TW200426517A - Positive photoresist composition for manufacturing a system LCD and method for forming resist pattern - Google Patents

Abstract

A positive photoresist composition for manufacturing a SYSTEM LCD, wherein the composition comprises an esterified reaction product which is obtained by a reaction of a polyphenol compound, which has a molecular weight of 1000 or less and has at least two benzene rings per molecule wherein at least two hydroxyl groups are bonded thereto, with a 1, 2-naphthoquinon diazide sulfonyl compound.

Description

200426517 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a photoresist composition for a system LCD and a method for forming a photoresist pattern [prior art] In the prior art, thin film transistors (TFTs), etc. In terms of photoresistive materials for the manufacture of liquid crystal display elements (LCDs), they are suitable for g, h, and i-line exposure, and because they are relatively inexpensive and highly sensitive, phenolic lacquer resins are used in alkali-soluble resins. Hereinafter, referred to as PAC) is the use of naphthoquinone diazide-based compounds. Phenolic lacquer-naphthoquinone diazide-based photoresist is often used (for example, refer to Japanese Patent Application Laid-Open No. 2000 — 1 3 1 8 3 5 (Japanese Laid-Open Patent Publication No. 2001-75272, Japanese Laid-Open Patent Publication No. 2000- 1 8 1 05), Japanese Laid-Open Patent Publication No. 2000-112120) The aforementioned photoresist is generally used to form a pixel portion of a display, and only Very rough pattern (about 3 ~ 5 // m) of the material but 'in recent years' in the next generation of LCD, tied to a glass substrate, can make the driver, DAC (digital analog converter), portrait Processor, video control The integrated circuit part of the controller, r AM, and the display part are formed at the same time. The so-called "system LCD" is being developed for high-performance LCD technology (for example, please refer to Semiconductor FPD World 2001.9, ρρ · 50-67).

In this specification, hereinafter, this type of LCD that can form an integrated circuit and a liquid crystal display portion on one substrate is conveniently referred to as a system LCD. • 5- (2) (2) 200426517 In this way, a system LCD substrate has recently been Low-temperature polysilicon, especially low-temperature polysilicon formed by low-temperature processing below 600 ° C, is expected to be appropriate because of its lower resistance and higher mobility compared to amorphous. Because of this, the development of the low temperature polysilicon system for substrate L c D is actively underway. [Problems to be Solved by the Invention] In the manufacture of system LCDs, in the photoresist material, the fine pattern of the integrated circuit part and the rough pattern of the liquid crystal display part, and the ability to form a good shape (linear characteristics) Improvements, high resolution, and improvement in DOF characteristics are strictly required. In addition, in order to manufacture a TFT made of low-temperature polysilicon, a low-temperature polysilicon film is formed on the glass substrate by low-temperature processing, and then P or B is injected into the low-temperature polysilicon film. With. Therefore, improvement in heat resistance relative to this is also required. In addition, in the manufacture of system LCD, in the photolithography step, the introduction of the i-line (365 nm) exposure process can be expected. Therefore, photoresist materials suitable for exposure at the aforementioned wavelengths, that is, suitable for i-line exposure processes, are required and imaginable. Furthermore, the decrease in the sensitivity of the photoresist material will cause a fatal decrease in productivity in the field of system-containing LCD and LCD manufacturing. Therefore, a photoresist material that satisfies the above characteristics and does not cause a decrease in sensitivity is desirable.

But so far, there are no examples of reports on system LCDs that meet these conditions. 6- (3) (3) 200426517 Manufacturing photoresist materials Realization is strongly expected. On the one hand, in the system LCD manufacturing steps, the transparent conductive film ITO (Indium Tin Oxide) film formed on the substrate or other underlying layers is etched in the same manner as the conventional LCD manufacturing steps, and the wet etching step may be performed. The imaginary one. Conventional photoresist materials for LCD manufacturing, from the viewpoints of reducing raw material costs and taking high sensitivity as the most important, etc., are alkali-soluble resins (mainly phenolic lacquer resins) used as resin components. The step-by-step process is used, but a resin with a large dispersion is used. Among the aforementioned resins, monomers used for the synthesis of such resins or dimers, trimers, tetramers, etc., which are by-products during synthesis, may be contained in a large amount. The aforementioned low-molecular-weight body exhibits its effect as an adhesive between a photoresist pattern and a substrate, and is considered to have good adhesion to the photoresist pattern substrate during a wet etching step. However, when using a photoresist composition with a large dispersion resin, it is difficult to achieve the high resolution required for system LCD manufacturing. Therefore, I think that for system LCD manufacturing, a step-by-step process can be used. It is desirable to remove the resin (fractional resin) photoresist composition with a low molecular weight as much as possible. However, when the present inventors used a photoresist composition of a stepped resin to form a photoresist pattern, the adhesion to the photoresist pattern substrate would be deteriorated, and it would be caused to the substrate during wet etching. This insight is obtained by the infiltration phenomenon of the etching solution on the film or the peeling phenomenon caused by the substrate of the photoresist pattern. (4) (4) 200426517 Therefore, the problem of the present invention is to provide an appropriate positive-type photoresist composition for the manufacture of a system LCD, which is excellent in adhesion to a substrate. [Means for Solving the Problems] The present inventors have deliberately reviewed to solve the aforementioned problems. As a result, it was found that a positive photoresist composition in which a product obtained by esterification reaction of a specific polyphenol compound and a 1,2-naphthoquinonediazidesulfonyl sulfonyl compound was compounded was excellent in adhesion to a substrate. In the manufacture of the system LCD, the formation of the photoresist pattern can also be used appropriately by the user, thus completing the present invention. That is, the first aspect of the present invention contains a polyphenol compound having a molecular weight of less than 1,000 and having at least two benzene rings in one molecule and having at least two hydroxyl groups bonded to at least one of the aforementioned benzene rings. Positive photoresist composition formed by esterification reaction with 1,2-naphthoquinonediazidesulfofluorenyl compound. In addition, a second aspect of the present invention is a method for forming a photoresist pattern for LCD manufacturing, in which an integrated circuit and a liquid crystal display portion can be formed on a substrate, which comprises: (1) having at least one molecule Two benzene rings' and at least one of the aforementioned benzene rings has at least two hydroxyl bonds, and the esterification reaction of a polyphenol compound containing a molecular weight of less than 1,000 and 1,2-naphthoquinonediazidesulfonylsulfonyl compound Step of applying a positive photoresist composition on a substrate to form a coating film, (2) heating the substrate having the above-mentioned coating film formed thereon, and forming a photoresist film on the substrate, (3) relative to The above photoresist film uses a mask pattern for forming a photoresist pattern below 2.0 // m and a mask pattern for forming a photoresist pattern exceeding 2.0 / im. 8-8 (5) (5) 200426517 The masking steps described by Fang for the selective exposure step, (4) the PEB step of the heat treatment is performed on the photoresist film after the selective exposure, and (5) the photoresist film is the same as the photoresist film after the heat treatment , The development process using an alkaline aqueous solution, in the above Board, can developing step by the pattern size of the resist pattern for integrated circuits and, more than 2.0 / zm display section of the liquid crystal forming the resist pattern at the same time. SUMMARY OF THE INVENTION Hereinafter, the present invention will be described in detail. The present invention relates to a photoresist composition and a photoresist pattern forming method suitable for use in the manufacture of a system LCD capable of forming an integrated circuit and a liquid crystal display portion on a substrate. "Positive Photoresist Composition" The positive photoresist composition of the present invention contains an esterification reaction product of a specific polyphenol compound and a 1-naphthoquinonediazidesulfofluorenyl compound (hereinafter referred to as (D ) Ingredients) are their special agents. The aforementioned polyphenol compound has at least two benzene rings in one molecule, preferably two to six, most preferably two benzene rings, and at least two of the aforementioned benzene rings, at least two, preferably two ~ 5, more preferably 2 ~ 3 hydroxyl-bonded polyphenylenefluorene compounds. The molecular weight of the polyphenol compound is 1,000 or less, and preferably 700 or less. The molecular weight is preferably 100 or more, and more preferably 200 or more. -9- 200426517

