and linearity). Further, as a substrate of the system LCD, a low-temperature polysilicon, in particular, a low-temperature polycrystalline silicon formed by a low-temperature process of 600 ° C or lower, is expected to be suitable because the amorphous germanium has a small electric resistance and a high mobility. Therefore, the development of a system LCD using a low-temperature polysilicon for a substrate is actively being carried out, and a composition suitable for the manufacture of a system LCD using a low-temperature polysilicon is expected to be developed in the manufacture of a system LCD as described above, in order to form fine light. The resist pattern is suitable for ghi line exposure. The diphenyl ketone-based PAC is difficult to apply, and it is suitable to use a non-diphenyl ketone-based PAC suitable for i-line exposure. Further, since it is necessary to form a fine photoresist pattern, as with the manufacture of the above-mentioned semiconductor element, the change in the photoresistance characteristics is strictly controlled, and it is expected that there is a demand for a photoresist composition excellent in stability. However, according to the inventors of the present invention, the light-containing composition of the non-diphenyl ketone-based PAC (3) (3) 1285789 is excellent in resolution, and it is difficult to preserve stability, and it is stored after preparation. Changes in photoresist characteristics such as sensitivity and resolution sometimes occur over time. Therefore, when storing the photoresist composition, it is necessary to strictly control the storage temperature at a temperature range of about 〇 to 2 (TC). Moreover, even if such temperature control is performed, there is still a problem that the storage stability is not allowed for six months. Therefore, due to the temporal change of the photoresist characteristics, the shape of the formed photoresist pattern is affected, and the cost of strict temperature control is high, and it is still not suitable for the manufacture of the system LCD. Patent Document 1 Japanese Patent Laid-Open No. 2000 - 1 3 1 83 Patent Document 2, JP-A-200-75272, JP-A No. 2000-1, No. 1, No. 2000-112, No. 2000-112120, Non-Patent Document 1 Semiconductor FPD World 2001.9, pp. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION Accordingly, an object of the present invention is to provide a system for manufacturing a system for forming an integrated circuit and a liquid crystal display portion on a substrate, comprising a non-diphenyl ketone system. A PAC photosensitive component, and a positive resistive composition having excellent stability, a method for preparing the positive resist composition, and a method for forming a resist pattern.

In order to solve the above problems, the present inventors have found that PAC -7-(4) 1285789 is an esterification reaction of a non-diphenyl ketone polyphenol compound with a 1,2-naphthoquinonediazide sulfonium compound. In the positive-type photoresist composition of the product, a positive-type photoresist composition obtained by using an anti-reducing agent such as benzoquinone is added, and the phenomenon that the photoresist characteristic changes over time during storage in the bottle is suppressed, and the stability is preserved. The invention is applied to materials for the manufacture of system LCDs, and the present invention has been completed. That is, the present invention provides that (A) an 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 ring-membered group having 3 to 6 carbon atoms; Independent hydrogen atom or a group of 1 to 6 carbon atoms; R9 may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in which case Q1 represents a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. Chemical formula (Π) R12

(wherein R12 and R13 each independently represent a hydrogen atom, a halogen atom, a carbonogen-8-(5) (5) 1285789 an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a carbon atom. a 3 to 6 cycloalkyl group; c is a residue of 1 to 3), or Q1 may be bonded to the end of R9, in this case, Q1 together with R9 and a carbon atom between Q1 and R9, a carbon chain a cycloalkyl group of 3 to 6; a, b an integer of Tables 1 to 3; d an integer of 0 to 3; a, b or d is 3 without each of R3, R6 or R8; n is an integer of 0 to 3. a naphthoquinonediazide esterified product of an esterification reaction product of a compound with a 1,2-naphthoquinonediazidesulfonium compound, (C) a compound having a phenolic hydroxyl group having a molecular weight of 1 000 or less, and (D) an anti-reduction The agent is dissolved in an organic solvent to form a positive-working photoresist composition for LCD production (hereinafter referred to as a positive-type photoresist composition of the present invention) in which an integrated circuit and a liquid crystal display portion are formed on a substrate. Furthermore, the present invention provides a method for preparing a positive resist composition in which the resin solution of the component (D) and the components (B) and (C) are blended in the organic solvent solution of the component (A). Further, the present invention provides a method comprising: (1) applying the positive-type photoresist composition to a substrate to form a coating film, and (2) performing heat treatment of the substrate on which the coating film has been formed (pre- a step of forming a photoresist film on a substrate, and (3) using a photoresist pattern for forming a photoresist pattern of 2.0 μm or less and a light for forming a photoresist pattern of more than 2.0 μm for the photoresist film. a step of selectively exposing both masks of the mask pattern, (4) a step of applying heat treatment (post-exposure baking: Ρ Ε Β) to the photoresist film after selective exposure, and (5) heating for the above The photoresist film after the treatment is subjected to development processing using an alkali aqueous solution, and a photoresist pattern for an integrated circuit having a pattern size of 2.0 μm or less is simultaneously formed on the substrate, and a photoresist pattern for a liquid crystal display portion exceeding 2.0 μm is formed. The light of the step (6) 1285789 The formation method of the resist pattern. [Embodiment] Hereinafter, the present invention will