[In the formula, a is an integer of 2 to 4, preferably 2 to 3, and b is an integer of 0 to 4, preferably 0 to 1.] The diphenyl ketone compound shown in the following; General formula (III) described later Among the non-diphenyl ketone compounds shown in), at least one of d to g is a compound of 2 or more; and the like. However, in particular, the diphenyl ketone compound represented by the general formula (I) is preferable because it has an excellent effect of improving adhesion to a substrate. The diphenyl ketone compound represented by the above-general formula (I) wherein the general formula (II) is as follows

HO OH

[In the formula, c represents 0 to 4, preferably an integer of 0 to 1.] The diphenyl ketone compound represented by the formula is particularly preferable because it has an excellent effect of improving adhesion to a substrate. More specifically, the compound of general formula (I) or (II) may be 2,3,4-trihydroxydiphenyl ketone, 2,3,4,4'-tetrahydroxydiphenyl ketone Wait. (D) Component, an additive that exhibits the effect of improving the adhesion with a very small amount of the compound, and can also show the effect of the adhesion improving agent. -10- (7) (7) 200426517 The compounding amount of the (D) component in the positive-type photoresist composition of the present invention is 0.1 to 50% by mass, and preferably 1 to 10, relative to the photoresist solidification component. quality%. (D) The compounding amount of the component is above the lower limit 値, and a sufficient adhesion improving effect can be obtained. On the one hand, below the upper limit 値, the occurrence of dross can be reduced. As an example of the 1,2-naphthoquinonediazidesulfofluorenyl compound used in the present invention, 1,2-naphthoquinonediazide-4 monosulfonamido compound or 1,2 dinaphthoquinonediazide As a 5-sulfofluorenyl compound, 1,2-naphthoquinonediazidesulfonic acid compound can be exemplified. In further specific examples, 1,2-naphthoquinonediazide-4-sulfofluorenyl chloride, 1,2-naphthoquinonediazide-5-sulfofluorenyl chloride, and the like can be mentioned. Halides of azide compounds. When the positive-type photoresist composition of the present invention contains the component (D), the other components are not particularly limited. Generally speaking, the positive photoresist composition and its components used in the formation of the photoresist pattern can be included in the composition of the present invention, that is, they can be used. As the positive-type photoresist composition which can be suitably used in the present invention, 3 may be exemplified as those having the following components (A) to (C). (A) Alkali-soluble resin (B) Naphthoquinonediazide esterified product (C) Phenol-containing hydroxy compound having a molecular weight of 1,000 or less Hereinafter, each of these components can be described in more detail. <(A) component> (A) component, alkali-soluble resin. -11-(8) 200426517 (A) component, there is no particular limitation. 'It can be selected according to the needs. The photoresist composition can usually be used arbitrarily by selecting one or two or more types of coating-forming materials. For example, phenols (phenol, ni-cresol, p-cresol, trimethylphenol, etc.) and aldehydes (formaldehyde, formaldehyde precursors, monohydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde Or ketones (methyl ethyl ketone, acetone, etc.), obtained in the presence of acid catalyst, phenolic resin; hydroxystyrene alone polymer; or, copolymer of hydroxystyrene and olefinic monomer, hydroxystyrene A hydroxystyrene resin such as a copolymer with acrylic acid or a methyl derivative thereof; copolymerization of acrylic acid or methacrylic acid with a derivative thereof or a methacrylic resin, etc. In particular, it contains m-cresol and -p- Cresol phenols and aldehydes aldehydes, the phenolic lacquer resins obtained by the condensation reaction, and the photoresist materials with excellent sensitivity are adjusted appropriately. (A) The component can be manufactured according to conventional methods. Glue according to (A) component The polystyrene content average molecular weight (Mw) of the permeation chromatography chromatography depends on the type, and is preferably from 2000 to 100,000, and more preferably from 3,000 to 10,000. '(A) composition system, Mw is 2000 ~ 100000 3000 ~ 30,000 The dispersion degree (Mw / number average molecular weight (μ) is in the range of 2 to 10 ', more preferably 2.5 to 7.0, and the reason is that SI lacquer resin (hereinafter referred to as step resin) is a good choice. Among users, xylenol propionaldehyde, 2 etc.) and / or other styrene-acrylic acid or acrylic acid, which contains methyl and has a resolution of olefin conversion quality or a pattern of 30000 〇, more preferably η) are divided into steps Division-12-200426517 By using such a stepped resin as the component (A), a positive photoresist composition having excellent resolvability can be obtained. The stepwise treatment is performed by, for example, separate precipitation treatment of molecular weight dependence of polymer solubility. Separate precipitation treatment, for example, first, dissolve the phenolic lacquer resin of the condensation product obtained as described above in a polar solvent. Alternatively, a weak solvent such as water, heptane, hexane, pentane, or cyclohexane can be added to the solution. Mix and stir. In this case, it was dissolved in a low-molecular weight polymer weakly. Therefore, by filtering out the precipitates, a stepped resin can be obtained in which the content of the low molecular weight polymer can be reduced. Examples of the polar solvent include alcohols such as methanol, ethanol, ketones such as acetone, methyl ethyl methyl ethyl ketone, glycol ether esters such as ethylene glycol monoethyl ether acetate, and tetrahydrofuran. And other cyclic ethers. &lt; (B) component &gt; (B) The component is a naphthoquinonediazide esterified product. (B) The component system is generally used in a positive type photoresist composition, as long as it is a photosensitive component (PAC) user. There is no particular limitation, and one or two or more types can be arbitrarily selected for use. Among them, the following general formula (ill)

••• (Π) [In the formula, R1 to R8 are each independently a hydrogen atom, a halogen atom, a fluorenyl group having 1 to 6 carbon atoms, and a carbon atom having 1 to 6 carbon atoms or a carbon atom. 13- (10) (10) 200426517 Cycloalkyl groups having 3 to 6 subunits; R1G and R11 are each independently hydrogen atom or alkyl group having 1 to 6 carbon atoms; R9 may be hydrogen atom or alkane having 1 to 6 carbon atoms Group, in this case, Q] is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the following chemical formula (IV)

(In the formula, 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; f represents an integer of 1 to 3), Q1 may be bonded to the terminal of R9. In this case, Q1 is a carbon atom between R9 and Q1 and R 9 and meanwhile, it represents a ring of carbon chain 3 to 6. Alkyl; d, e represent integers of 1 to 3; g represents integers of 0 to 3; integers of 0 to 3. ] The esterification reaction product of the compound shown below with 1,2-naphthoquinonediazidesulfonylsulfonyl compound (non-diphenyl ketone PAC) is suitable for i-ray photolithography due to its high sensitivity. , So it is better. In addition, under these conditions, under low NA conditions (for example, NA is 0.3 or less), the resolution is also excellent, and it is appropriate to form a photoresist pattern with a good shape. It is also preferable to use a point of linearity or DOF (depth of focus). In addition, as described above, the alkyl group, the alkoxy group, and the cycloalkyl group may have a substituent if necessary, even if they do not contain a substituent. In terms of the phenol compound of the aforementioned general formula (III), for example, Q1 is not bonded to the terminal of R9, R9 is a hydrogen atom or an alkyl group of 14 to 6 carbon atoms (11) 200426517, and Q1 is the aforementioned chemical formula (IV ), A ternary compound of which η is 0, and Q1 is not bonded to the terminal of R9, R9 is a hydrogen atom or a carbon alkyl group, Q1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and η is 1, preferably a linear polyphenol compound. Triphenol-type compounds, more specifically, triphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-methane, and bis (4-hydroxy-2,3,5— Trimethylphenyl) —: phenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -zeta phenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) 1: phenylmethane, bis (4-hydroxy-3,5-dimethylphenyl), 1: phenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -ζphenylmethane, Bis (4-hydroxy-2,5-dimethylphenyl,)-ylphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -ylphenylmethane, bis (4-hydroxy One 3,5-Dimethylphenyl) Dihydroxyphenylmethane, Bis (4 Monohydroxy-2,5-Dimethylbenzene 3,4-Dihydroxyphenylmethane, Bis (4-monohydroxy-2,5 —Dimethyl) —2,4-dihydroxyphenylmethane, bis (4-monohydroxyphenyl) -oxy—4-hydroxyphenylmethane, bis (5-cyclohexyl-4—hydroxy: methylphenyl) One 4-hydroxyphenylmethane, bis (5-cyclohexyl · yl one 2-methylphenyl) -3-hydroxyphenylmethane, bis (5--4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, 1 cyclohexyl-4 4-hydroxy-2-methyl Phenyl)) — 3,4 via methane and so on. In terms of linear polyphenol compounds, more specifically, [Hydroxyhydroxybenzenes with a phenolic number of 1 to 6-3, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, and a hydroxyl group. —Cyclo-3,4—yl) monophenylphenyl—3—methyl-2 — -4 —hydroxycyclohexylbis (5-ylphenyl) can be exemplified by -15- (12) (12) 200426517 2,4 One bis (3, 5-dimethyl-1, 4-hydroxybenzyl) one 5-hydroxyphenol, 2,6-bis (2,5-dimethyl-4, 4-hydroxybenzyl) one 4-methylol, etc. A linear 3-nuclear phenolic compound; 1,1-bis [3-(2-hydroxy-5 -methylbenzyl) -4 -hydroxy-5 -cyclohexylphenyl] isopropane, bis [2,5 — Dimethyl-3— (4-hydroxy-5—methylbenzyl) —4 monohydroxyphenyl] methane, bis [2,5-dimethyl-3— (4-hydroxybenzyl) —4-monohydroxy Phenyl] methane, bis [3- (3,5-dimethyl-4 4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl -4-Hydroxybenzyl) -4-Hydroxy-5 -ethylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4 4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4 Monohydroxy-5-ethylphenyl] methane, bis [2-hydroxy-3— (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2-hydroxy One 3- (2-hydroxy-5—methylbenzyl) _5-methylphenyl] methane, bis [4-hydroxy-3_ (2-hydroxy-5—methylbenzyl) —5-methylbenzene Linear] 4-core phenolic compounds such as methane, bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl) methane, etc .; Bis [2-Hydroxy-3— (4-Hydroxybenzyl) -5—methylbenzyl] -6-cyclohexylphenol, 2,4—Bis [4-Hydroxy-3— (4-Hydroxybenzyl) — 5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-2—3- (2-hydroxy-5—methylbenzyl) —4-hydroxybenzyl] — Linear 5-nuclear phenol compounds such as 4-methylphenol. In addition, the so-called "nucleus" of the three-core or five-core bodies means the benzene -16- (13) (13) 200426517 ring. In addition to the triphenol compound and the linear polyphenol compound, the phenol compound of the general formula (111) can be exemplified by bis (2,3,4-trihydroxyphenyl) methane and bis (2,4 — Dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl ~ 4, -hydroxyphenylmethane, 2- (2,3,4 trihydroxyphenyl)-2-(2 ,, 3 ,, 4,1-trihydroxyphenyl) propane, 2-(2,4-basic group)-2-(2,4 -biphenylyl) group, 2-(4 -hydroxyphenyl)-2 -(4, -hydroxyphenyl) propane, 2- (3 monofluoro-4 -hydroxyphenyl) 2- (3, monofluoro-4, monohydroxyphenyl) propane, 2- (2,4-di (Hydroxyphenyl)-2_ (4, -hydroxyphenyl) propane, 2- (2,3,4 dioxophenyl) _2-(4'-Cyclophenyl) propane, 2- (2,3 Bisphenol-type compounds such as, 4-trihydroxyphenyl) -2- (4- · hydroxy-3,5, -dimethylphenyl) propane; 1- [1- (4-hydroxyphenyl) isopropyl Yl] -4-[^, 丨 -bis (4-hydroxyphenyl) ethyl] benzene, 1_ [1- (3-methyl-1 4 —Cyclophenyl) isopropyl] —4— [1,1-bis (3-methyl—4 ~ hydroxybenzene g) ethyl] benzene, and other polynuclear branched compounds; 1,1 ~ bis ( 4 Once phenyl) cyclohexane and other condensation phenol compounds. These phenol compounds can be used singly or in combination of two or more. Among them, those having a 'triphenol-type compound as a main component' are highly sensitive, and have better resolvability and heat resistance. In particular, bis (5-cyclohexyl-1, 4-meryl, 2-methylphenyl), 3,4-dihydroxyphenylmethane [hereinafter referred to as (Bl,). ], Bis (4-monophenyl-2,3,5-trimethylphenyl)-2 once via phenylphenylmethane [hereinafter referred to as (B3 '). : 1 is better. In order to adjust the solution-17- (14) (14) 200426517, the photoresist composition having excellent balance of photoresistance characteristics, sensitivity, heat resistance, DOF characteristics, linearity, etc., can be made linear. A polyphenol compound such as a bisbenzene selective compound, a polynuclear branched compound, and a condensed phenol compound, etc., is preferably used in combination with the triphenol compound. In particular, the bis-benzene discretionary compound ′ is used in combination with bis (2,4-dihydroxyphenyl) methane [hereinafter referred to as (B2 ’)] to adjust a photoresist composition having excellent overall balance. In addition, hereinafter, the respective naphthalene diazide esters of the aforementioned (B 1,), (B 2 ,,), (B 3,) are abbreviated as (B 1), (B 2), (B 3). When (B1) and / or (B3) are used, the amount of each of these in the (B) component may be 10% by mass or more, and more preferably 15% by mass or more. Also in the case of using (B 1) '(B2) and (B3) all, as far as the effect is concerned, the respective blending amount (B1) is 50 to 90% by mass, preferably 60 to 80% by mass, ( The blending amount of B2) is 5 to 20 mass%, preferably 10 to 15 mass%, and the blending amount of (B3) is 5 to 20 mass%, preferably 10 to 15 mass%. The method of esterifying all or a part of the phenolic hydroxyl group of the compound represented by the general formula (III) with naphthoquinonediazidesulfonic acid can be carried out according to a conventional method. For example, naphthoquinonediazidesulfofluorenyl chloride can be obtained by condensing with a compound represented by the general formula (111). -18- (15) (15) 200426517 Specifically, for example, a compound represented by the above general formula (111) and naphthoquinone-1,2-diazide-4 (or 5) -sulfonyl chloride Organic solvents such as compounds, epoxyhexane, n-methylpyrrolidone, dimethylacetamide, tetrahydrofuran, etc. are dissolved in accordance with the quantitative determination. Next, one or more basic catalysts such as triethylamine, triethanolamine, pyridine, alkali carbonate, bicarbonate, etc. are added for reaction, and the resulting product is washed with water and dried to prepare the desired substance. The component (B) is preferably exemplified as described above. In addition to the naphthoquinonediazide esterified product, other naphthoquinonediazide esterified product can be used. For example, an esterification reaction product of a phenol compound such as polyhydroxydiphenyl ketone or alkyl gallate, and a naphthoquinonediazidesulfonic acid compound can be used. The amount of the component (B) is preferably 80% by mass or less, particularly 50% by mass or less, from the viewpoint of improving the effect of the present invention. The compounding amount of the component (B) in the photoresist composition is 20 to 70% by mass, preferably 25 to 60% by mass based on the total amount of the component (a) and the following (C) component. When the compounding amount of the component (B) is equal to or more than the above-mentioned lower limit, a faithful image of the pattern can be obtained, and the transferability can be improved. It can be lower than the above upper limit 値, can prevent the deterioration of sensitivity, can improve the homogeneity of the formed photoresist film, and can obtain the effect of improving the resolution. &lt; (C) component &gt; -19- (16) (16) 200426517 The positive-type photoresist composition of the present invention 'in addition to the above-mentioned (A) component and (B) component' Furthermore, the sensitizer may contain (C) A phenol-containing hydroxy compound having a molecular weight of 1,000 or less. This (C) component is excellent in sensitivity improvement effect. Therefore, by using the (C) component, in the process of i-line exposure under low n A conditions, suitable materials with high sensitivity and high resolution can be obtained. LCD manufacturing materials can be better suitable for system LCDs with better linearity. Of materials. (C) The molecular weight of a component is 1,000 or less, Preferably it is 700 or less. In addition, it is more preferably 200 or more ', and preferably 300 or more, from the viewpoint of the above effects. As for the component (C), the phenol-containing hydroxy compound used as a sensitivity-improving material or a general photoresist composition for a sensitizer is not particularly limited as long as it satisfies the above-mentioned molecular weight requirements. You can choose one or two or more. Then, the following general formula (v

[In the formula, R21 to R 2 8 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkane having 3 to 6 carbon atoms. R3G, R31 are each independently 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. (20) (17) 200426517, in which case, Q2 is A hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a group represented by the following chemical formula (VI)