be described in detail. <<Positive Photoresist Composition for LCD Manufacturing>> &lt; (A) Component&gt; (A) Component The alkali-soluble resin (A) component is not particularly limited, and can be used as a film formation of a positive photoresist composition. Among the substances, one or more of them may be used arbitrarily. For example, phenols (phenol, m-cresol, p-cresol, xylenol, trimethylhydrazine, etc.), and aldehydes (formaldehyde, formaldehyde precursor, propionaldehyde, 2-hydroxybenzazole, 3-hydroxybenzaldehyde) , 4-hydroxybenzaldehyde, etc. and/or ketones (butanone, acetone, etc.) phenolic enamel resin condensed in the presence of an acidic catalyst; styrene-based monomer, hydroxystyrene and other benzene a copolymer of a vinyl monomer, a hydroxystyrene resin such as a copolymer of hydroxystyrene and acrylic acid or methacrylic acid or a derivative thereof; a copolymer of acrylic acid or methacrylic acid and a derivative thereof, an acrylic acid or a methacrylic resin, or the like . In particular, a phenolic lacquer obtained by condensation reaction of a phenol selected from at least two of m-cresol, p-cresol, 3,4-xylenol and 2,3' 5-trimethylphenol with an aldehyde containing formaldehyde Resin, suitable for the modulation of photoresist materials with high sensitivity and excellent resolution. The component (A) can be produced by a general method. The mass average of the component (A) by gel permeation chromatography is -10- (7) (7) 1285789. The molecular weight varies depending on the type, but based on sensitivity and pattern formation. It is 2,000 to 100,000, and 3,000 to 300,000 more preferably (A) components can be produced by a general method. &lt;(B)Component&gt; The component (B) is a naphthoquinonediazide telluride, and an esterification reaction product of the phenol compound of the above general formula (I) and a 1,2-naphthoquinonediazidesulfonium compound ( Hereinafter, it is called non-diphenyl ketone type PAC). The positive resist composition containing the non-diphenylketone-based PAC has high sensitivity and high resolution. Moreover, it is suitable for photolithography using i-line, and is also preferable in characteristics such as 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 atom number of 1. a linear or branched alkyl group of 6 having a linear or branched alkyl alkoxy group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms; R1() and R11 are each independently a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms; R9 may be a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, in which case Q1 represents a hydrogen atom and a carbon atom. a straight or branched alkyl group of 1 to 6 or a residue of the above formula (II), or Q1 may be bonded to the end of R9, in which case Q1 together with R9 and a carbon atom between Q1 and R9, carbon a cycloalkyl group of 3 to 6; a, b an integer of Tables 1 to 3; d an integer of 0 to 3; n an integer of 0 to 3. While Q1 and R9 together with the carbon atom between Q1 and R9 form a cycloalkyl group having a carbon chain of 3 to 6, Q1 is bonded to R9 to form an alkylene group having 2 to 5 carbon atoms. The phenolic compound of the general formula (I) is ginseng (4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxyl-11-(8) ) 1285789 2,3,5-trimethylphenyl)- 2-hydroxyphenylmethane, bis-dimethylphenyl)- 4-hydroxyphenylmethane, bis(4-hydroxyl)-3-hydroxyphenylmethane, double (4 Monohydroxy-3,5-monohydroxymethane, bis(4-hydroxy-2,5-dimethylphenylene, bis(4-hydroxy-2,5-dimethylphenyl)-3-(4-hydroxyl- 2,5-Dimethylphenyl)-2-hydroxybenzol-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, 5-dimethylphenyl)- 3,4 — once benzotrim, double 1-dimethylphenyl)- 2,4-dihydroxyphenylmethane, bis(4-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexa-4)-4-hydroxyphenylmethane, bis(5-ring) Benzyl 4-hydroxy-3-hydroxyphenylmethane, bis(5-cyclohex-4-hydroxy-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methyl-2-hydroxyphenylmethane) Phenolic compound; 2,4-double (3,5-dimethyl-4-hydroxybenzyl, 2,6-double 2,5-dimethyl 4-hydroxybenzyl) triphenylcyclophenol compound; 1,1 pair of [3 -(2-hydroxy)-4-hydroxy-5-cyclohexyl]isopropane, double [2, (4-hydroxy-5-toluomethyl)- 4-hydroxyphenyl]methyldimethyl 3-(4-hydroxybenzyl-tetrahydroxyphenyl)-methyl, 5--methyl-4-yl- Benzyl]-4-yl---5-A-3-[3,5-monomethyl- 4-benzyl)- 4-an-alkane, double [3—(3,5-di-ethyl-4-1 Hydroxymethyl)tolyl]methane, bis[3 _(3,5-diethyl-4-(4-hydroxy-3,5-3,5-dimethylphenyl)-2-)-4-hydroxybenzene Methyl-hydroxyphenylmethane, bis-alkane, bis(4-hydroxyl, bis(4-hydroxy-2(4-hydroxy-2,5-hydroxyphenyl)-3hydroxyl-2-tolyl-2-tolyl)-toluene Base) - 2 - £ base) - 3 ' 4 - ) 5-hydroxyphenol 4- 4-cresol isoline _ 5 - toluylmethyl 5 - monomethyl-3-oxane, bis[2,5-alkane, double [3 _ (3 phenyl]methane, bis 5-ethylphenyl]methyl-4-hydroxy-5-hydroxybenzyl)-4-12- 1285789 Ο)-hydroxy-5-ethylphenyl] , bis[2-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)-5-tolyl]methane, bis[2-hydroxy-3-(2-hydroxy-5-tolylmethyl) a 5-[tolyl]-methyl, double [4-one-three-(2-hydroxy-5-toluomethyl)-5-tolyl]methane, bis[2,5-dimethyl-3-(2- A 5-tetraphenylcyclophenol compound via a 5-methyl-toluomethyl)- 4- phenylene group; 2,4-bis[2-hydroxy-3-(4-hydroxybenzyl)-5-toluene Base]-6-cyclohexanol, 2,4-bis[4-hydroxy-3-(4-hydroxybenzyl)-5-toluomethyl]-6-cyclohexanol, 2,6-double [2 , 5-dimethyl 3-(2-hydroxy-5-toluomethyl)-4-hydroxybenzyl] 4- 4-cresol, linear pentacene phenolic compound, etc. linear polyphenolic compound; double (2,3 , 4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4-trihydroxybenzene- 4'-hydroxyphenylmethane, 2- (2,3,4-three Hydroxyphenyl)-2-(2',3',4'-trishydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl ) Alkane, 2_(4-diphenyl)-2-(4'-phenyl)propyl- 2-(3-fluoro-4-yl-phenyl)-2-(3'-fluoro- 4'-phenyl ) Bingyuan, 2 - (2,4-dihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2- (4'- Hydroxyphenyl)propane, 2-(2,3,4-di-phenylene)_ 2 -(4' _ _ 3',5'---toluene) bisphenol-type compound such as propane; -(4-hydroxyphenyl)isopropyl]-4-iso[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1 -[1 -(3 -methyl-4-hydroxyphenyl) a polyphenylene ring-branched compound such as 1,1,1,1,3,3,4,4-hydroxyphenylethyl, benzene, etc. 1,1 bis(4-hydroxyphenyl)cyclohexane A condensed phenol compound