(〇H) j (In the formula, R32 and r33 are each independently hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, or 3 to 6 carbon atoms Cycloalkyl; j represents an integer of 0 to 3), Q2 is a bondable with the terminal of R29, in this case, Q2 is a carbon atom between R29 and Q, Q 2 and R2 9 and at the same time, carbon chain 3 The ring base of ~ 6; h, i represents an integer of 1 ~ 3; k represents an integer of 0 ~ 3; m represents an integer of 0 ~ 3] The phenol compound shown in the figure can well display the above characteristics and is better. Specifically, for example, as exemplified in the component (B), in addition to the compound represented by the general formula (III), bis (3-methyl-4-hydroxyphenyl) -4isopropylphenylmethane, bis (3-methyl-4-hydroxyphenyl) monophenylmethane, bis (2-methyl-4-hydroxyphenyl) -phenylmethane, bis (3-methyl-2-hydroxyphenyl) -benzene Methane'bis (3,5-dimethyl-4 4-hydroxyphenyl) -phenylmethane, bis (3-ethyl-4 4-hydroxyphenyl) -phenylmethane, bis (2-methyl-4 Triphenyl compounds such as monohydroxyphenyl) monophenylmethane and bis (2-tertiarybutyl-4,5-dihydroxyphenyl) monophenylmethane can be used appropriately. Among them, bis (2-methyl-1, 4-hydroxyphenyl) phenylmethane, 1— [1—M-hydroxyphenyl) isopropyl] —4— [1,1—bis (4—basic group) —B Basic] This is preferably -21-(18) 200426517 (C) The amount of the component, the effect of the component) is 5 ~ 70 mass%, preferably 10 ~ &lt; Organic solvent &gt; The positive photoresist of the present invention If the composition, and then the organic solvent, is the limitation of the use of the photoresist composition, one or two or more combinations can be selected to contain propylene glycol monoalkyl ether acetate and excellent cloth properties. The point is better. In addition, although both propylene glycol monoalkyl ethers can be used, the film thickness of the propylene glycol monoalkyl ether acetate can be uniformly applied to each of the propylene glycol monoalkyl ether acetates alone, or can be applied by spin coating or the like. 100% by mass is preferred. Propylene glycol monoalkyl ether acetate, such as those having or branched alkyl groups. Among them, C2 and below (referred to as PGMEA) are particularly excellent because they have excellent film thickness uniformity in large glass. On the one hand, 2-heptanone is not particularly limited. In addition, the naphthoquinonediazide ester is a suitable solvent when combined with a non-diphenyl group. In terms of (A 60% by mass range. It is preferable to contain an organic solvent. Those that are generally used are not particularly used./ Or 2-heptanone, which has excellent uniformity of the film thickness of the acetate and 2 —The case where the organic solvent of heptone is mixed with the homogeneity of the user is a multi-organic solvent containing a linear alcohol monomethyl ether acetate with a carbon number of 1 to 3 (photoresist film on a glass substrate [ However, as mentioned above (β-ketone-based photosensitive component group-22- (19) (19) 200426517 2-heptanone), PGMEA is superior in heat resistance, and has the characteristics of being able to impart dross to reduce photoresist composition It is a very good solvent. When 2-heptanone can be used alone or mixed with other organic solvents, it is better to make 2-heptanone contain 50 to 100 mass in all organic solvents. In addition, Preferable solvent can be mixed with other solvents. For example, when mixed with alkyl lactate such as methyl lactate, ethyl lactate, etc. (preferably ethyl lactate), it has excellent film thickness uniformity to form a photoresist film. Those with excellent photoresist patterns are preferred. When propylene glycol monoalkane is used in combination In the case of ether acetate and alkyl lactate, the mass ratio of acetic acid monoalkyl ether acetate to propylene glycol monoalkyl ether acetate is preferably 0.1 to 10 times the amount, preferably 1 to 5 times the amount of alkyl lactate to be blended. 7-Organic solvents such as butyrolactone or propylene glycol monobutyl ether can also be used. When r monobutyrolactone is used, it is 0.01 to 1 times the mass ratio of propylene glycol monoalkyl ether acetate, A blending amount in the range of 0.05 to 0.5 times is desired. In addition, in terms of other organic solvents that can be blended, specifically, for example, the following may be mentioned. That is, acetone, methyl ethyl ketone, and cyclohexanone Ketones such as methyl isoamyl ketone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or the like Monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, or monophenyl ethers, and their polyols; epoxides like cyclic ethers; and methyl acetate, -23- (20) 200426517 ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl propionate 'ethoxypropane Ester esters, etc. In the case of using these solvents, it is expected that the amount is less than or equal to% in all organic solvents. &Lt; Other ingredients &gt; The positive type photoresist composition of the present invention does not damage The scope of the present invention can be added with compatible additives as needed. For example, addition resins used for the performance of barrier films, plasticizers, storage stabilizers, and active agents to make the image more visible. Sensitizers or dyes for preventing halation, and those containing conventional additives such as adhesion improvement. These can be used in combination of more than one type according to needs. In terms of dyes for preventing halation, UV absorption can be used, such as 2,2 ', 4,4'-tetrahydroxydiphenyl ketone, 4-dimethylamino-dihydroxydiphenyl ketone, 5-amino-3-methyl-1 1-benzene -4-hydroxyphenylazo) -pyrazole, 4-dimethylamino- 4'-azobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4-diyl Azobenzene, curcumin, etc.). Surfactants can be added, for example, for prevention of glow marks. For example, Fulorate FC-430, FC431 (manufactured by Commerce, Sumitomo 3M) can be used. And other surfactants, XR-104, MegafuckR — 08 (commodity methoxy 50 quality improvement light, interface effect is higher, or a secondary agent (-2, 4, -4 mono (hydroxy ethoxyethylamine product name 5 Fluorine series name of EF122C, Da-24- (21) (21) 200426517 (manufactured by Ben Ink Chemical Industry Co., Ltd.), etc. &lt; Modulation method &gt; The positive type photoresist composition of the present invention can be, for example, (A ) ~ (D) and other components are dissolved in an organic solvent and prepared by filtration. In addition, the amount of the organic solvent used is preferably to dissolve the components (A) to (D) and other components and adjust them appropriately to obtain uniformity. The photoresist composition is preferably a solid component [(A) to (D) component and other components] having a concentration of 10 to 50% by mass, and more preferably 20 to 35% by mass. Type photoresist composition to modulate the photoresist The solid content Mw (hereinafter, referred to as the photoresist molecular weight) of the composition is preferably in the range of 5000 to 30,000, and more preferably Mw is 6000 to 10000. When the aforementioned photoresist photoresist molecular weight is in the above range, the sensitivity is not reduced. It can achieve high resolution, and at the same time, it can obtain a positive photoresist composition with excellent linearity and D Ο F characteristics, and also excellent heat resistance. The photoresist molecular weight is smaller than the above range. Resolution, linearity, D Ο F The characteristics and heat resistance may be insufficient. When the above range is exceeded, the sensitivity may be significantly reduced, and the coating property of the photoresist composition may be impaired. In this specification, the photoresist molecular weight is measured by the GPC system. Device name: SYSTEM 11 (product name, manufactured by Showa Denko) Precolumn: KF- G (product name, manufactured by Shodex) column: KF- 805, KF-803, KF-802 (product name '-25- (22) (22) 200426517