such as an alkane. -13- (10) (10) 1285789 These may be used alone or in combination of two or more. Among them, the phenolic compound is the main component, and the sensitivity is high, and the resolution is better, especially bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane [below Abbreviation (Β Γ ). ], bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane [hereinafter referred to as (B3·). ] is better. It is also a photo-resist composition that is excellent in overall resolution of photo-resistance characteristics such as modulation resolution, sensitivity, heat resistance, DOF characteristics, and linearity, and is a linear polyphenol compound, a bisphenol type compound, a polyphenyl ring branched compound, and a condensation type. A phenol compound or the like is preferably used together with the above-mentioned phenolic compound, particularly a bisphenol type compound in which bis(2,4-dihydroxyphenyl)methane (hereinafter referred to as (B2') is used. When used, it can produce an overall balanced excellent photoresist composition. Hereinafter, each of the naphthoquinonediazide esters of the above (B1') ' (B2,) and (B3,) is abbreviated as (Β 1 ), (B 2 ), and (B 3 ). When (B1) and (B3) are used, the amount of the component (B) is preferably 10% by mass or more, more preferably 15% by mass or more. Further, it may be preferably 90% by mass or less and more preferably 85% by mass or less. Since (Β 1 ), (B 2 ), and (B 3 ) are all effective, the amount of each compound is (Β 1 ) 50 to 90% by mass, and 60 to 80% by mass is more preferable, (B2 The compounding amount is 5 to 25% by mass, more preferably 10 to 5% by mass, and the amount of (B3) is 5 to 25% by mass, more preferably 10 to 15% by mass. The phenolic hydroxyl group of the above compound of the general formula (I), all or a part of the naphthoquinonediazide sulfonation method, may be a general method. For example, naphthoquinonediazidesulfonium chloride can be obtained by condensing the compound of the above general formula (I). -14- (11) 1285789 Specifically, for example, the compound of the above general formula (I), and naphthalene 1 , 2 - 1 azo nitrogen 4 (or 5) - alkyl chloride can be dissolved in a specific amount. An organic solvent such as dioxane, N-methylpyrrolidone, dimethylacetamide or tetrahydrofuran, which is reacted with one or more kinds of basic catalysts such as triethylamine, triethanolamine, pyridine, sodium carbonate or sodium hydrogencarbonate. The obtained product was washed with water and dried to prepare. (B) Component As described above, in addition to the preferred naphthoquinonediazide esters exemplified above, other naphthoquinonediazide compounds generally used as photosensitive components of the positive-type photoresist composition may be used, for example, An esterification reaction product of a phenol compound such as hydroxydiphenyl ketone or an alkyl gallate and a naphthoquinonediazidesulfonic acid compound. These other naphthoquinonediazide compounds may be used singly or in combination of two or more. The amount of the other naphthoquinone diazide compound used is 80% by mass or less, particularly preferably 50% by mass or less, based on the component (B), which is preferable in the effect of the present invention. The compounding amount of the component (B) in the resist composition is 20 to 70% by mass based on the total amount of the components (A) and (C), and more preferably 25 to 60% by mass. Above the lower limit 値, you can faithfully image the pattern and improve transferability. By setting it below the above upper limit ,, deterioration of sensitivity can be prevented, and the uniformity of the formed photoresist film can be improved, and the effect of improving the resolution can be obtained. The required photoresist characteristics for photoresist compositions in system LCD fabrication are as follows. For example, with the system L C D, in the manufacturing field of L C D, there is a need for high sensitivity based on the control of the production and handling of the -15-(12) 1285789. In the manufacture of LCDs, glass substrates larger than those in the semiconductor field are used. Therefore, in order to enlarge the exposure area, it is preferable to use an exposure procedure under the condition that NA (the number of apertures of the lens is low). Among them, the system LCD has an integrated circuit portion on the substrate in addition to the display portion, and the substrate has a tendency to be larger, and the use is lower than that in the conventional LCD manufacturing, for example, 0.3 or less, especially 0.2 or less. Exposure procedures with low NA conditions are preferred. For the exposure procedure under the low NA condition described above, the resolution tends to deteriorate. In the system LCD, for example, the pattern size of the display portion is about 2 to ΙΟμιη, and the integrated circuit portion is formed to be 0.5 to 2.0. The fine size of μπι is necessary, so it is necessary to form a high resolution of the fine photoresist pattern. Further, it is required that the photoresist pattern of the display portion having a large difference in size and the photoresist pattern of the integrated circuit portion can be formed at the same time, and the linear characteristics must be correctly formed. In the present invention, as the (Β) component, an esterification reaction product of a specific phenol compound of the general formula (I) and a 1,2-naphthoquinonediazide sulfonium compound can be used to obtain high sensitivity in, for example, a low enthalpy condition. A positive photoresist composition having a high resolution and a good linearity and the like. &lt;(C) Component> The component (C) is a compound containing a phenolic hydroxyl group. The use of the (C) component can achieve excellent sensitivity improvement, and the i-line exposure under low-lying conditions -16- (13) (13) 1285789 The program has high sensitivity, high resolution and excellent linearity. Positive photoresist composition. The molecular weight of the component (C) is 1 Torr or less, more preferably 700 or less, and substantially 200 or more, and particularly preferably 300 or more. The component (C) is a compound containing a phenolic hydroxyl group generally used as a sensitivity enhancer or a sensitizer in the photoresist composition. Preferably, those having the above molecular weight conditions are not particularly limited, and one or two kinds may be optionally used. the above. In particular, the following general formula (III)