(Shodex) detection • UV 41 (product name, manufactured), measured at 28nm. Bath agent, etc .: Tetrahydrofuran was passed through at a flow rate of 1.0 ml / min, and measured at 3 5 t. Measurement sample preparation method: The photoresist composition to be measured is adjusted to a solid content concentration of 30% by mass, and this is diluted with tetrahydrofuran to prepare a measurement sample having a solid content concentration of 0 "% by mass. 20 microliters of the above-mentioned measurement sample was poured into the above apparatus for measurement. In the preparation of the positive-type photoresist composition of the present invention, the method of adjusting the molecular weight of the photoresist to be in the above-mentioned appropriate range, for example, to make (1) the Mw after mixing all the components is in the above-mentioned range, relative to the component (a) before Perform separate operations and other methods to adjust the Mw of the (A) component to an appropriate range in advance, (2) prepare multiple (A) components with different Mw, and mix them appropriately to adjust the Mw of the solid component to the range above. Method, etc. In particular, the above-mentioned modulation method (2) is more preferable in terms of adjustment of the molecular weight of the photoresist and the ease of adjustment of the sensitivity. The above-mentioned positive-type photoresist composition of the present invention can improve the adhesion to the substrate by blending (D) component. Therefore, in order to improve the resolvability, a stepped resin that removes low-molecular-weight substances is used. Among them, since it has sufficient adhesion to the substrate, it can be a material with both high resolution and good adhesion. Among them, in the case where the positive photoresist composition contains the above (A) ~ (C) components, the sensitivity is high, which is suitable for i-line exposure. Under low NA conditions, its resolution is also high, and D 0 F 'is linear. The photoresistance characteristics of the same are also -26- (23) (23) 200426517 Excellent 'is a suitable material for system LCD manufacturing.

In the present invention, the reason why the adhesion improving effect is obtained by containing the (D) component is not clear, but it is considered that the hydroxyl group and the hydrogen bond of the (D) component are bonded to the hydrophilic portion of the substrate. "Photoresist Pattern Forming Method" Hereinafter, an example of an appropriate method for forming a photoresist pattern at the time of manufacturing a system LCD using the positive type photoresist composition of the present invention will be described. First, the positive-type photoresist composition of the present invention is applied to a substrate with a spinner or the like to form a coating film. The substrate is preferably a glass substrate. As for glass substrates, users of amorphous silica usually use low-temperature polysilicon in the field of system LC. With regard to this glass substrate, the positive photoresist composition of the present invention is excellent in resolvability under low NA conditions, and it is possible to use a large substrate having a size of 500 mm x 600 mm or more, especially a size of 550 mm x 650 mm or more. The upper limit of this substrate is not particularly limited. Next, the glass substrate on which the coating film is formed is subjected to a heat treatment (pre-baking) at, for example, 100 to 140 ° C to remove the residual solvent to form a photoresist film. The heating temperature can be changed as needed. As for the pre-baking method, it is preferable to perform adjacent baking in which the gap is maintained between the hot plate and the substrate. In addition, with respect to the photoresist film, selective exposure is performed using a mask depicted in a mask pattern. As for the light source, an i-line (3 65 nm) may be used to form a fine pattern. In addition, the exposure process used in this exposure is preferably below 0.3, preferably 0.2 or less, more preferably 0.1 5 or less under low NA conditions. -27- (24) (24) 200426517 is better. Next, heat treatment is performed on the photoresist film after selective exposure (post-exposure baking: PEB). In the PEB method, there are, for example, adjacent baking that maintains the gap between the hot plate and the substrate, and direct baking that does not maintain the gap. There is no warping of the substrate. In order to obtain the diffusion effect caused by PEB, it is better to perform direct baking after performing adjacent baking. In addition, the heating temperature can be selected according to needs, but the heating temperature is preferably 90 ~ 150 ° C, especially 100 ~ 140 ° C. Compared with the photoresist film after the PEB, if a developing solution is used, such as a 10 to 10% by mass aqueous solution of tetramethylammonium hydroxyl, when an alkaline aqueous solution is used for development processing, the exposed portion is dissolved and removed, and it can be used on the substrate. A photoresist pattern for an integrated circuit and a photoresist pattern for a liquid crystal display part are formed at the same time. The imaging solution can be selected according to needs. Furthermore, the developing solution remaining on the surface of the photoresist pattern can be washed away with a washing solution such as pure water to form a photoresist pattern without the developing solution. In this photoresist pattern formation method, in the case of manufacturing a system LCD, in the step of performing the above-mentioned selective exposure, as the above mask, a mask pattern for forming a photoresist pattern having a thickness of 2.0 // m or less is used. And, the mask drawn by both sides of the photoresist pattern forming mask pattern exceeding 2.0 // m is better.