[wherein R21 to R2 8 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; R3G, 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, an alkyl group having 1 to 6 carbon atoms Or the remainder of the formula (IV) below

-17- (14) (14) 1285789 (wherein R32 and R33 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 carbon atom; a cycloalkyl group of 3 to 6; g is an integer of 0 to 3), or Q2 may be bonded to the end of R29, in which case Q2 together with a carbon atom between R29 and Q2 and R29 has a carbon number of 3 to 6 a cycloalkyl group; e, f an integer of Tables 1 to 3; h an integer of 0 to 3; when e, f^h is 3, each has no R23, R26 or R28; m represents an integer of 3) The compound is preferred because of the above characteristics. More specifically, for example, as exemplified in the above (B) component, in addition to the phenol compound of the general formula (I) for the naphthol diazide compound, bis(3-methyl-4-hydroxyphenyl)-4 Isopropylbenzenemethane, bis(3-methyl-4-hydroxyphenyl)phenylmethane, bis(2-methyl-4-hydroxyphenyl)phenylmethane, bis(3-methyl-2-hydroxyphenyl)phenylmethane , bis(3,5-dimethyl-4-hydroxyphenyl)benzenemethane, bis(3-ethyl-4-hydroxyphenyl)phenylmethane, bis(2-methyl-4-hydroxyphenyl)phenylmethane, bis ( 2_3rd-stage 4,5-dihydroxyphenyl)phenylmethane and the like phenyl type compound can be applied. Among them, bis(2-methyl-4-hydroxyphenyl) phenylmethane, 1-[丨一(4-hydroxyphenyl)isopropyl]- 4-[1,1-bis(4-hydroxyphenyl)B Base benzene is preferred. The compounding amount of the component (C) is preferably from 1 〇 to 70% by mass, and more preferably from 20 to 60% by mass based on the component (A). &lt;Component (D)&gt; The component (D) is an anti-reducing agent. The use of anti-reducing agent can save the stability and stability, and is suitable for the positive photoresist composition of the system LCD. The present inventors have found that one of the causes of poor stability of the composition of the photo-resistance-18-(15) 1285789 composition using a conventional non-diphenyl ketone-based PAC is a non-diphenyl ketone ratio than a diphenyl ketone-based PAC. Low, so the photo-resistance group using the PAC is relatively low, so the reduction effect in the photoresist composition is easy to deteriorate in the duration of the photoresist characteristics during storage, especially the sensitivity history, by which the reduction is prevented. The cooperation of the materials used preserves the problem of stability. Anti-reducing agents can be used, for example, those generally used as free radical inhibitors. Such an anti-reducing agent is, for example, a compound contained in JP-A No. 10-2 2 2 2 8 9 , and an oxime-based compound such as benzoquinone or naphthoquinone is suitable. Phenylhydrazine has o-benzoquinone, p-benzoquinone, etc., and p-benzoquinone is preferred. Naphthalene is 1,2-naphthoquinone, 1,4-naphthoquinone, 2,6-naphthalene 1 '4-Cai|Kun is compared good. The amount of the component (D) in the positive resist composition is such that all solids other than the component (D) contained in the resist composition are about 1 to 1.0 mass%/〇. Further, the anti-reducing agent used in the present invention is itself reduced in the resist composition during storage. Therefore, in the photoresist composition anti-reducing agent', there is a reducing substance corresponding to the anti-reducing agent, which increases with the storage time. The reducing substance is hydroquinone when it is, for example, an anti-reducing agent, benzoquinone, and is a positive-type resist composition containing a reducing substance which is positively added to a normal product such as hydroquinone, that is, in the absence of an anti-system The acidity of the PAC acid product deteriorates during the bottle, and the bulletin of the lock reaction is solved. Among them, 〇 醌, etc., in relation to the composition, in the positive light, instead of its presence amount. The photoresist group -19-(16) (16) 1285789 may also be a positive-type photoresist composition of the present invention, which can be obtained by a method for preparing a positive-type photoresist composition of the present invention. &lt;Organic solvent&gt; The organic solvent is not particularly limited as long as it is generally used for the photoresist composition, and one or more kinds may be used; propylene glycol monoalkyl ether acetate, and/or 2-heptanone may be used. The coating property is excellent, and the film thickness uniformity of the photoresist film on the large glass substrate is excellent. Although both propylene glycol-based ether acetate and 2-heptanone can be used, if they are used alone or in combination with other solvents, the film thickness uniformity is good when applied by a spin coating method or the like. . Preferably, the propylene glycol-alkyl ether acetate is contained in an amount of from 50 to 100% by mass based on the total of the organic solvent. A propylene glycol-alkyl ether acetate system, for example, a linear or branched alkyl group having 1 to 3 carbon atoms, wherein propylene glycol-methyl ether acetate (hereinafter referred to as PGMEA) is glazed by a large glass substrate. The film thickness uniformity of the resist film is extremely excellent and is particularly preferable. On the other hand, the 2-heptanone is not particularly limited, and when the (B) naphthoquinonediazide compound is combined with the non-diphenylketone-based photosensitive component, it is a suitable solvent. The 2-heptanone is superior to PGMEA in heat resistance, and has a photoresist composition which can reduce the generation of dross, and is an excellent solvent. When 2-heptanone is used alone or in combination with other organic solvents, the content of the entire organic solvent is preferably from 50 to 100% by mass. -20- (17) (17) 1285789 These preferred solvents can be used in combination with other solvents. When a lactic acid ester such as methyl lactate or ethyl lactate (preferably ethyl lactate) is blended, the film thickness of the photoresist film is excellent, and a photoresist pattern having a good shape can be formed. When the propylene glycol-alkyl ether acetate is used in combination with the alkyl lactate, the alkyl lactate is preferably added in an amount of 0.1 to 10 times, 1 to 5 times the mass ratio of the propylene glycol-alkyl ether acetate. Better. Organic solvents such as 7-butyrolactone and propylene glycol-butyl ether can also be used. When 7-butyrolactone is used, the blending amount thereof is preferably 10 to 1 times, more preferably 0.05 to 0.5 times, based on the mass ratio of propylene glycol-alkyl ether acetate. Other organic solvents which can be blended are as follows. 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, and diethyl a diol-acetate, or a polyol such as methyl ether, monoethyl ether, -propyl ether, -butyl ether or monophenyl ether; and a derivative thereof; such as a cyclic ether of dioxane; Ester, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate and the like. When such a solvent is used, it is preferably 50% by mass or less based on all the organic solvents. When the amount of the organic solvent to be used is preferably a component which dissolves the solid components (A) to (D), and other components used as necessary later, it is appropriately adjusted to obtain a uniform positive resist composition. Preferably, the solid component concentration can be as high as 50 mass. /〇, 20 to 35 mass% is better. Positive Light -21 - (18) (18) 1285789 The solid content of the resist composition is equal to the total of (A) to (D) components and other components used as necessary. The positive resist composition of the present invention may contain a compatible additive if necessary, such as an additional resin or a plasticizer for improving the performance of the photoresist film, etc., without departing from the object of the present invention. The stabilizers and surfactants are preserved, and the coloring agent which is more visible to the developed image is added, and the sensitizer, the anti-smudge dye, the adhesion enhancer and the like which are used for enhancing the sensitizing effect are added. The anti-halation dye can be used as a UV absorber (for example, 2,2', 4,4* tetrahydrodiphenyl ketone, 4 dimethylamine-2', 4'-dihydroxydiphenyl ketone, 5-amine one 3 —String-1 1 Benzene 4-(4-hydroxyphenylazo)D-biazole, 4-dimethylamine-4'-hydroxyazobenzene, 4-diethylamine-4'-ethoxyazobenzene , 4 - diethylamine azobenzene, curcumin, etc.). The surfactant may be added, for example, to anti-glare or the like, and may be, for example, FLUORAD FC-430, FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), EFTOP EF122A, EF122B, EF122C, EF126 (trade name, TOCHEM PRODUCTS) A fluorine-based surfactant, XR-104, MEGAFAC R- 08 (trade name, manufactured by Dainippon Ink Chemicals Co., Ltd.). The positive photoresist composition of the present invention is preferably prepared so that the Mw (hereinafter referred to as the photoresist molecular weight) contained in the solid content of the photoresist composition may be in the range of 5,000 to 30,000, more preferably the Mw system 6000. To 1 0000. When the amount of the photoresist is in the above range, it is possible to achieve a high resolution without a decrease in sensitivity, and a positive resist composition having excellent linearity and D0F characteristics and excellent heat resistance. • 22- (19) (19) 1285789 When the molecular weight of the photoresist is less than the above range, the resolution, linearity, D〇F characteristics, and heat resistance are insufficient. When the above-mentioned range is exceeded, the sensitivity is remarkably lowered, which may impair the coating of the photoresist composition. Sexuality. In the present specification, the term "resistance molecular weight" is measured using the following GPC system. Device name: SYSTEM 11 (product name, manufactured by Showa Denko Co., Ltd.) Front column: KF-G (product name, manufactured by Shodex Co., Ltd.) Column ·· KF — 8 05, KF — 8 03, KF — 8 02 (Product name , manufactured by Shodex Co., Ltd. Detector: UV 41 (product name, manufactured by Shodex Co., Ltd.), measured at 280 nm. Solvent, etc.: Flow through a tetrahydrofuran at a flow rate of 1 · 0 / min and measure at 35 ° C. The preparation method of the measurement sample was prepared by preparing a photoresist composition to be measured to a solid concentration of 30% by mass, and diluting it with tetrahydro-d-flethane to prepare a measurement sample having a solid concentration of 0.1% by mass. The measurement was carried out by injecting 20 μl of the measurement sample into the apparatus. Further, in the manufacture of the system LCD, instead of the g-line (436 nm) exposure for the conventional LCD manufacturing, the photolithography using the shorter-wavelength i-line (365 ηη) exposure has a tendency to improve the resolution. On the other hand, the (B) component and the optional component (C) are the positive-type photoresist composition of the present invention using a non-diphenylketone-based compound, and the components (B) and (C) are The absorption of the i-line is suppressed, so it is suitable for the i-line exposure program and can reach higher resolution. -23- (20) (20) 1285789 In the preparation of the positive-type resist composition of the present invention, the method of preparing the resist molecular weight to have the above-mentioned suitable range is, for example, (1) the M w after mixing all the components becomes the above Scope, before the mixing, the (A) component is subjected to a classification operation, etc., and the Mw of the component (A) is first adjusted to an appropriate range, and (2) a plurality of (M) components having a different Mw are prepared, and the mixture is appropriately adjusted. The method of Mw of the solid component in the above range. Among these modulation methods, the modulation method of the above (2) is preferable because the adjustment of the molecular weight of the photoresist and the sensitivity adjustment are easy. <<Modulation Method of Positive Photoresist Composition for System LCD Manufacturing>> The positive photoresist composition of the present invention preferably has (A) component, (B) component, (C) component, and (D) component The