As described above, in the manufacture of a system LCD where the fine pattern of the integrated circuit part and the rough pattern of the display part are formed at the same time, the high resolution that can form the fine pattern can be obtained, and in the wet etching step, The level of adhesion to the substrate of the positive photoresist composition is also important. The LCD -28- (25) (25) 200426517 of the present invention has a positive photoresist composition for manufacturing, and has high adhesion to a substrate. When the aforementioned positive photoresist composition is used to form a photoresist pattern, it has The effect of suppressing the infiltration phenomenon or peeling phenomenon during wet etching. Therefore, the system LCD is used as an appropriate material. In addition, the positive photoresist composition for LCDs of the present invention is also excellent in resolvability, and a photoresist pattern capable of faithfully reproducing a fine pattern of a mask pattern can be obtained. Therefore, in the above step of simultaneously forming the photoresist pattern, the photoresist pattern for an integrated circuit having a pattern size of 2.0 / zm or less and the photoresist pattern for a liquid crystal display portion exceeding 2.0 # m on the substrate Models can be formed simultaneously [Embodiment] Hereinafter, the present invention will be described in detail with examples. However, the present invention is not limited to these examples. Examples 1 to 4 and Comparative Examples 1 to 2 The following components (A) to (D) were used in the types and blending amounts (parts by mass) described in Table 1 below. D) The total mass of the ingredients uses a surfactant (product name "R-08"; manufactured by Dainippon Ink Chemical Industry Co., Ltd.) in an amount equivalent to 450 p pm. These are dissolved in an organic solvent (2-heptanone ), Adjusted to a concentration of 30% by mass. This solution was filtered through a membrane filter having a pore size of 0.2 / im to prepare a positive photoresist composition. The photoresist molecular weight of the obtained positive-type photoresist composition is shown in Table 1. -29- (26) (26) 200426517 In Comparative Example 1, X 1 used in place of (D) component is an esterification reaction product of a polyphenol compound equivalent to (D) component of the present invention. (A) Ingredient (A1): Use m-cresol / p-cresol / 3, 5-xylenol di 51/27/22 (mole ratio) mixed phenol and formaldehyde, synthesize according to the conventional method, and implement step by step Treated phenolic resin (Mw 2 17000, M w / M n = 5.2) (B) Ingredient (Bl): 2,6 —bis [2,5 — dimethyl-1 3 — (2 —hydroxyl 5 1 Methylbenzyl) -4-hydroxybenzyl] -4-methylphenol 1 mole and -naphthoquinonediazide-5 -sulfofluorenyl chloride (hereinafter referred to as "5-NQD") 2 mole The component (C1) of the esterification reaction product (C): 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4 monomethylphenol (D) component (D1): 2 , 3,4-trihydroxydiphenyl ketone 1 Mole and 5-NQD1 Mole with esterification reaction product (D2): bis (5-cyclohexyl-4-hydroxy-2-methylphenyl)- Esterification reaction product of 3,4-dihydroxyphenylmethane 1 mole and 5-NQD 2 mole (XI): 2,6-bis (2,5-dimethyl-2,4-hydroxybenzyl)- 4 -30- (27) (27) 200426517 Esterification reaction product of monomethylphenol 2 mol and 5-NQD1 mol (A) component ((B) component (C) component (D) Component photoresist distribution combined amount) (Mixed amount) (Mixed amount) (Mixed amount) Example 1 Al (100) B 1 (25) C 1 (25) Dl (5) 7 000 Example 2 Same as above Same as above D1 (10) Same as above Example 3 Same as above Same as above Dl (2) Same as above Example 4 Same as above Same as above D2 (5) Same as above Comparative example 1 Same as above Ibid x 1 Article 1 (5) Same as above Comparative example 2 Same as above fte Same as above ※ 丨: Test example 1 of esterified product of polyphenol compound which should not be used as component (D) of the present invention About the positive photoresist composition obtained in Examples 1 to 4 and Comparative Examples 1 to 2, the following ( Each item of 1) to (5) is evaluated individually. The results are shown in Table 2 below. (1) Linear evaluation

A large-size substrate photoresist coating device (apparatus name: TR3 6000 manufactured by Tokyo Chemical Industry Co., Ltd.) was used to apply a positive-type photoresist composition to a glass substrate (550 mm x 650 mm) formed from a Ti film. After that, the temperature of the hot plate of the apparatus was set to 1000 ° C, and the first baking was performed for 90 seconds by opening the adjacent baking at an interval of about 1 mm. Next, the temperature of the hot plate was set to 90 ° C -31 (28) (28) 200426517, and the second drying was performed for 90 seconds by opening adjacent baking at 0.5 mm intervals to form a film thickness of 1.4. 8 // m photoresist coating. Secondly, through the test pattern mask (standard), which can simultaneously draw the mask pattern for the reproduction of the photoresist pattern of the 3.0-m line and the gap (L &amp; S) and 1.5 // m L &amp; S Line), an i-line exposure device (device name: FX — 702J, manufactured by Nikon Corporation; NA = 0.14) was used, and selective exposure was performed at an exposure amount (Eoρ exposure amount) that enables faithful reproduction of 3.0 / zm L &amp; S. Next, the temperature of the hot plate was set to 120 ° C, and the 0.5 m m interval was opened, and a heating treatment was performed for 30 seconds by the proximity baking '. Secondly, direct baking was performed at the same temperature without opening intervals for 60 seconds. Secondly, at 2. 3 ° C, 2.38% by mass of TMAH (tetramethylammonium hydroxide) aqueous solution (product name "NMD — 3" Tokyo Application (Manufactured by Chemical Industry Co., Ltd.), using a developing device with a slit coater nozzle (device name: TD-3 9000 demonstration machine, manufactured by Tokyo Ind. Co., Ltd.), as shown in FIG. ZZ, the liquid was loaded on the substrate in 10 seconds. After keeping it for 5 5 seconds, it was washed with water for 30 seconds and spin-dried. Thereafter, the cross-sectional shape of the obtained photoresist pattern was observed with an S EM (scanning electron microscope) photograph, and the actual pattern size was evaluated to evaluate the reproducibility of the 1.5 / mL &amp; S photoresist pattern. (2) Sensitivity evaluation: Sensitivity is expressed by the exposure amount (EoP) (mJ), which can be faithfully reproduced with a photoresist pattern of 1.5 // mL &amp; S. The smaller the 则, the better the sensitivity. (3) DOF evaluation: -32- (29) (29) 200426517 In the above EO exposure exposure, the DOF is moved up and down appropriately, and the 1.5 μm L &amp; S is obtained within the range of the dimensional change rate of ± 10%. The range of the focus depth (total depth width) is expressed in // m units. The larger 値 is, the better the characteristic is. (4) Evaluation of resolution: The smaller the 所示 shown by the limit resolution in the above EO exposure, the higher the resolution. (5) Adhesiveness evaluation: The same as the method described in the linearity evaluation described above, a photoresist pattern of 3,000 m L &amp; S was formed. The substrate formed by the aforementioned photoresist pattern was immersed in an etching solution set at 25 ° C (ammonia hydrogen peroxide water: NH3 / H202 / H20 = 1/1 5/3 0 (mass ratio) mixed solution) In the middle, wet etching of the underlying Ti film is performed. After the aforementioned wet-etching treatment, the photoresist pattern was peeled off using methyl ethyl ketone (MEK), and the shape of the patterned Ti film (Ti pattern) was observed from the top and the presence of corrosion was investigated. The above immersion time is measured in several times, and the penetration time (min) when the corrosion of the T I pattern can be confirmed is expressed by the adhesion evaluation by the infiltration phenomenon of the wet etching solution. It can be confirmed that the longer the immersion time during corrosion, the better. (30) (30) 200426517 Table 2 Straightness DOF Resolution Adhesiveness (β π) (m J) (β m) (β m) (min) Example 1 1.4 50 20 1.2 .2 7 Example 2 1.4 40 15 1 .2 8 Example 3 1.4 60 20 1 .2 6 Example 4 1 .4 70 20 1 .2 5 Comparative Example 1 1 .4 90 20 1 .2 4 Comparative Example 2 1.4 70 20 1.2 4 It can be confirmed that the photoresist pattern obtained by using the positive photoresist composition of Examples 1 to 4 has high adhesion to the substrate. In addition, the positive-type photoresist composition of each example using stepped resin and non-diphenylketone-based PAC will have high sensitivity, high resolution, linear characteristics, and DO F characteristics required for system LCD manufacturing. Excellent material. In contrast, the photoresist pattern obtained by using the positive photoresist composition of the comparative example had poor adhesion to the substrate. [Effect of the Invention] As described above, the positive photoresist composition and the photoresist pattern formation method of the present invention can form a photoresist pattern with good adhesion to a substrate, and is suitable for the manufacture of a system LCD. [Brief description of the icon] -34- (31) 200426517 [Figure 1] Shows that for low linearity evaluation, a positive photoresist composition is coated on a glass substrate, baked and dried, and patterned. After exposure, the state where the developing solution is filled with liquid from the substrate end X through the Z in a developing device with a gap coater is schematically shown. -35-