other components are dissolved in an organic solvent as necessary to prepare. The preparation may be carried out by mixing the component (D) with other components at the same time as the preparation of the positive photoresist composition, preferably by using an organic solvent compounded with the component (A) of the component (D). A method of modulating a positive photoresist composition to prepare a positive photoresist composition for manufacturing a system LCD of the present invention. The method for preparing a positive resist composition for manufacturing a system for LCD of the present invention is a resin solution obtained by mixing the component (D) in an organic solvent solution of the component (A), and the component (B) and (C) ) A method of mixing ingredients. According to the investigation by the inventors of the present invention, in the preparation of the positive-type resist composition for manufacturing a system for LCD of the present invention, the component (D) is simply added to an organic solvent containing the component (A), and sometimes it cannot be prevented. The quality of the photoresist composition -24-(21) 1285789 has changed over time, even if it is the same product, there will be variations in the characteristics of each batch. As a result of investigation by the inventors of the present invention, it has been found that the deterioration of the photoresist composition is caused only by the deterioration of the PAC, but the deterioration of the organic solvent solution of the component (A) stored for the photoresist modulation causes the above-mentioned respective The reason for the variation in photoresist characteristics between batches. That is, the component (A) is stored in an organic solvent solution, which deteriorates with time, resulting in variation in photoresist characteristics between the batches. Therefore, in the preparation method of the positive resist 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, and is usually 20 to 60% by mass, and usually 35 to 55% by mass is particularly preferable. Next, the solution (I) prepared as described above is blended with the component (D) to obtain an organic solvent solution (solution (II)) (D) containing the components (A) and (D). There is a problem of particle generation after the modulation, and it should be based on the following methods. 1. At room temperature (20 to 25 ° C), in the organic solvent used in the organic solvent of the solution (I), the concentration of the component (D) may be from 1 to 20% by mass, and stirred for more than 10 minutes. Completely dissolved into a solution. 2) The solution of the above component (D) is added in small portions to the solution (I) to obtain a solution (Π). Next, in the solution (II), the component (B) and the component (C) are added, and if necessary, an ultraviolet absorber, a surfactant, etc. are added, and if necessary, a solvent is added to adjust the concentration to a uniform solution (ΠΙ) to obtain the positive photoresist of the present invention. Composition. (22) (22) 1285789 The type of the solvent may be the same as or different from the organic solvent used in the solution (I) or (Π). The resulting solution (m) may also be filtered by a filter or the like. Surprisingly, in the present invention, the preparation solution (Π) is added only to the component (D) required for the stability of the component (A) in the solution (I), and the positive photoresist composition can be prepared by using the solution (11). A stable positive photoresist composition. In other words, it is not necessary to add an additional stabilizer such as the addition of the component (B) to the component (B). As described above, in the preparation method of the present invention, as a result of maintaining the storage stability of the component (A), the storage stability of the positive photoresist composition using the component (A) is also ensured. <<Method of Forming Resistivity Pattern>> An example of a suitable method for forming a photoresist pattern when the system LCD is manufactured using the positive-type photoresist composition of the present invention will be exemplified below. First, the positive resist composition of the present invention described above 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 LCDs which are generally used for non-crystalline cerium oxide, it is preferred that the glass substrate be a glass substrate or the like which is formed by forming a low-temperature polysilicon layer. The glass substrate has a high resolution under low NA conditions due to the positive resist 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. Subsequently, the glass substrate on which the coating film has been formed is subjected to heat treatment (prebaking) at 100 to 140 ° C to remove residual solvent to form a photoresist film. The prebaking method is preferably performed by maintaining a gap between the hot plate and the substrate. -26- (23) (23) 1285789 For the above-mentioned photoresist film, selective exposure was performed using a photomask with a mask pattern. In order to form a fine pattern, the light source is preferably an i-line (3 65 nm). The preferred exposure procedure for this exposure is N A 0.3 or less, 〇 . 2 or less, and a lower NA condition exposure procedure of 0.15 or less. Next, the photoresist film after selective exposure is subjected to heat treatment (post-exposure baking: PEB). The PEB method has a gap between the hot plate and the substrate, and a direct baking without leaving a gap; in order to avoid warpage of the substrate, the diffusion effect of the PEB is obtained, and the baking is performed immediately after baking. The method is better. The heating temperature is 90 to 150 ° C, and the temperature is from 1 to 14 (TC is preferably used for the photoresist film after the PEB described above, and a developing solution such as a 1 to 10% by mass aqueous solution of tetramethylammonium hydroxide aqueous solution is used. Applying the image forming treatment, dissolving and removing the exposed portion, simultaneously forming a photoresist pattern for the integrated circuit and a photoresist pattern for the liquid crystal display portion on the substrate. Further, the developing solution remaining on