Claims (1)

200426517 Π) Patent application scope 1 · A positive photoresist composition for LCD manufacturing, which can form integrated circuits and liquid crystal display parts on a substrate, characterized in that it contains: at least two benzene rings in one molecule And at least one of the aforementioned benzene rings has an esterification reaction product between a polyphenol compound having a molecular weight of 1000 or less and at least two hydroxyl groups, and a 2-naphthyldiazide sulfofluorenyl compound. Shen Ying Ho As Benzene &lt; 2 The compound is a diphenyl ketone compound represented by a light-blocking I) type (IH) b [wherein, a represents an integer of 2 to 4 and b represents an integer of 0 to 4]. 3. The positive photoresist composition according to item 1 of the patent application range, in which the aforementioned diphenyl ketone-based compound is the following general formula (11) HQ 0Η &gt; A diphenyl ketone compound represented by (0H) c / (Π) [wherein, c represents an integer of 0 to 4]. 4 · If the positive photoresist composition in item 1 of the patent application scope contains, (A) an alkali-soluble resin; (B) contains: the following general formula (111) -36- (2) 200426517 (〇H) e …… (m) [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 atom Cycloalkyl groups of 3 to 6: R1 () and R11 represent independent hydrogen atoms or alkyl groups of 1 to 6 carbon atoms; R9 may be a hydrogen atom or an alkyl group of 1 to 6 carbon atoms. In this case, Q] represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or the following chemical formula (IV) , Alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, or cycloalkyl group having 3 to 6 carbon atoms; 表示 represents a residue represented by an integer of 1 to 3), Q1 It can be bonded to the terminal of R9. In this case, the carbon atoms between Q1 and R9 and Q1 and R9, meanwhile, represent a cycloalkyl group of carbon chain 3 to 6; d, e represent integers of 1 to 3; g represents an integer of 0 to 3; η is an integer of 0 to 3; an esterification reaction product of the compound shown and a 1,2-naphthoquinonediazidesulfonylsulfonyl compound, a naphthoquinonediazide Esters, and (C) points -37- (3) (3) 200426517 A phenolic hydroxyl-containing compound having a molecular weight of less than 1 000. 5. The positive photoresist composition according to item 4 of the patent application, wherein the (A) component is a phenolic lacquer resin having a mass average molecular weight of 3000 to 30,000 and a dispersion degree of 2.5 to 7.10. 6. —A method for forming a photoresist pattern for LCD manufacturing, in which an integrated circuit and a liquid crystal display portion can be formed on a substrate, which comprises the following steps: (1) having at least 2 benzene rings in a molecule, and An esterification reaction product of at least one of the aforementioned benzene rings having at least two hydroxyl groups and containing a polyphenol compound having a molecular weight of 1,000 or less and a 1,2-naphthoquinonediazidesulfonylsulfonyl compound, so that A step of applying a positive photoresist composition on a substrate to form a coating film, (2) a step of heating a substrate having the above-mentioned coating film formed thereon, and a step of forming a photoresist film on the substrate, (3) relative to the above photoresist For the film, selective masking exposure is performed using a mask pattern for both photoresist pattern formation masks below 2.0 // m and mask patterns for photoresist pattern formation above 2.0 // m Step (4) Perform a heat-treated PEB step on the photoresist film after the selective exposure described above, and (5) Perform a development process using an alkaline aqueous solution on the photoresist film after the heat treatment described above. Can make the pattern size 2.0 The photoresist pattern used for integrated circuits below / z m and the photoresist pattern used for parts of liquid crystal displays exceeding 2.0 // m, and the development steps at the same time. 7 · The photoresist pattern forming method according to item 6 of the patent application range, wherein the step of performing the above-mentioned (3) selective exposure is an exposure using an i-line in the light source and under a low NA condition of NA 0.3 or less Process to carry on. -38-