the surface of the resist pattern is pure The photoresist pattern is washed away to form a photoresist pattern. In the method for forming a photoresist pattern, in the step of selectively exposing the system LCD, the photomask is patterned to have a photoresist of 2.0 μm or less. It is preferable that the mask pattern for pattern formation and the mask pattern for forming the mask pattern for the resist pattern of more than 2.0 μm are preferable. Thus, the positive photoresist composition for LCD of the present invention has a high resolution and a mask. The fine pattern of the pattern is faithfully reproduced by the photoresist pattern. Therefore, in the step of simultaneously forming the photoresist pattern, on the substrate, the pattern size can be simultaneously formed by -27-(24) (24) 1285789. Photoresist pattern for integrated circuits below μιη And a photoresist pattern for the liquid crystal display portion exceeding 2.0 μm. As described above, the positive photoresist composition of the present invention has high sensitivity due to the non-diphenyl ketone-based PAC, and is suitable for i-line exposure, etc. It also has high resolution under low NA conditions. Due to the combination of anti-reducing agents, the duration of long-term storage in the bottle changes, and the temporal changes of photoresist characteristics (sensitivity, size, film thickness, etc.) are suppressed, and the preservation stability is excellent. Moreover, in order to prevent this change in duration, it is necessary to strictly control the storage temperature in the range of, for example, 〇 to 20 ° C, and the positive-type photoresist composition of the present invention has a large storage temperature tolerance range, and can be controlled, for example, to -10 to + 2 5 ° C. And linear, DOF and other characteristics are also good, suitable for the manufacture of system LCD. EXAMPLES Hereinafter, the present invention will be described in detail by way of examples. Modulations using the following Examples 1 to 3 and Comparative Example 1 The positive resist composition is evaluated as follows (1) to (3). Evaluation method (1) Preservation stability evaluation: Dimensional duration evaluation The positive resist composition prepared in the following examples or comparative examples , each prepared, at 2 5 C. Samples stored for six months (i), and samples (ii) stored in cold storage (5 °C) for six months. 曝光ορ exposure when using the above sample (ii) (1.5pmL &amp; S resist pattern Under the exposure amount (mJ) which can be faithfully reproduced, the dimensional change rate of the 1.5 μπι L&amp;S pattern when the photoresist pattern is formed in the same manner as in the above test (28) (25) 1285789 (i) is obtained. The formation of the photoresist pattern was carried out as follows: The sample was coated on a tantalum wafer by a spin coater, and dried on a hot plate at 90 ° C for 30 seconds to obtain a photoresist film having a film thickness of 1.05 μm. The film was selectively exposed by an i-ray exposure apparatus (product name, FX 702J&quot;, NIKON Corporation, NA = 0, 14), and subjected to PEB (post-exposure baking) treatment at 1 l ° ° C for 90 seconds. Next, a 2.3% by mass concentration of TMAH aqueous solution (product name ''NMD-3〃, manufactured by Tokyo Yinghua Industry Co., Ltd.) was used for imaging at 23 °C and 90 seconds, and pure water was used for 30 seconds. The treatment was washed and then subjected to a drying step to form a 1·5 μm L&amp;S pattern. (2) Evaluation of the resolution: The limit resolution of the above sample (i) was determined by using the above sample (ii) at the exposure amount of Εορ. (3) Linear evaluation: Each of the above-mentioned samples (i) was applied to a glass substrate on which a Ti film was formed by a photoresist coating apparatus for a large substrate (device name: TR3 6000, manufactured by Tokyo Ohka Kogyo Co., Ltd.). After (550nm X 650mm), the hot plate temperature is 100 °C, and the first drying is performed for 90 seconds by the adjacent baking at intervals of about 1 mm, and then the hot plate temperature is 90 °C, and the temperature is maintained at 0.5 mm. The adjacent baking was applied to the second drying for 90 seconds to form a photoresist film having a film thickness of 1.5 μm. Secondly, through the test mask that simultaneously depicts the reticle pattern with 3.0μιη lines and spacing (L&amp;S) and 1.5μιη L&amp;S photoresist pattern. 29· (26) (26)1285789 (Standard Line)), using an i-line exposure device (device name: FX-702J, manufactured by NIKON Corporation; ΝΑ = 0·14), to selectively reproduce the exposure amount of ·5μιη L&amp;S (Εορ exposure) exposure. Next, the temperature of the hot plate was 120 ° C, and the interval of 〇 5 mm was maintained, and the heat treatment was performed for 30 seconds in the vicinity of baking, and then the heat treatment was performed by direct baking without gap at the same temperature for 60 seconds. Next, a 2.38 mass% butyl]^8 1 aqueous solution using a slit-coating nozzle developing device (device name: TD-3 9000 demonstration machine, manufactured by Tokyo Yinghua Industrial Co., Ltd.), as shown in Fig. 1, from The substrate end portion X was held by Y to Z for 10 seconds on the substrate for 10 seconds, and then washed with water for 30 seconds and spin-dried. Then, an SEM (scanning electron microscope) photograph of the cross-sectional shape of the obtained photoresist pattern was observed, and the reproducibility of the resist pattern of 3.0 μm L &amp; S was evaluated. A dimensional change rate of ± 10% or less is A, and more than 10% to 15% or less is Β ‘ more than 15% is C. (Example 1) The following components (A) to (D) were prepared as follows: (A1) Mixed phenols 1 using m-cresol/3,4-dimethylphenol = 8/2 (mole ratio) Moer, synthesized with formaldehyde 0.82 molar method,

Mw = 20000, Mw / Mn = 5.2 phenolic lacquer lacquer. (B) Ingredients: (B1): bis(5-cyclohexyl-4-hydroxy-2-phenyl)- 3,4-dihydroxyphenylmethane (ΒΓ) 1 molar and 1,2-naphthoquinone Nitrogen 5- 5 - -30- (27) (27) 1285789 Alkyl chloride [hereinafter abbreviated as (5 - NQD). 2 molar esterification reaction product (B2): bis(2,4-dihydroxyphenyl)methane (B2') 1 molar and 5 - NQD 2 molar esterification reaction product (B3): double ( 4-Hydroxy-2,3,5-trimethylphenyl)-2-hydroxybenzoic acid (B3,) 1 molar and 5 - NQD 2 molar esterification reaction product (C) Composition: (C1): double (5_cyclohexyl-4-hydroxyl-2-tolyl)-3,4-dihydroxyphenylmethane (D) Component: (D 1 ): p-benzoquinone organic solvent:

(El) : PGMEA (Examples 1 to 3, Comparative Example 1) The component (A) described in the following Table 1 was dissolved in an organic solvent (E1), and the following Table 1 was blended. The component (D) of the compounding amount (parts by mass) is dissolved in a solution. To the solution, the component (B) and the component (C) in the amounts (parts by mass) of the following Table 1 were added and dissolved, and the mixture was filtered through a filter having a pore size of 0.2 μm to prepare a positive resist composition. The photoresist molecular weight of the resulting positive photoresist composition is shown in Table 1. Each of the above-mentioned (1) to (3) was evaluated for each of the obtained positive-type photoresist compositions. The results are shown in Table 2 below. -31 - (28) 1285789 Table 1 (4) Ingredients (combination amount) (Β) Component (mixing ratio) (combination amount) (C) Component (combination amount) (D戚(mixing amount) (Ε) component (mixing amount) Photoresistance molecular weight Example 1 Al(15) Β1/Β2/Β3 (mixing ratio 6/1/1) (combination amount 5.5) Cl(4.5) Dl(0.3) El(75) 10000 Example 2 Same as above as above D1 (Ol) Same as above. Example 3 Same as above, the same as above, Dl(0.5) Same as above, Comparative Example 1 Same as above, same as above \ ✓ \ \Ν Same as above 2

Dimensional duration evaluation (%) Resolution evaluation (μπι) 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 + 3·6 Note] ) 1.4 A Note 1) 25t, one month result

The positive-type resist compositions of Examples 1 to 3 were superior in dimensional evaluation and good in storage stability as compared with the resist composition of Comparative Example 1 which was not blended with an anti-reducing agent. Also, the resolution is still high under low NA conditions (ΝΑ = 0·14), and the linearity is also good. -32- (29) 1285789 Effect of the Invention As described above, the positive resist composition of the present invention is excellent in storage stability and is suitable for the manufacture of a system LCD. [Simple diagram of the diagram] Figure 1 shows the linear evaluation of the low-NA condition. The positive-type photoresist composition is applied to a glass substrate, baked and dried, and after pattern exposure, the image is imaged by a slit applicator. A schematic diagram of the device for ejecting the developing solution from the end of the substrate X to Z.

-33-

Claims (1)

1285789 Pickup, Patent Application No. 93 1 14496 Patent Application Revision of Chinese Patent Application Revision Amendment of April 26, 1996 of the Republic of China 1 · A positive photoresist composition that forms an integrated circuit and liquid crystal on a substrate A partial positive photoresist composition for LCD manufacturing is characterized by: (A) an alkali-soluble resin, (B) containing the following general formula (I) (OH)b ··〇) [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 carbon number of 3 to 6 a cycloalkyl group; R1G, R11 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; when R9 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q1 represents a hydrogen atom, and the number of carbon atoms is 1 to 6 alkyl or the following chemical formula (II) (wherein R12 and R13 each independently represent a hydrogen atom, a halogen atom, a carbon atom of 1285789, an alkyl group of 1 to 6, an alkoxy group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms; a residue represented by an integer of 1 to 3), when Q1 is bonded to the end of R9, Q1 together with R9 and a carbon atom between Q1 and R9, and a cycloalkyl group having a carbon chain of 3 to 6; a, b Table 1 An integer of up to 3; d is an integer from 0 to 3; a, b or d is 3 without each of R3, R6 or R8; η is an integer of 0 to 3) and the compound is represented by 1,2-naphthoquinone An esterification reaction product of a sulfonium compound, a naphthoquinonediazide compound, (C) a phenolic hydroxyl group-containing compound having a molecular weight of 1 000 or less, and (D) a lanthanoid compound as an anti-reducing agent dissolved in an organic compound It is obtained from a solvent. 2. The positive resist composition of claim 1, wherein the reducing material corresponding to the component (D) is contained. 3. A positive-type photoresist composition as claimed in claim 1, wherein the component (D) is benzoquinone. 4. The positive-type photoresist composition of claim 2, wherein the reducing substance is hydroquinone. A method for preparing a positive-type optical Φ-blocking composition according to any one of claims 1 to 4, characterized in that the (D) is compounded in the organic solvent solution of the component (A) A resin solution obtained by mixing the components with the components (B) and (C). A method for forming a photoresist pattern, comprising: (1) applying a positive-type photoresist composition according to any one of claims 1 to 4 on a substrate to form a coating film a step of (2) heat-treating (pre-baking) the substrate formed by the coating film to form a photoresist film on the substrate, and (3) drawing a light of 2. Ομπι for the photoresist film -2- 1285789 The step of forming a mask pattern for resisting pattern formation, selectively exposing the mask with both mask patterns for forming a photoresist pattern exceeding 2. Ομιη, and (4) for the photoresist after selective exposure a film, a step of heat treatment (post-exposure baking: ΡΕΒ), and (5) applying a development process using an alkali aqueous solution to the photoresist film after the heat treatment, simultaneously forming a pattern size 2 on the substrate Ομιη The following step of the resist pattern for the integrated circuit and the photoresist pattern for the liquid crystal display portion exceeding 2.0 μm. Ί · The method for forming a photoresist pattern according to item 6 of the patent application, wherein the step of performing selective exposure is to use an i-line as a light source, and the NA is exposed to light under a low NA condition of 0.3 or less. Conductor.